JPS6043659A - Formation of color image - Google Patents

Abstract

PURPOSE:To obtain a highly fast magenta image having no subsidiary absorption in the visible region by using 1H-pyrazolo-[1,5-b]-pyrazole compd. for a magneta coupler and reacting it with the oxidized product of an aromatic primary amine developing agent. CONSTITUTION:A coupler represented by formula I (X is H or a coupling releasable group; R1-R3 are each H, halogen, alkyl, or aryl, and when R1-R3 or X is a bivalent group, a dimer or higher polymer may be formed) is reacted with the oxidized product of an aromatic primary amine developing agent to form a magenta dye. As a result, unnecessary absorption having a yellow component near 430nm wavelength is removed and a magenta image free from color mixing and fast to light and heat is obtained. Color image stability and light fastness can be enhanced by using in combination a compd. represented by formula II in which R10 is H, alkyl, or the like; R11-R15 are each H, OH, alkoxy, or the like.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to an imaging method in which a novel magenta color image 141 is formed by coupling reaction with the oxidation product of an aromatic-grade amine oxidized by silver halide. More specifically, the present invention relates to an image forming method using a novel magenta coupler, /H-pyrazolo(/,,tb)-pyrazole.

Using the exposed silver halide as an oxidizing agent, the oxidized aromatic/amine color developing agent and coupler react to form indophenol, indoaniline, indamine,
It is well known that azomethine, phenoxazine, phenazine and similar dyes can be produced and color images can be formed.

Of these, in order to form one magenta color image, j
-Pyrazolone, cyanoacetophenone, indacilone,
Pyrazolobenzimidazole and pyrazolotriazole couplers are used.

Hitherto, most of the magenta color image-forming couplers that have been put into practical use and have been studied are mostly j-pyrazolones.

However, the dyes in which the J-pyrazolone couplers are formed have unnecessary absorption with a yellow component near 30 nm, which causes color turbidity, and they also have relatively good fastness to light and heat. However, it is still not at a fully satisfactory level.

The inventors of the present invention have found that it is necessary to improve the problems of terpyrazolone couplers (as a result of searching for a bone nucleus that exhibits a new magenta color, it shows no sub-absorption in the visible region, and has a high quadraticity of the color 1 image. A series of couplers that are synthetically friendly have been achieved.Therefore, the objects of the present invention are to provide a coupler that is excellent in color reproduction, has excellent color development speed, and maximum color density, is excellent in synthesis, and has a leaving group at the coupling active position. By introducing a new magenta color image that can be made into so-called 2-equivalent and reduce the amount of silver damage used [
It is an object of the present invention to provide image-forming couplers and to provide a method for forming magenta colored image hoe using these couplers.

The above object has been achieved by a color image forming method using silver halide, which is characterized in that a coupler represented by the following general formula (I) is reacted with an oxidation product of an aromatic-amine developing agent.

However, in the formula, X represents a hydrogen atom or a coupling-off group, R1, R2, and R3 represent a hydrogen atom or a substituent, and RI VR2, T1.3, or X forms a multiprecipitate of λ mer or more. In general formula (I), preferably R1, R2, R3
is a hydrogen atom, a halogen atom, an alkyl group, an aryl group,
Heterocyclic group, cyano group, alkoxy group, aryloxy group, heterocyclic group, acyloxy group, carbamoyloxy group, silyloxy group, sulfonyloxy group, acylamino group, anilino group, ureido group, imide group, sulfamoylamino group group, carbamoylamino group, alkylthio group, arylthio group, heterothio group, alkoxycarbonylamino group, aryloxycarbonylamino group, sulfonamide group, carbamoyl group, acyl group,
Represents a sulfamoyl group, a sulfonyl group, a sulfinyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, and X is a hydrogen atom, a halogen atom, a carboxy group,
or represents a group that bonds with the carbon at the coupling position via an oxygen atom, nitrogen atom, or sulfur atom and is a group that decouples. R1, R2, R3, or X is a divalent group and forms a bis body. Good too.

The coupler group represented by the general formula (I) may also be in the form of a polymer coupler present in the main chain or side chain of the polymer (in particular, a polymer derived from a vinyl monomer having a moiety represented by the general formula Preferably, in this case R1,
R2, R3, and X are vinyl groups or linking groups.

For more details, see R'1. R2 and R3 are each a hydrogen atom,
Halogen lff, child (E!'IJ, chlorine atom, bromine atom, etc.) to alkyl group (e.g. methyl 7, propyl group, t-butyl group, trifluoromethyl group, tridecyl group, 3-C2,'4 -di-t-amylphenoxy)propyl group, allyl group, λ-dodecyloxyethyl group, 3-
phenopropyl group, cohexylsulfonyl-ethyl group, cyclopentyl group, he/cyl group, etc.), aryl group (e.g., phenyl group, ψ-1-butylphenyl group, λ
, lig-t-amylphenyl group, kutetradecanamidophenyl group, etc.), heterocyclic group (e.g., λ-furyl group, 2-chenyl group, 2-pyrimidinyl!, 2-benzothiazolyl=1+, ff'), cyano group, alkoxy group (e.g. methoxy group, ethoxy group, comethoxyethoxy group, 2-dodenyloxyethoxy7 group, comethanesulfonylethoxy L'J), oryloxy group (e.g. phenoxy group, 2 -methylphenoxy group, Hiro-t-7' tylphenoxy group, etc.), heterocyclic oxy group (e.g., λ-benzimidazolyloxy group, etc.), acyloxy group (e.g., acetoxy group, hexadecanoyloxy group, etc.), Carbamoyloxy group (e.g. N-
phenylcarbamoyloxy group, heethylcarbamoyloxy group, etc.), 7lyloxy group (e.g., trimethylsilyloxy group, etc.), sulfonyloxy group (e.g., dodecylsulfonyloxy group, etc.), acylamino group (
For example, an acetamide group, a benzamide group, a tetradecanamide group, an α-(2,≠-di-1-amylphenoxy)butyramide group, a γ-(3-t=i-di-1-amylphenoxy)butyramide group, an α-(4'- (≠
-hydroxyphenylsulfonyl) phenoxy) decanamide L, etc.), anilino groups (e.g. phenylamino g,
2-l.

