CA1257128A - Silver halide color photographic material - Google Patents

Abstract

ABSTRACT OF THE DISCLOSURE

A silver halide color photographic material that has at lease one silver halide emulsion layer on a support is disclosed. Said silver halide emulsion layer contains at least one magenta coupler having the following formula:

Description

z~

SILVER HALIDE COLOR PHOrrOGRAPHIC
MATERIAL

Field of the Inventlon:
The prPsent invention relates to a silver halide color phokographic material that containR a magenta coupler aapable o~ effective color formatlon and whlch ~o~m~ a ; magenta dye image having improved keeplng ~uallty, par-ticularly in terms o~ light fastness. More speci~ically, the invention relates to a ~llver halide color photographic material containing a novel lH~pyrazolo~3,2-c}S-triazole derived magenta coupler.

Background of the Invention:
.
The formation of dye images in most silver halide color photographic materials depends on the reduction o~
exposed silver halide grains with an aromatic primary amine color developing agent and the subsequent coupling of the resultant oxidativn product of the color developing ~ agent with couplers that respectively form yellow, magenta - and cyan dyes.
Pyrazolone type couplers are commercially used as couplers for providing magenta dyes, but they have an un-wanted secondary absorption and their keeping quality, particularly their resistance to formalin gas, is relatively low.

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A variety oflH-pyra~olo[3,2-o]-S-triazole derived magenta couplers have been proposed to ov~rcome these problems of the conventional pyrazolone type couplers.
Reference should be had to U.S. Patent No. 3,725,067, as well as British Patent Nos. 1,252,418 and 1,334,515.
The compounds disclosed in these patents avoid the pxoblem o~ secondary absorption but the improvement is inadequate in terms of rasistance to formalin gas and is insignificant in respect of the production of a light-fast magenta dye image. The compound disclo~ed in Research Disclosure No. 12~43 has no commercial value because of its low color formation. The lH-pyrazolo[3,2-c]-S-triaæole ~ype magenta aoupler disclosed in Unexamined Publlshed Japanese Patent Application No. 42045/1983 features significant improve-ments in formalin resistance and color formation but little improvement has been achieved in terms of the pro-duction of a light-fast image.
Improved color development has also been achieved by the couplers described in Unexamined Published Japanese Patent Application Nos. 99437/198A and 125732/198A but the dye images produced by these couplers are still low in light fastness. The coupler disclosed in Unexamined Published Japanese Patent Application No. 99437/1984 depends on the concomitant use of additives for providing a light-fast image. The coupler disclosed as Compound

2~

No. 19 in Unexamined Published Japane~e Pat~nt Applica-tion No. 125732/1984 produces a dye image having slightly improved ligh~ ~astness but the improvement is far from being satisactory.
In short, the lH-pyrazolo[3,2-c]-S-tria201e derived magenta couplers that have been considerecl useful because of the absence o~ secondary absorption and their high resistance to ~ormalin gas fall far short of ~atisfying the re~uirement for providing dye images with improved light fastness.

Summar~ f the Invention:
The primary object, therefore, of the present $n-ven-tion is to provide a silver hal.ide color photographic material that contains a magenta coupler capable of ef-fective color formation and which forms a magenta dyeimage having improved light fastness and resistance to formalin gas.
This object of the invention is achieved by a silver halide color photographic material that has at least one silver halide emulsion layer on a support, said silver halide emulsion layer containing at least one magenta coupler having the following formula:
X H

N -~ 2 .~

~æsq~z~

wherein R1 is a tertiary alkyl group; R~ is a prlmary-alkyl group; and X is a halo~en atom.
As a result of various studies made to achieve the stated object, the inventors have ound a lH-pyrazolo~
[3,2-c]-S-triazole derived magenta couplex that exhibits effective color formation and which provides a magenta dye image having improved formalin resistance and light ~astness.
Detailed Desc~ption of the Invention:
The tertiary alkyl group represented by Rl may be substituted at the tertiary carbon, i.e. the carbon atom directly coupled to the lH-pyrazolo[3,2-c~-S-triazole nucleus. A cyclic ring including the textiary carbon is also included within the meaning of the "tertiary alkyl group". In short, R1 represents all alkyl groups wherein the tertiary carbon is bonded to anything but hydrogen.
The alkyl bonded to the tertiary carbon may have a substituent such as halogen or alkoxy.
Typical examples of the tertiary alkyl as Rl include t-butyl, 1,1-dimethyl-2-methoxy-ethyl, 1,1-dimethyl-2-chloro-ethyl, l-methyl-l~methoxy-ethyl, l-methyl-l-phenyl-ethyl, l,l-di-n-amyl~hexyl, 7,7-dimethylnorbornan-1-yl, l,l-dimethyl-butyl, l-ethyl-l-methyl-propyl and adamantyl.
The primary alkyl group represented by R2 is an alkyl group having two hydrogen atoms bonded to root carbon atom ~Z~