Roanilino group, λ-chloro-3-tetradecanamideanilino group, λ-chloro-dodecyloxylponylanilino group, N-acetylanilino group, λ-chloror
-(α-(3-1-butyl-guhydroxyphenoxy)dodecanamido)anilino group, etc.), ureido group (e.g. phenylureido group, methylureido group, N, N
dibutylureido group, etc.), imide group (e.g., N-
Sufushisoimide group, 3-penzylhydantoinyl group, F
-(2-ethylhexanoylamino)phthalimide group,
), sulfamoylamino groups (e.g., N,N-dipropylsulfamoylamino group, N-methyl-N-decylsulfamoylamino group, etc.), alkylthio groups (e.g., methylthio group, octylthio group, tetrazolylthio group), group, no phenoxyethylthio group, 3-phenoxypropylthio group, 3 (l/l t-butylphenoxy)
propylthio group, etc.), arylthio group (e.g., phenylthio group, λ-butquin-j-1-octylphenylthio group, 3-pentadecylphenylthio group, λ-carboxyphenylthio group, gutetradecanamidophenylthio group, etc.), heterocyclic thio groups (e.g., nobenzothiazolylthio group, etc.), alkoxycarbonylamino groups (e.g., methoxycarbonylamino group, tetradecyloxycarbonylamino group, etc.), aryloxycarbonylamino groups (e.g., phenoxycarbonylamino &, 2.≠-tert-butylphenoquine group, etc.), sulfonamide group (e.g. methanesulfonamide group, hexadecanesulfonamide group, benzenesulfonamide group, p-toluene ester/l) / honamide group, octadecanesulfonamide group, λ-methyloxy-o-t-butylbenzenesulfonamide group, etc.), carbamoyl group (for example, N-ethylcarbamoyl i, N.

N-dibutylcarbamoyl group, N-(2-dodecyloxyethyl)carbamoyl: N-dodecylcarbonyl group, N-(J-(,2.

Googie tcrt-amylphenoxy)propyl)carbamoyl group, 'J), acyl group (e.g. acetyl group, (2,/I-ditert-amylphenoxy)acenal group, benzoyl group, etc.), sulfamoyl group (for example, N-ethylsulfamoyl group, N,N-diethylsulfamoyl group, N (2-dodecyloxyethyl)
Sulfamoyl group, N-ethyl-N-dodecylsulfamoyl group, N.

N-diethylsulfamoyl group, etc.), sulfonyl group (
For example, methanesulfonyl group, octanesulfonyl group,
Benzenesulfonyl group, toluenesulfonyl group, etc.), sulfinyl group (e.g., octanesulfinyl group, dodecylsulfinyl group, phenylsulfinyl group, etc.), alkoxycarbonyl group (e.g., methoxycarbonyl group, butyloxycarbonyl group) (IFI, e.g., phenyloxycarbonyl group, 3-pentadenyloxycarbonyl group, etc.), and X is a hydrogen atom. ,...Rogen atoms (e.g. chlorine atom, bromine atom, iodine atom, etc.),
A carboxy group or a group linked via an oxygen atom (e.g.
Acetoxy group, propanoyloxy group, benzoyloxy group,! , ≠-dichlorobenzoyloxyquinethoxyoxaloyloxy group, pyruvinyloxy group, cinnamoyloxy group, phenoxy group, cucyanophenoxyl group, ≠-methanesulfonamidophenoxy group, goomethanesulfonylphenoxy group, α-naphthoxy group , 3-ntadecylphenoxy group, benzyloxycarbonyloxy group, ethoxy group, λ-cyanoethquine group, benzyloxy group, 2-phenethyloxy group, λ-phenoquinethoxynoyl group, j-phenyltetrazolyl Oxy) pj
, 2-benzothiazolyloxy, etc.), groups linked via a nitrogen atom (e.g., benzenesulfonamide group, N-
Ethyltoluenesulfonamide group, veptafluorobutanamide group, λ.

! , 4t, j, t-pentafluorobenzamide group, octane sulfonamide group, p-cyanophenylureido group, N, N-diethylsulfamonoylamino group, l-
Bi is a lysyl group, s, r-dimethyl-, ≠-dioxo-3-oxazolidinyl group, /-benzyl-ethoxy-3
-hydantoinyl group, λN-/,/-dioxo 3 (λ
H)-ogino/, 2-benzisothiazolyl group, -1oxo/, 2-dihydro-7-pyridinyl group, imidazolyl group, pyrazolyl group, 3. ! -diethyl-7゜λ,
≠-triazole/-il,! - or t-furomobenzotriazol-7-yl, termethyl-/, Z,
3. ≠-triazol-/-yl group, benzimidazolyl group, 3-benzyl-/-hydantoinyl group, /-benzyl-y-hexadecyloxy-3-hydantoinyl group, S-methyl-/-tetrazolyl group, etc.), arylazo group (For example, Hiro-methoxyphenylazo group, goupi,
F roylakunophenylazo group, 2-naphthylazo group,
3-methyl-l-hydroxyphenylazo group, etc.), a group linked by a sulfur atom (e.g.) engineering diruthio group, 2-
Carboxyphenylthio group, 2-methoxy-j-1-octylphenylthio group, Hiro-methanesulfonylphenylthio group, goo-octanesulfonamidophenylthio group,
-1-butoquinphenylthio 15.2-(2-hexanesulfonylethyl)-j-tert-octylphenylthio group, benzylthio group, 2-cyanoethyl minor thio group, /-
Ethoxycarbonyltridecylthio group! - Phenylru 2.3. II, j-tetrazolylthio group, λ-benzothiazolylthio group, λ-dodecylthioterthiophenylthio group, 2-phenyl-3-dodecyl-7,2, Hiro-triazolyl-yo-thio group, etc.) .

R1% When R, 2, Ra or
Ethylene group, /, 10f silene group, -CI2CH2-0
-CH2CH2-1, etc.), substituted or unsubstituted phenylene group (e.g. ll≠-phenylene group, t,3-phenylene group, -N)I Co-R2-CONI (- group (R2 is substituted or Represents an unsubstituted alkylene group or phenylene group, for example -Nl-ICOCH2CH2CONH-1H
3 -NHCOCH2C-CH2CONH-■ C[]3 -8-R2-8-i&(R2GXft;/cJ'l
Represents a non-la-substituted alkylene group, for example, -8-C1
42C1-12-s-1H3 -8-CH2C-CH12-8-, etc.), and X-exposed C1:1]3 represents the above monovalent group converted into a divalent group at an appropriate place.

When the vinyl monomer includes those represented by general formula (I), the linking group represented by R1, R2, R3, and X is an alkylene group (tM-substituted or unsubstituted alkylene group, for example, Methylene group, ethylene group, i, io-decyleno group, -CH2Ci-120CI-12C1■, 2-1gin),
Phenylene group (substituted or 1c is an unsubstituted phenylene group,
For example, /, cuphenylene group, /, 3-phenylene group, CI (3cl.

-NtlCO-1-CON[-1-1-〇-1, -0C
It includes groups formed by combining O- and aralkylene 7 groups (for example, (, etc.)).

Preferred linking groups include the following.

-NHCO-1-CH2CH2-1 1 -CONH-Cto12CH2NHCOAcol-12cH
20-CH2C1-1゜-N[1co-Also, the vinyl group may be substituted in addition to those represented by general formula (I) (preferable substituents are hydrogen atom, chlorine atom, or carbon number 1-H). lower alkyl, l1ii: (e.g.
methyl group, ethyl group).

Copolymers may also be made with monomer-free, non-color-forming ethylene-like monomers, including those represented by formula (I).

Acrylic acid, α
- chloroacrylic acid, α-alacrylic acid (e.g. methacrylic acid) and esters or amides derived from these acrylic acids (e.g. acrylamide,
n-dutylacrylamide, t-dutylacrylamide, diacetone acrylamide, methacrylamide, methyl acrylate', ethyl acrylate, n-propylacrylate, n-butylacrylate to -butylacrylate, 1so-butylacrylate, 2-ethyl Xyl acrylate, n-octyl acrylate, lauryl acrylate, methyl methacrylate-1, ethyl methacrylate, n-butyl methacrylate and β-
hydroxymethacrylate), methylene dibisacrylamide, vinyl esters (e.g. vinyl acetate, vinyl propionate and vinyl laurate), acrylonitrile, methacrylateryl, aromatic vinyl compounds (e.g. styrene and its derivatives, vinyltoluene,
divinylbenzene, vinylacetophenone and sulfostyrene), itaconic acid, citraconic acid, chloro/acid,
vinylidene chloride, vinyl alkyl ether (e.g. vinyl ethyl ether), maleic anhydride, maleic ester, N-vinyl-2-pyro+)
These include door, N-vinylpyridine, and 2- and hiro-vinylpyridine. Two or more types of the non-color-forming ethylene type f@phase monoi liquid used here can also be used together. Examples include n-butyl acrylate and methyl acrylate, styrene and methacrylic acid, methacrylic acid and acrylamide, methyl acrylate and diacetone acrylamide, and the like.

As is well known in the polymeric color coupler art, non-chromogenic ethylenically unsaturated mono-dodecenes for copolymerization with solid water-insoluble premature fillers are dependent on the physical and/or chemical properties of the copolymer formed, such as solubility. The binder of the photographic colloidal composition can be selected such that its compatibility with, for example, gelatin, its flexibility, thermal stability, etc. are favorably influenced.

The polymer coupler used in the present invention may be either water-soluble or water-insoluble, but among these, polymer coupler latex is preferable, with a typical magenta power f of -1° according to the present invention. Specific examples of these vinyl monomers are shown below, but the invention is not limited thereto.

(11 ■ (J=0 = exploratory epsilon) g pi and 5 f2d d 8 0 a a and "-1 U g U 舊■ υ=0 = = U Kan Coupler can generally be synthesized by the method shown below.

1. Bone nucleus synthesis C3H% i) b) R6 \ (R6 represents a protecting group such as an acyl group, a benzyl group, a silyl group, and R7 is an alkyl group, an aryl group, a heterocyclic group, an amino group, an acylamino group, Represents a sulfonamide group, an alkoxy group, an aryloxy group, etc., and R4 and Y have the same meanings as above.) OOMe (R8 is a hydrogen atom, an alkyl group, an aryl group, a heterocyclic group, an alfkyl/carbonyl group, etc., and Y represents the same meaning as above.) 2. Polymer coupler synthesis Methods for synthesizing polymer couplers include, for example, solution polymerization and emulsion polymerization, and solution polymerization is first described in US Pat.
Qi (JJ coupler and non-chromogenic ethylene-like monomer) containing a moiety represented by general formula (I) can be synthesized by the method described in Acrylic acids such as acrylic acid, α-chloroacrylic acid, methacrylic acid or esters or amides thereof derived from acrylic acids (e.g. acrylamide, n-butylacrylamide, n-butyl methacrylate, methyl methacrylate, ethyl methacrylate, etc.)) in a suitable ratio in a resistant organic solvent (e.g., dioxane; methylcerenlube, etc.),
Initiate polymerization at an appropriate temperature (30 to 100") (physical action, ultraviolet light, high energy range, etc., or chemical action, hydrogen oxide, benzoyl peroxide, azobis alkyl After the polymerization reaction is completed, the ffi polymer can be isolated by extrusion into an organic solvent, concentration, or pouring into water. Regarding the polymerization method, see US Patent 3.
37θ, can be synthesized by the method described in No. 52.

3. Method for introducing coupling-off groups (1) Method for linking oxygen atoms.
-t)') A dye is formed from a pyrazole type coupler by the method shown in Example/, which is hydrolyzed in the presence of an acid catalyst to form a ketone body, and this ketone body is converted into a ketone body by hydrogenation using pb-carbon as a catalyst. addition, Zn=reduction with acetic acid or dogen with sodium borohydride, resulting in hydroxy-/H-
Pyrazolo (/, J--L)) hyrazole can be synthesized. By reacting this with various halides, the desired coupler connecting oxygen atoms can be synthesized. (U.S. Patent No. 3.2, No. 437, Japanese Unexamined Patent Publication No. 7-70-7
(See No. 7) (2) Methods for connecting nitrogen atoms There are roughly three methods for connecting nitrogen atoms. The seventh method is described in U.S. Patent No. 3. As described in Hiroshi/Ri, No. 3, the coupling active site is nitroned with a suitable nitrosating agent, and then reduced by an appropriate method (e.g., using pd-carbon as a catalyst). hydrogenation method, chemical reduction method using stannous chloride, etc.)
/H-pyrazolo(/, t-4)3 pyrazole is reacted with various...rides to mainly synthesize amide compounds.

The first method is described in U.S. Pat. No. 3,723. In the direction described in OA No. 7, i.e., a suitable chlorogenating agent, such as sulfuryl chloride, chlorine gas, bromine, N-chloroco-phosphate imide, N-promosimide, etc. (therefore, the ≠ position is ...Rogenization, and then Tokuko Shoj6-≠!r/ 3
Using the method described in No.j, the nitrogen heterocycle is reacted with a suitable base catalyst, triethylamine, sodium hydroxide, diazabicyclo(
2,2,,2) It is possible to synthesize a coupler which is substituted in the presence of octane, anhydrous potassium carbonate, etc. and linked to the hiro position with a nitrogen atom. Among compounds linked by oxygen atoms,
Compounds having a niphenoxy group at the j-position can also be synthesized by this method.

The third method is effective when introducing a tπ or 10π electron system aromatic nitrogen heterocycle at the μ position, and is
As described in No. 36177, more than twice the molar amount of t for the coulogen compound synthesized by the first method.
By adding a π or 10π electron system aromatic nitrogen heterocycle, so
≠ position by heating at 0 to /j00C without solvent, or by heating at 30° to /300 in an aprotic polar solution such as dimethylformaldehyde, N-methylpyrrolidone, sulfolane or hexamethylphosphotriamide. An aromatic nitrogen heterocyclic group connected via a nitrogen atom can be introduced.