which is directly bonded to the lH-pyrazolo[3,2-c]-S-triazole ring.
The primary alkyl group represented by R2 may be substituted by aryl, hetero ring, halogen, cyano, a group that is bonded by carbonyl (e.g. alkoxycarbonyl, acyl or carbamoyl~, or a group that is bonded by a hetero atom (e.g. nitro, alkoxy, alkylthio, arylthio, alkylsulfonyl, arylsulfonyl; alkylsulfinyl, arylsulfinyl or dialkylamino).
Particularly preferred substituents are alkylthio, arylthio, alkylsulfonyl, arylsulfonyl, alkylsulfinyl and arylsuIfinyl.
If the heterocyclic group is a compound such as lH-pyrazolo[3,2-c]-S-triazole-3-yl, a bis type lH-pyrazolo-[3,2-c]-S-triazole compound is formed and this is of course a magenta coupler lncluded within the scope of the present invention.
The halogen atom represented by X includes chlorine-bromine and fluorine.
The lH-pyrazolo[3,2-c]-S-triazole derived magenta couplers in accordance with the present invention are illustrated by, but by no means limited, to the following compounds.

.~

(1~

(~)C,, Hg~N
N--N--I C7HIa (2) (t~C4~
C7 H, 5 ~3) It)C4Hg ~`N tC5H
N _11 (C~12 ) 3 b-tC5H
t~) C~ H
: C8Hl7 ~ ~ 11 , C5 ~ 1 ~C2 H5 (5) Br H
~t)C4 Hg ~ N~
N--N ~ )3 ~ ~HSO2 ~3 Cl '~ H2 5 3L~2S~ L2 E3r ~3 (t)C4 E~ ~,N~N
N ~N (CH2 ~3NHSQ2 ~ oC,2 ~125 (7) Cl H3 C~ H
C~ 2 1 ~`N
CH3 N--N~LC7H,s `. (8) C~ H
(t)C4 ~ N
N--N CE~CH2SO2clsH37 ( 9 ) C~ H
~t) C4 Hg ~ ~N
~--~ CE12 C~12 C~ S~;~,CI~ 7 (10) (t)Cg Hg ~
C~ CH2 SC 1~ H3 7 ~L257 (11) ce c N ~ L CH2 o~ lC5 H"
(12) C~ H

~C7~15 :~: (13) C~3 ~ H
C~--C ~`N
OCH 3 C 7H~ 5 (1~) : Br H
~t3C4 ~9~
~15 H3 1 ~15) 2 )3~COCl~Q~3S02~3 Cl2 ~25 (16) F H

(t)C~Hg ~ ~N
C7 ~ ~ 5 (~7) Lc~i2C}12S~c~2~2 , (18) ( t j C4Hg~N~N
N~ l,>CH~COOCI4 H~g (19 :~ Br .(t)C4Hg~ ~ CI~L3 JL C~ C~ 13 (,'~3 C~3 : (20) ~1 3 ce H
CH3~ 11 C7 ~1l a ~,.

~2S7~2~3 ~213 _~(C1~12)~ HCOC~ 302r~l/
t)C.~ gJ~L~ C12 ~25 C~3 :' . .

The method for synthesizing a typical compound i~
de~cribed below, Th~ general re~erence W~8 to Re~earch Di~closure No. 12443.
Sy~th _ nd_(l3:
The reaction scheme is shown below:

~H?~HC~2 ~--~
11 + C7~il5 COO~ 7H,5 ~E~2 ~I) S ~l'l ~1 I ) + C~I3{~ r ~tJ~q ~ ~C7Hl s ~ 3 ( ) H
(t)C4H9 1 ~ C~ H, 6 (m~ .
ce H
(t)C4E~ r~
C7~ 1 5 Compound (I) (1) Synthesis of compound (I):
A mixture of capric acid (500 g) and thiocarbohydrazide (lO0 g~ was refluxed for 8 hours without solvent. After cooling the mixture, the resulting crystal was recovered by filtration, washed with water and recrystallized from a mixed solvent of alcohol/water to obtain a white end product.
(2) Synthesis of compound (II):
A mixture of 64.3 g of compound (I) and 53.7 g of t-butyl-bromomethyl ketone was boiled in alcohol for 5 hours under agitation. The solvent was distilled of and the residue was dissolved in methanol and neutralized by addition of 10~ sodium carbonate. After adding water, the organic layer was extructed with ethyl acetate~ which was then distilled off and the residue was purified by column chromatography on silica gel using benzene-acetone as a solvent.