(3) Method of connecting sulfur atoms A coupler in which an aromatic mercapto or heterocyclic mercapto group is substituted at the 7-position is described in U.S. Pat. , heterocyclic mercaptans and their corresponding sulfides...
Gut[i/)I-pyrazolo[/, J゛,
-1) It can be synthesized by adding it to J pyrazole couplers. A method for introducing an argyl mercapto group into the G position is the method described in U.S. Pat. A method of synthesizing in a step using K and S-(alkylthio)isothiourea, hydrochloride (or bromine hydrochloride) is effective.

Synthesis Example 1 (Exemplary Coupler (1))! , j-dimethyl-/H-pyrazolo[/, j-b) Synthesis of pyrazole (synthesis scheme) (Intermediate A) a) Synthesis to intermediate J-(2-oxopropyl)-j-methylpyrazole (
After reacting 2,6-dimethyl-γ-pyrone with hydrazino hydrate to quantitatively obtain J-(j-hydrazino)-j-methylpyrazole, this was reacted with sodium nitrite in a resistant aqueous solution. , quantitatively converted to 2-oxoprolyl derivative. References n, , G., Jones and M.
, J. Mann+, J. Am.

Chem, So'c,, 73.110111 (/9
63).

R, N, Ca5tle and M, (')noda,
,T.Org.

Cb'em,, Hitoshi 11111. j(/9 otl),)ri.

jg and hydroxyla pink hydrochloride. 5g of ethanol A
Added to Oml. After dropping 2 g of sodium hydroxide (f) dropwise thereto, the mixture was heated under reflux for a while. After being concentrated under reduced pressure to remove ethanol, it was extracted with ethyl acetate; /l = (j 0m1X 3 ) The ethyl acetate layer was dried over anhydrous magnesium sulfate and then concentrated to obtain 11 g of an oily crude product.

b) Synthesis of coupler (1) 3-(,a-oximinopropyl)-termethylpyrazole λJ was dissolved in DMF♂ml under nitrogen stream.
Cool to 0C. Add sodium hydride (0% in
m1neral oil) 0.211g, and
The mixture was stirred at C for 10 minutes and then at room temperature for 70 minutes. This was mixed with 0-(2,41-dinitrophenyl)hydroxylamine/--2 g"lDt at room temperature for io minutes. This was poured into jOml of saturated brine and extracted with ethyl acetate (rOml x 3).

After drying the ethyl acetate layer over anhydrous (magnesium chain acid), it was ginned and subjected to silica gel column chromatography (30JJ
, CHU3:MeOt-1=j O: / ) to obtain a mixture (/:/) of 2-amino body (target object) and /-amine body (0.11Ofi). Dissolve this as a mixture in 10m ethyl alcohol, add hydrochloric acid λ, θm
After adding e, the mixture was heated under reflux for 2 hours. After adding 20 d of water,
Concentrate under reduced pressure to remove ethanol, and extract with 1#1 ethyl acetate fc (30 ml x 3). After drying the n1 acidic acid layer over anhydrous magnesium sulfate, it was concentrated and subjected to silica gel column chromatography (20 g, hexane: ethyl acetate = 2:
/) to obtain 301n& solid.

Elemental analysis theoretical value H (A, 7/%).

(C7HgN3=:/jj,/7) C(A2.20%
).

N (3/, θ ratio) Experimental value 1-1 (7,70 sections).

C (section 12, 37).

N (3/, //) The NMR spectrum in deuterated chloroform is j, rza (
br, /F()pprrl, 3. j Hiro (d,, 2H.

, ding ='i, q! -1Z) ppm, 2, 611 (
s, t) ppm, indicating that it has a methylene structure.

Synthesis Example 2 (Exemplary coupler t, ;!1))/tl<t-
Chloro-j-methyl-2-[3-[Hiro-(-2,-[Hiro-(4t-hydroxyphenylsulfonyl)phenoki/
[dodecanamide) phenyl] propyl] pyrazolo (/
, t-b) Synthesis of pyrazole (synthesis scheme) (hereinafter, φ represents a phenyl group) Intermediate A Intermediate B HN -N -N 0 The method described in Japanese Patent Application No. 111312/1980 33 g of l-benzyl-2-amino-3,j-dimethylpyrazolium iodide (intermediate A), synthesized using 37g tributylamine added now/10
0~/200-(-≠hours of heating and distillation. Excess DMF
was removed under reduced pressure, chloroform was added to the residue, and organic compounds were extracted. After drying the chloroform solution over anhydrous sodium sulfate, the solvent was removed to obtain a residue. This residue was separated and purified using silica gel column chromatography to obtain target intermediates B, 2 and 9 in the non-polar portion.

2rg of this intermediate B was dissolved in 3ooml of ethanol, 10ome of concentrated sulfuric acid was added thereto, and the mixture was heated under reflux for 4 hours. After neutralization with an aqueous sodium hydroxide solution, extraction was performed with ethyl acetate to obtain a tax acylated product /7#9,
This was dissolved in 10 ml of tetrahydrofuran (THF), 10% pd-carbon was added thereto, and the mixture was hydrogenated in an autoclave for 2 hours under a hydrogen pressure of 10 atm and a temperature of 00C. pd-carbon filtered T[I
F (17) was briefly distilled under reduced pressure to obtain 7.19 g of crude amine (intermediate C).
ome acetonitrile and ioOml dimethylacetic acid
2-[Hiro-(4t-benzyloxyphenylsulfonyl)phenoxy]dodecanoyl chloride (2-[Hiro-(4t-benzyloxyphenylsulfonyl)phenoxy]dodecanoyl chloride) (2-[Hiro-(4t-benzyloxyphenylsulfonyl)phenoxy]dodecanoyl chloride) was dissolved in Doamide and heated at 7o0VC on a steam bath.
Tokukai Akira! Za-'72011! (synthesized by the method described in the specification) was added thereto, and the mixture was heated and stirred for several hours. Ethyl acetate was added to the reaction solution, an extraction operation was performed, and the ethyl acetate layer was dried over anhydrous sodium sulfate, and then the solvent was removed. residue 2/
, 7fi in 200 ml of THF and the log of /
0% p d-carbon was added and hydrogenated at room temperature for 72 hours.

After the reduction, the pd-carbon was filtered, the filtration was concentrated, and the residue was purified by silica gel column chromatography to obtain a powder of the four-toothed rat mother nucleus of the coupler. 1 This compound/
11 g was dissolved in 10 oml of chloroform, and 3.3 g of N-chlorosuccinimide was added and stirred. The precipitated succinimide was filtered, the filtrate was thoroughly washed with water, dried with anhydrous sulfuric acid, and then the solvent was removed to obtain 9 liters of colorless coupler (21) powder. Analysis (C39'-147N4SO5α=7/ri, j)
ll theoretical value t1 (A, j relation), c” (at./
, 2%), iN (7,72%) Experimental value 1-1 (4, rg factor), c (xt, lμ factor).

N (7.1r/%) The coupler of the present invention may be added to a light-sensitive material or may be used by being added to a color developing bath. The amount added to the photosensitive material is λ×l0-3 mol to rxio per mol of silver halide.
moles, preferably /X10''1 to jX/0 moles, and the amount of the polymer coupler added should be adjusted so that only the above-mentioned amount of the color-developing portion is included in the polymer coupler's local area. 0°00/-0.1 mol per bath/θoocc,
Preferably 0.0! -0°0! Moles are appropriate.

In the present invention, couplers that can be used in addition to the coupler of the present invention include the following colored Suginari couplers,
That is, in the color development process, a color-developing compound is produced by atomization coupling of an aromatic compound with a grade amine developer (for example, a phenylene diamine derivative, an aminophenol derivative, etc.), for example, as a magenta coupler. !
-pyrazolone coupler, virazolobenzimitazole coupler, /anoacetylcoumarone coupler', i;
There are i-chain acylaceto nitrile couplers, yellow platers include acylacetamide couplers (e.g. benzoylacetanilides, piparoylacetanilides), etc., and cyan couplers include naphthol couplers, phenol couplers, etc. . These couplers are preferably non-diffusible and have a hydrophobic group called a ballast group in their molecules, or are polymerized. The coupler may be either di-equivalent or di-equivalent to silver ions. It may also be a colored coupler that has a color correction effect or a coupler that releases a development inhibitor during development (so-called DIR coupler).

In addition to DIR couplers, colorless DIr, which is a colorless product of the coupling reaction and releases a development inhibitor, is also used.
It may also contain an L-coupling compound.

Two or more of the above couplers etc. can be used in the same layer in order to satisfy the characteristics required for photosensitive materials,
Of course, the same compound may be added to two or more different layers.

In order to introduce the coupler into the silver halide emulsion layer, known methods such as those described in US Pat. No. 2, J, 2.2.027 can be used. For example, phthalic acid alkyl esters (dibutyl phthalate, dioctyl phthalate, etc.), phosphoric acid esters (diphenyl phosphate, triphenyl phosphate, tricresyl phosphate, dioctyl butyl phosphate), citric acid esters (such as acetyl tributyl citrate), benzoic acid esters (e.g. octyl benzoate), alkylamides (e.g. diethyl lauryl abado), fatty acid esters (e.g. dibutoxyethyl succinate, diethyl azelate), trimesic acid esters (e.g. tributyl trimesate), etc. Boiling point about 300C to 1ro
After dissolving 0c in an organic solvent such as lower alkyl acetate such as ethyl acetate or butyl acetate, 70 ethyl pionate, secondary butyl alcohol, methyl isobutyl ketone, β-ethoxyethyl acetate, methyl cellosolve acetate, etc., it is converted into a hydrophilic colloid. distributed. The above-mentioned high boiling point organic solvent and low boiling point organic solvent may be used in combination.

Also, Tokko Akira! /-32133, Tokukai Shoj/-! Tata≠
The dispersion method using polymers described in No. 3 can also be used.

When the coupler has an acid group such as carboxylic acid or sulfonic acid, it is introduced into the hydrophilic colloid as an alkaline water fermentation solution.

Polymer coupler latex can be obtained by first taking out a hydrophilic polymer coupler made by polymerizing a single coupler, and then reconcentrating it in an organic solvent and dispersing it in the form of a latex in a hydrophilic colloid. The solution of the lipophilic polymer coupler obtained above may be directly dispersed in the form of a latex. Alternatively, a polymer coupler latex prepared by an emulsion polymerization method or a core polymer coupler latex may be directly added to the gelatin silver halide emulsion.

For water-soluble polymeric couplers, see US Pat. No. 3: l
rz, rio issue, same 3, 2.2/, ta j, 2 issue, same, 3
．． ．． 299, No. 0/3, RD-/9033, etc. Regarding the polymer coupler latex, a method of dispersing a lipophilic polymer coupler in the form of a latex in an aqueous gelatin solution is described in U.S. Patent J.
, 41! U.S. Pat. No. 11,010,2/120 describes a method of directly adding a polymer coupler latex prepared by emulsion polymerization to a gelatin silver halide emulsion.
/ No. 3, 370, No. 52, No. 3, 92t, No. 3, No. 3, 3.7t 7. Gua No. 2, British Patent/, 2 Hiroshi 7
．． It can be made by the method described in A♂za issue.

These methods are also applicable to the formation of homopolymers and copolymers.

A preferred embodiment of the present invention is when a silver halide photosensitive material containing the coupler of the present invention is used.

The light fastness of the magenta color image formed from the magenta coupler used in the present invention is improved by using it in combination with a color image stabilizer represented by the following general formula (II).

',';i, R1o represents a hydrogen atom, an alkyl group, an aryl group, a heterocyclic group, R11, Rt2, R1
3, R14% R15 is a hydrogen atom, a hydroxy group,
It represents an alkyl group, an aryl group, an alkoxy group, or an acylamino group, and R13 represents an alkyl group, a hydroxy group, an aryl group, or an alkoxy group. Also RIO and R11
may be ring-closed with each other to form a j-membered or t-membered ring,
R12 in this case represents a hydroxy group or an alkoxy group. Furthermore, RIO and R11 may be ring-closed to form a methylenedioxy ring. Furthermore, R13 and Tt14 may be ring-closed to form a j-membered hydrocarbon ring (in this case, RIO represents an alkyl group, an aryl group, or a heterocyclic group).

These compounds are described in US Pat. 33, No. 0/6, 3. Riko, Tag Hirogo, Dohiro1.2j Hiro.

21! No. specification, JP-A-11-2/, No. 00g, same j'
≠-/'16,130, British Patent Publication, 2,0
No. 77.1131, 2,01,2. Specification III,
U.S. Patent No. 3.714t, No. 337, 3° H. 32,30
θ No., J, j74A, No. 627, No. 3.373.
Specification No. 030, JP-A-Shoj2-/No. 2.22! No. 3
3-203.27, same j3-/7.72, same jr
-t32/specification, British patent l.3ψ7.sst,
British Patent Publication λ, O6t, ? No. 71 Specification 1, Tokukosho,
T! It also includes compounds described in US Pat. No. 3,700, US Pat.

The photographic color formers used are conveniently selected to provide intermediate scale images. The maximum absorption band of the cyan dye formed from the cyan color former is approximately 100 to 720 nm.
The maximum absorption band of the magenta dye formed from the magenta color former is between about It is preferable that it is between.

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

The photosensitive material produced using the present invention may contain an ultraviolet absorber in the hydrophilic colloid layer. [+1 For example, benzotriazole compounds substituted with aryl groups (e.g. those described in US Pat. 332.

tl/), benzophenone compounds (e.g., those described in JP-A-Sho Guar, No. 27.5'), taihynic acid ester compounds (e.g., US Pat. No. 3.70!, 1)
No. 03, J, qo7.3ys- No. K'M+], butadiene compounds (for example, US Patent ≠).