(3) Synthesis of compound (III):
Thirty grams of compound (II) was dispersed in 500 ml of n-dodecane and the dispersion was boiled under agitation for 6 hours with a nitrogen gas blown into the dispersion.
After leaving the dispersion to cool down, the solid crystal was recovered by filtration, purified by column chromatography on silica gel using benzen/acetone as a solvent and recrystallized from hexane to obtain -the end product (III).

1~

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(4~ Synthesi6 of compound (I):
Five point three grams of compound (III) was ~issolved in chloroform and, to the solution, and equivalent amount of N-chlorosuccinimide was added. The mixture was held at room temperature for 30nunutes to perform reaction. The chloroform was distilled off and the residue was extracted with ethyl-acetate and washed well with water. The ethyl acetate was then distilled off and residual purified by column chromatography on silica gel using benzene~acetone as a solvent to obtain the end product. The end product was identified as compound (1) by NMR spectrum and Mass spectrum.
Other compounds were synthesized by the method used in the production of compound (1?. When the acid used in the reaction with thiocarbohydrazide was solid, methyl cellosolve, or ethylene glycol was used as a solvent.
The silver halide color photographic material of the present invention may contain conventional dye forming couplers.

1~

7~8 Xnown open chain ketomethylene ~ouplQrs may be u~ed as yellow-formlng couplers. Benzoylacetanilide and plvaloylacetanilide compounds are particularly useful.
Speaiflc examples of the usable yellow fo~ming couplers are de~crlbed ln U.S. Patent Nos. 2,875,057, 3,2~5,506, 3,408,194, 3,551,15S, 3,582,32~, 3,725,072, and 3,891,445;
German Patent No. 1,547,868, German Patent Applicatlon (OLS) Nos. 2,219,917, 2,261,361 and 2,414,006; British.
Patent No. 1,425,020; Japanese Patent Publication No.
1~783t1976, Unexam~ned Published Japanese Patent Applica-tlon No~. ~6133/1972, 73147/1983, 102036/1976, 6341/1975, 12334~/1975, 130442/1975, 21827/1976, 87650/1975, 82424/1977 and 115219/1977.
Usable cyan ~orming couplers are pheno].ic and naphtholic compounds. 5pecific examples are found in U.S. Patent No8~ 2,369,929, 2,434,272, 2,474,293, 2,521,908, 2,895,826, 3,034,892, 3,311,476, 3,458,315, 3,476,563, 3,583,971, 3,591,383, 3,767,411 and 4,004,929; German Patent Applica-tion (OLS) Nos~ 2,414,830 and 2,454,329; and Unexamined Published Japanese Patent Application Nos. 59838/1973, 26034/1376, 5055/1973, 146828/1976, 69624/1977 and 90932/
1977.
As magenta forming couplers, one or more of the couplers prepared in accordance with the present invention 3L~.5~

may be used. They may also be used in combination with known mage~ta couplers such as pyrazolone compounds, indazolone compounds, cyanoacetyl compounc1s, pyrazollno-benzimldazole compounds and pyraxolotriazole compounds.
S It should however be emphasized that at least one of the magenta couplers incorporated in the c;ilver halide color photographic material of the present invention must be the coupler defined in accordance with the invention.
The coupler o~ the present inventlon may also be used in combination with colored couplers capable of color correction, or development inhibitor releasing couplers (DIR couplers) that are effective for producing improved image quality.
The magenta coupler of the present invention and the respective couplers associated thereto may be introduced into silver halide emulsion layers by any known method such as one described in V.S. Patent No. 2,322, 027.
For example, the couplers are dispersed in hydrophilic colloids after being dissolved in high-boiling organic solvents or low-boiling organic solvents. Examples of the former type include alkyl esters of phthalic acid ~e,g, dibutyl phthalate and dioctyl phthalate), phosphate esters (e.g. diphenyl phosphate, triphenyl phosphate, tricresyl phosphate and dioctylbutyl phosphate~, citrate esters (e.g. tributyl acetylcitrate), benzoate esters ' 1~