0 Hiro J., No. 2.2) or pendioxidol compounds (e.g., U.S. Pat. No. 3,7oo,
as) can be used. Additionally, U.S. Patent 3. Gutata, 74j-bow, Tokukai Shoj F-11
Those described in No. 163j can also be used. UV-absorbing couplers (e.g. α-naphthol-based cyan dye-forming couplers) and UV-absorbing polymers may be used. good.

The light-sensitive material produced using the present invention may contain water-soluble dyes as filter dyes in hydrophilic colloids or for the purpose of preventing irradiation. Such dyes include oxonol dyes, hemioxonol dyes, styryl dyes, merocyanine dyes, cyanine dyes and azo dyes. Among them, ogisonol dyes; hemioxonol dyes and melonanine dyes are useful.

The photographic emulsion used in the present invention may be spectrally sensitized with methine dyes or others. The dyes used include
cyanine dye, merocyanine dye, complex cyanine dye,
Included are complex merocyanine dyes, holopolar cyanine dyes, heba cyanine dyes, styryl dyes and hemioxonol dyes. Particularly useful dyes are cyanine dyes,
JA for merocyanine dyes and complex merocyanine dyes
It is a dye. As the basic heterocyclic nucleus, any of the nuclei commonly used for cyanine dyes 5jiK can be applied to these dyes. That is, pyrroline nucleus, oxazinone nucleus, thiazoline nucleus, pyrrole 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 these A nucleus in which an aromatic hydrocarbon ring is fused to the nucleus, Sochi, indolenine nucleus, benzindolenine nucleus, indole nucleus, benzoxadole nucleus, naphthoxazole nucleus, benzothiazole nucleus, naphthothiazole nucleus, benzoselenazole nucleus, benzimidazole 4 yen,
Quinoline, etc. can be applied. These nuclei may be substituted on carbon atoms.

Merocyanine dyes or complex merocyanine dyes include a pyrazoline-yone nucleus, a thiohydantoin nucleus, and a cortioxazoline-λ nucleus as a nucleus having a ketomethylene structure.
, goudion nucleus, thiazolidine-λ, goudion nucleus, rhodanine nucleus, thiobarbic acid nucleus! ~ can be applied to the member heterocyclic nucleus.

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

A typical example is US Patent 2. tzaza, sps number, same λ, 2
No. 77.22Y, 3,327. OtO No. 3. r2
2. o Evening No. 2, same No. 3. j27. A<No. 41, 3, 1/
7. ．． ! Ri 3 bow, 3.62g, Ri t4, 3. t
lt, Hiro♂O@, same 3. t72゜Zari R No. 3. t7
4'2J, 3,703, J77, 3.7A
P, 30/issue, same 3゜za/gu, to2 issue, same 3. Za37
．． gt2, 7.02A, 707, British patent/,
3'll Hiro, λ1/ issue, same/, 307, 103, special public Akihiro 3-Ko 23 issue, same ta j-/2.37. No. f, JP-A-Shoj2-/10. It is described in t/za issue, j2-/θri, ri 2j.

Along with the sensitizing dye, it is a dye that itself does not have a spectral sensitizing effect or a substance that does not substantially absorb visible light,
A substance exhibiting supersensitization may also be included in the emulsion. for example,
Aminostyl compounds substituted with nitrogen-containing heterocyclic groups (for example, U.S. Pat.
2/2/), aromatic organic acid formaldehyde condensates (for example, those described in US Pat. No. 3,7 G3.!; No. 10), cadmium salts, azaindene compounds, and the like. US Patent 3. T/! , A13, 3.
A/j, tg/issue, same 3. t, /7, 2ri No. 5, same 3.
The combinations described in t3ta, no. 72/ are particularly useful.

Photographic part of the light-sensitive material of the present invention] I! Any known method can be used for this, and any known treatment liquid can be used. Further, the treatment temperature is usually selected between 0C and 0C, but it may be lower than 1g0C or higher than jOoC. Depending on the purpose, forming a silver image 1- Development processing (black and white photographic processing);
Alternatively, any color photographic process consisting of a development process to form a single dye image can be applied.

Color developers generally consist of an alkaline aqueous solution containing a color developing agent. The color developing agent is a known primary aromatic amine developer, such as phenylenecyamines (e.g., guamino-N, N-diethylaniline, 3-methyl-Hiro-
Amino-N, N-diethylaniline, ≠-amino-N-
Ethyl-N-β-hydroxyethylaniline, 3-methyl-guamino-N-ethyl-he-β-hydroxyethylaniline, 3-methyl-guamino-N-ethyl-
N-β-methanesulfamide ethylaniline, Hiro-amino-3-methyl-N-ethyl-N-β-methoxyethylaniline, etc.) can be used.

In addition to this, , F, AoMason: Ij” ['hoto
-graphicProcessing Cbemistry (published by Focal Press, /9
t6) (1) P22A-222, U.S. Patent 2, 79
3, No. 01j, 2. In addition, the color liquid may be used as described in Jt92.3t≠, JP-A-Shoda r-tμ933, etc. In addition, alkali metal sulfites, carbonates, borates, and phosphoric acids may be used. It may contain a phenomenon suppressor or antifoggant such as a salt, a buffering agent, bromide, iodide, and an organic antifoggant. Also, if necessary, a water softener, hydroxylamine, etc. may be included. preservatives such as benzyl alcohol, organic solvents such as ethylene glycol, color accelerators such as polyethylene glycol, quaternary ammonium salts, amines, dye-forming couplers, competitive couplers, fogging agents such as sodium boron hydride. , /-phenyl-3-pyrazolidone [9 drugs, viscosity-imparting agents, US Pat.

Or! , No. 7.23, a polycarboxylic Fll-based chelating agent, published by OLS 2. It may also contain antioxidants such as those described in No. t22,910.

After color development, the photographic emulsion is usually bleached.

The bleaching process may be carried out simultaneously with the fixing process or separately.6 Bleaching agents include, for example, iron (in).
, cobalt (river), chromium (W), copper (1[), etc., polyvalent intermediate compounds, hydroxide, quinone, nitrone compounds, etc. are used. For example, ferricyanide, dichromate, organic complex salts of iron (Ill) or cobalt (Ill), amino acids such as ethylenediaminetetraacetic acid, nitrilotrietatonic acid, 7,3-diamino-1-propanoltetraacetic acid, etc. Complex salts of polycarboxylic acids or organic acids such as citric acid, tartaric acid, and malic acid; persulfates, permanganates, and nitrosophenols can be used. Of these, potassium ferricyanide, sodium iron(Ill) ethylenediaminetetraacetate, and ammonium iron(1) ethylenediaminetetraacetate are particularly useful. Iron (Ill) complex salt of ethylenediaminetetraacetate is also present in a stand-alone bleaching solution.
-Also useful in bath bleach-fix solutions.

For bleaching or bleach-fixing solutions, U.S. Pat.
No. 0, copper 3.2 g/, No. 26≦, special public Akira! t-1'jO
In addition to the bleaching accelerators described in Japanese Patent Application Publication No. T, No. 1983-TJ732, etc., and the thiol compounds described in Japanese Patent Application Laid-open No. 33-TJ732, it is also possible to add occasional additives.

The silver halide emulsion used in the present invention is usually prepared by combining a water-releasable silver salt (e.g. silver nitrate) solution and a water-soluble halide salt (e.g. potassium bromide) solution in the presence of a water-soluble polymer solution such as gelatin. Create by mixing. As the silver halide, in addition to silver chloride and silver bromide, mixed silver halides such as silver chlorobromide, silver iodobromide, silver chloroiodobromide, etc. can be used.

...Average grain size of silver halide grains (grain diameter for spherical or approximately spherical grains; for cubic grains,
The particle size (expressed as an average based on the projected area) is preferably λμ or less, and particularly preferably O1 hiroμ or less. The particle size distribution may be narrow or wide.

These silver halide grains may have any shape such as cubic, octahedral, or a mixture thereof.

Further, the emulsion may be tabular, and in particular, an emulsion in which tabular grains having a length/thickness ratio of 5 or more, particularly r or more, has a total projected area of SO or more may be used.

Alternatively, two or more types of silver halide photographic emulsions formed separately may be mixed. Furthermore, halogenated 9r! [Even if the crystal structure of the twins is uniform inside, there are cases where the inside and outside have a different layered structure, and British patent 63! ,za≠
It may also be of the so-called conversion type, as described in US Pat. No. 1, US Pat. Also, those of the type that mainly form latent 1-elements on the surface,
The inner layer formed inside the particle may be any type of shell. These photographic emulsions are by Mees, Tbe
Theory of Photo, o゛graphic
Process” (The Theory of Photographic Process), published by MacMiIlan: p.
Written by Qrafkides, “Ch.
imiePhotographique” (shimmy・
Photographic), published by Paul MOnte1 (l
It is also described in the literature such as 1957) and is generally accepted.

Chimie et Ph by Glafkides
ySiquePhotogr'aphtc1ue(Pa
Published by ul Monte1, 19t7), G, F
, Duf in '4 Photography
cEmulsion Chemistry (The
Published by FocalPress, 1966), V, TJ
, Zel ikmanet al λ(making
and CoatingPhotographic
Emulsion (published by The Focal Press,
It can be adjusted using the method described in 2003/2013/2013). That is, any of the acidic method, neutral method, ammonia method, etc. may be used, and the method for reacting the soluble silver salt with the OT-soluble halogen salt may be one-sided mixing method, simultaneous mixing method, or a combination thereof. Good too.

It is also possible to use a method in which the particles are formed in an excess of shrimp ions (so-called back-mixing method).

As one type of simultaneous mixing method, it is also possible to use a method in which the pAg in the liquid phase in which silver halide is produced is kept constant, ie, the so-called Chondrald 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.

Two or more types of silver halide emulsions formed separately may be mixed and used.

In the process of silver halide grain formation or physical ripening, a cadmium salt, a zinc salt, a lead salt, a thallium salt, an iridium salt or a complex salt thereof, a rhodium salt or a complex salt thereof, an iron salt or an iron complex salt, etc. may be allowed to coexist.

As the silver halide emulsion, a so-called primitive emulsion which is not chemically sensitized can be used, but it is usually chemically sensitized. For chemical sensitization, the above-mentioned book by Glafkides or Zelikman et al.
agender PhotographyscbeiP
rosesse mit Silver-haloge
niden'' (AkademischeVerlags
gesellschaft.

196g) The method described in VC can be used.

The photographic emulsion layer or other hydrophilic colloid layer of the light-sensitive material prepared using the present invention may contain coating aids, antistatic properties, smoothness improvement, emulsification dispersion, adhesion prevention, and photographic property improvement (e.g.
Various surfactants may be included for various purposes such as development acceleration, high contrast, and sensitization.

For example, saponins (steroids), alkylene oxide derivatives (e.g. polyethylene glycol, polyethylene glycol/polypropylene glycol condensate, polyethylene glycol alkyl ethers or polyethylene glycol alkyl aryl ethers, polyethylene glycol ester>A, delJ ethylene grenol sorbitan esters) , polyalkylene glycol alkylamines or amides, silicone polyethylene oxide adducts), glycidol r1 form (e.g. alkenylsuccinic acid polyglycerides, alkylphenol polyglycerides), 11-fatty acid esters of polyhydric alcohols aL sugar alkyls Nonionic surfactants such as esters; alkyl carboxylates, alkyl sulfonates, alkylbenzene sulfonates, alkylnaphthalene sulfonates, alkyl sulfates, algyl phosphates, N-acyl-N-alkyl taurines, Acidic groups such as carboxyne groups, sulfo groups, phospho groups, sulfate ester groups, phosphate ester groups, etc. such as sulfosuccinates, sulfoalkyl polyoxyethylene alkylphenyl ethers, and polyoxyethylene alkyl phosphates Anionic surfactant containing foundation;
Amino acids, aminoalkylsulfonic acids, aminoalkyl sulfates or phosphates, alkyl betaines, amphoteric surfactants such as amine oxides; alkylamine salts, aliphatic or aromatic secondary ammonium salts, pyridinium, Cationic surfactants such as heterocyclic q-class ammonium salts such as imidazolium, and phosphonium or sulfonium salts containing aliphatic or heterocycles can be used.

Example 1 A coupler (1) of the present invention and a comparative coupler represented by the following chemical structure A, respectively /. 7mmol to 10r
nl! Dissolved in ethanol, in which the color developing main beam is Hiro-he-ethyl-N-(2-methanesulfonamidoethyl)amino-λ-methylaniline/sulfate/. 3 mmol suspension, then anhydrous sodium carbonate 12.
An aqueous solution of 9 mmol fjml of water was added and stirred at room temperature.

In this mixture, add 2.0% potassium persulfate. An ioml aqueous solution containing mol of Hiromu was gradually added dropwise.

After stirring well at room temperature for 7 hours, add 300ml of ethyl acetate and
Add 0ml of water and perform extraction operation fc. After washing the ethyl acetate layer with saturated brine, the solvent was removed and the residue was separated by silica gel column chromatography. Elution was carried out with ethyl ether. Magenta obtained from the coupler (1) of the present invention The NMR spectrum of the dye in deuterated chloroform (COCe3) is as follows.

7, jJ (d, /H, J=f, &Hz) ppm.

Otsu, tl, -4,4'! ;(m,,2[-1)pprr
i, A, , 2j (s, /H) ppm, 4', O, r (b
r, /II) ppm, J, Aff-j, 2(m, 4H)
ppm.