i7~8 (e.g. octyl benzoate), alkylamides (e.g~ cliethyl lauryl-amide), aliphatic acid esters (e.g. dibutoxyethyl succlnate and dioctyl azelate) and trimesic acid ester3 (e.g. trl~
butyl trimesate). The low-hoiling organic solvents are those which boil at ~etween about ~0C and 150C, and examples are lower alkyl acetates (e.g. ethyl acetate and butyl acetate3, ethyl propionate, secondary butyl alcohol, methyl l~obutyl ketone, ~-ethoxyethyl acetate and methyl cellosolve acetate. The hlgh-boiling organlc solvents may be used ln combinatlon with the low-boillng organic solvents.
Dispersion methods using polymers may also be used and such mekhods are descxibed in Japanese Patent Publica-tion No. 39853/1976 and Unexamined Published Japanese Patent Appllcation No. 59943/1976.
The magenta coupler of the present invention is incorporated in a silver halide emulsion layer l1sually in the amount of from 0.005 to 2 moles, preferably from 0.03 to 0.5 mole, per mole of silver halide.
The magenta coupler of the present invention forms a satisfactorily light-fast dye image, but even higher light fastnass may be obtained by using an anti-f~ding agent or by overlaying the emulsion layer of interest with a layer containing an ultraviolet absorber.
Illustrative anti-fading agents include hydroquinone .~

derivatives of the type described in U.S. Patent Nos.
2,360,290, 2,418,613, 2,673,314, 2,701~197, 2,704,713, 2,728,659, 2,732,300, 2,735,765, 2,710,801 and 2,816,028, as well as sritish Patent No. 1,363,921; gallic acid derivatives as describded in U.S. Patent Nos. 3,457,079 : and 3,069,262; p-alkoxyphenols of the type described in U.S. Patent Nos. 2,735,765 and 3,698,909, as well as Japanese Pa~ent Publication No. 20977/1974 and 6623/
1977; p-oxyphenol derivatives of the type described in U.S. Patent Nos. 3,~32,300, 3,573,050, 3,574,627 and 3,764,337, as well as Unexamined Published Japanese Patent Application Nos. 35633/1977, 147434/1977 and 152225/1977; and bisphenols as described in U.S. Patent No. 3,700,455.
Exemplary ultraviolet absorbers includes aryl-substituted benzotriazole compounds (as described in U.S.
Patent No. 3,533,794), 4-thiazolidone compounds (as de-scribed in U.S. Patent Nos. 3,314,794 and 3,352,681), : benzophenone compounds (as described in Unexamined Published Japanese Patent ~pplication No. 2784/1971), cinnamic acid ester compounds (as described in U.S. Patent Nos.
3,705,805 and 3,707,375), butadiene compounds (as described in U.S. Patent No. 4,045,229), and benzoxidole compounds (as described in U.S. Patent No. 3,700,455). Other com-pounds usable as UV absorbers are found in U.S. Patent No. 3,499,752 and Unexamined Published Japanese Patent Application No. 48535/1979.
hny o~ the silver halides that are incorporated in conventional silver halide emulsions may be used in the present invention and they include silver bromide, silver chloride, silver iodobromide, silver chlorobromide and silver chloroiodobromide. In order to provide sensitivity for the desired spectral wavelength region, the silver halides used in the present invention may be spectrally sensitized by suitable selected sensitizing dye~. Usa~le dyes include cyanine, merocyanins, complex cyanine, complex merocyanine, holopolar cyanine, hemicyanine, styryl and hemioxonole d~eq.
U~eful ~ensitizing dyes are described in, for example, German Patent No. 929,080, U.S. Patent Nos. 2,231,658, 2,493,748, 2,503,776, 2,519,001, 2,912,329, 3,656,95g, 3,672,897, 3,694,217, 4,025,349 and 4,046,572; British Patent No. 1,242,588; and Japanese Patent Publication Nos. 14030/1969 and 24344/1977.
These sensitizing dyes may be used either individually or in combination. Combined sensitizing dyes are often used for the purpose oE supersensitization, as typically described in UOS. Pa-tent Nos. 2,688,545, 2,977,229, 3,397,060, 3,522,052, 3,527,641, 3,617,293, 3,628~964, 3,666,480, 3,672,898, 3,679,42~, 3,703,377, 3,769,301, 3,814,609, 3,B37,862 and 4,026,707; British Patent Nos.
1,344,281 and 1,507,803; Japanese Patent Publication Nos. 4936/1968 and 1237S/1978; and Unexam:ined Published Japanese Patent Application Nos. 110618/1977 and 109925l1977.
The silver halide emulsion used in the present in-vention may incorporate a variety of known photographic additives such as those described in Research ~isclosure ~o. 17643.
T}le silver halide color photographic material of the present invention may use any support material that is properly selected from among known materials depend-ing on the specific object, such as plastic films, plastic laminated paper, baryta paper and synthetic paper.
The silver halide color photographic material of the invention may adopt any of the layer arrangements commonly used in the photographic industry.
The so arranged silver halide color photographic material of the invention is exposed and thereafter sub-jected to color development by a variety of photographic processing techniques. The color developer used to process this photographic material may contain any of the known aromatic primary amine color developing agents that are extensively used in various color photographic processes. Such developing agents include aminophenolic and p-phenylenediamine derivatives. These compounds are ~g generally used in salt forms, such as hydrochlorides or sulfates, which are stabler than the free state.
These compounds are used in concentrationC; that generally range from about 0.1 to about 30 g, preferably from about 1 g to about 1.5 g, per liter o~ the color de~eloper.
Illustrative aminophenolic developing agents include o~aminophenol, p-aminophenol, 5-amino-2-oxytoluene, 2-amino-3-oxytoluene, and 2 oxy-3-amino-1,4-dimethylbenzene.
P~rticularly useful primary aromatic amino color 1~ developing agents are N,N'-dialkyl-p-phenylenediamine compounds wherein the alkyl or phenyl group may have a suitable substituent. Among these compounds, the follow-ing are particularly advantageous: N,N'-diethyl-p-phenylene-diamine hydrochloride, N-methyl-p-phenylenediamine hydrochloride, N,N'-dimethyl~p-phenylenediamine hydro-chloride, 2-amino-5-(N-ethyl-N-dodecylamino)-toluene, N-ethyl-N-~-methanesulfonamidoethyl-3-methyl-4-aminoaniline sulfate, N-ethyl-N-~-hydroxyethylaminoaniline, 4-amino~
3-methyl-N,N'-diethylaniline, and 4-amino-N-(2-methoxyethyl)-N-ethyl-3-methylaniline-p-toluene sulfonate.
In addition to these primary aromatic amino color developing agents, the color developer used in the processing of the photographic material of the present invention may contain a veriety of additives that are commonly incorporated in color developers and such additives in-2a ~2~