(t, 3H, J-6, Hz) pl)m
If tppm is absorbed, add the following structural formula B to iRa. The melting point of this dye was /7j to /7r0c.

The visible absorption spectra of magenta dyes formed from magenta dye B and comparative coupler A in ethyl acetate are shown in FIG. The absorption values of the two were normalized to the highest concentration of lactol and compared to 0.

As shown in Figure 1, the dye obtained from the coupler of the present invention has λ in the magenta region even though it is a simple bone nucleus.
max, and it can be seen that there is no sub-absorption near ti-oo-4'sonm that exists in the dye □ formed from comparative coupler A.

Example 2 To 1/3 g of the comparative coupler C shown below, add and dissolve trioctyl phosphate (rml), ethyl acetate (tz ml), and dissolve this solution in a 70% aqueous solution of seratin containing sodium di-sec-butylnaphthalenesulfonate/ 00 g, and stirred and emulsified using a homogenizer emulsifying machine to obtain an emulsion. This emulsion was mixed with green-sensitive silver chlorobromide emulsion (Br≠j mole, α!j mole) 3009 (containing 3.3 g of silver), and coating aids; sodium dodecylbenzenesulfonate, hard 11'A agent: 2-
Hydroxyg and 6-dichloro-s-triazine were added and coated on a cellulose triacetate support. Furthermore, a gelatin coating solution was applied as a reinforcing layer on top of this layer and dried to obtain film A.

r/α On the other hand, the coupler (5) of the present invention is /2. /9, use
Film B was created in the same manner as the above film person.

Similarly, a film C was prepared in the same manner as the above film A except that the coupler (21) of the present invention was used /J', 29 and the prismatic silver chlorobromide emulsion 2oog was used.

The above films A to C were exposed with a photosensitive needle at 100 lux for 1 second and processed with the following processing solution.

It can be seen that the two-equivalent coupler represented by compound 1) gives a high color density in the developing solution, and gives a high color G degree with a small amount of coated silver. It can also be seen that the light fastness of the color ('I) produced from the novel framework of the present invention is more robust than that of the color f& formed from the conventional j-pyrazolone type coupler.

[Brief explanation of drawings]

FIG. 71 1 is an absorption spectrum. A This is actually an absorption spectrum of the dye produced from coupler A of Example 1 (comparative example). B. Absorption spectrum of the dye produced from the coupler (], ) of Actual Example 1 (invention). The horizontal axis represents the wavelength, and the vertical axis represents the absorption intensity. It shows what is normalized to O. Patent Applicant Fuji Photo Film Co., Ltd. Procedural Amendment 1. Display of incidents Showa! Special application No. 1 13 Mag No. 2,
Title of the invention Color image forming method 3, relationship with the case of the person making the amendment Patent applicant Address 210 Nakanuma, Minamiashigara City, Kanagawa Prefecture Target of the amendment Elms and drawings in the "Detailed Description of the Invention" in the specification & Contents of the amendment (1) The statement in the "Detailed Description of the Invention" column of the specification is amended as follows. Correct "dodecyl" in line O of page 6 to "dodecane". 2, page 7, line 3, "butyramide" is corrected to "butanamide." 3. On page 7, the line ``[phenoxy)butyl'' is corrected to ``[phenoxy)butane.'' 4. Correct "N, N's" on page 7/line 4' to r, N, N-J. &Page 7/, correct "Kushiso" in line 1 to "Kushin". ・Correct "Phenoxyl group" in line 2 to "Phenoxy group" on Page 6, 10. 7. Correct "sulfamoyl" in line 5 of page 1 to "sulfamoyl". 8, page 1, line ♂, "benzyl-ethoxy" is corrected to "benzyl-yo-ethoxy". 9. Correct "triazole" on page 1/line j to "tetrazole" IQ, and "thiophenyl" on page 1.2/line 3 to "chenyl." 11. The statement on page 13, line ψ is amended to r -NHCOR20-CONHu (R20 is substituted or 13 Correct "represents" in lines 13 to 4' of page 1j to "is." 14 Correct "represents" to "is." [α-alkylacrylic acid] is corrected to “α-alkylacrylic acid”. The l&7th member “β-hydroxyquine” is corrected to “β-hydroxyquine terme”. " is corrected to "methylenebis". The structural formula of the compound (support) on page 23 of page 19 is corrected to "compound on the top left of page 23, page 20". 21, second column of page 26 Correct "0 1 (R4CO) 20 R4-C- (halide)" in the reaction formula to "11 (R4CO) 20 or Ra-C- (halogen)". 22, page 2, line IO Correct “l000” to “1000C”. 23 Correct rpbJ on the 7th line of the 22nd page to PdJ. 24 Correct rpdJf on the 20th line of the 22nd page to PdJ. 25 Correct the rpdJf on the 20th line of the 22nd page to PdJ. "Aromatic compound" from line 1' to line 79
is corrected to "aromatic nitrogen-containing". 26, page 37, line 3, "aromatic nitrogen" is corrected to "aromatic nitrogen-containing". Correct "/at 00" to "/j00c". 28, 37th line, "aromatic nitrogen" is corrected to "aromatic nitrogen-containing". 29 Correct with the compound in the upper row of the reaction formula on page 32. 30, page 33, line ♂, “resistant aqueous solution” is corrected to “acidic aqueous solution”. 31, on the third page, the line ``oximino'' is corrected to ``oximino''. Correct the "0" in the third row of 3z to "0". 3, the third is negative, and 12) p d-c [H] J in the reaction formula at the bottom is 1-. 2) Correct as Pd-CC11]J. 34-Correct ``, z ) pd-c CH) J in the second column of the reaction formula to ``, 2 ) Pd -C(H) J'' on page 37. 3ii. Correct 1111 as follows. 36 Correct the rpdJ of the third and negative/second row to PdJ. 37 Correct the rpdJ of the third page row to PdJ. 38. Correct the I pdJ of the 32nd page to PdJ. Correct it as “Pd”. Delete "R13," on the 3rd line of page 39≠j. 40 Nails 1 Gua H/Correct "benzooxidol" in lines 7 to 1 to "benzoxazole.""Aminostyril" in line j of page 41 is corrected to "aminostyril." Correct "COCl1!3" in the 7th line of No. 42 A/Sada to "rcDα3". 4a, page t3, line λ, "Figure-/" is corrected to "Essential/Figure". 44 No. 6, amend "Table 1" on page 10 line to "Table below". (2) Amend the drawing as shown in the attached sheet.

Claims (1)

[Scope of Claims] A color image forming method using silver halide, which comprises reacting a coupler represented by the following general formula (I) with an oxidation product of an aromatic-amine developing agent. R3 However, X represents a hydrogen atom or a coupling-off group, ) (1, R2, R3 represents a hydrogen atom or a substituent, R], R2, Ra or may be formed.