clude alkali agents (e.g. sodium hydroxide, sodium carbona~e and potassium carbonate), alkali metal sulfites, alkali metal bisulfites, alkali metal thiocyanates, alkali metal halides, benzyl alcohol, water softeners and thickeners. The p~ of the color developer is usually at least 7 and most generally ranges from about 10 to about 13.
After color development, the photographic materia:L
of the present in~ention is processed by a solution having the fixing ability. If this solution is a fixing bath, its use is preceded by a bleaching step- The bleaching bath used in the bleaching step or the bleaching agent used in a bleach-fixing bath is made of a metal complex salt of an organic acid. 'rhis metal complex salt has the ability not only to oxidize metallic silver (i.e., formed as a result of development3 into silver halide but also to ensure complete color formation by a color former. The structure of this metal complex salt is such that an organic acid such as an aminopolycarboxylic acid, oxalic acid or citric acid is coordinated to a metal ion such as iron, cobalt or copper. The organic acids most preferred for use in forming metal complex salts are polycarboxylic acids or aminopolycarboxylic acids. The polycarboxylic acids or aminopolycarboxylic acids may be in the form of alkali metal salts, ammonium salts or ~1 wa~er-soluble salts.
Typical examples of polycarboxylic acids or amino-polycarboxylic acids are listed below:
(1) ethylenediaminetetraacetic acid;
(2) diethylenetriaminepentaaeetic aeid;
(3) ethylenediamine~N~ oxyethyl)-N,N',N'-triace~ic acid;
i4) propylenediaminetetraacetic acid;
(5) nitrilotriacetic acid;
(6) cyclohexanediaminetetraacetic acid;
(7) imi~odiaeetic acid;
(8) dihydroxyethylglycincitric acid (or tartaric acid);
~9) ethyletherdiaminetetraacetic acid;
(10) glyeoletherdiaminetetraacetic acid;
(11) ethylenediaminetetrapropionic acid;
(12) phenylenediaminetetraacetic acid;
(13) ethylenediaminetetraaeetie acid disodium salt;
~14) ethylenediaminetetraacetic acld tetra~trimethyl-ammonium) salt;
(15) ethylenediaminetetraacetic acid tetrasodium salt;
(16) diethylenetriaminepentaacetic acid pentasodiu~ salt;
(17) ethylenediamine-N~(~-oxyethyl)-N,N',N'-triacetic acid sodium salt;
(18) propylenediaminetetraacetic acid sodium salt;
(19) nitrilotriacetic acid sodium salt; and 2~ (20) cyclohexanediaminetetraacetic acid sodium salt.

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In addition to metal complex salts of these organic acids which are used as bleaching agents, the bleaching bath used in processing the color photo~raphic makerial of the present invention may contain a variety of ad-ditives, and preferred additives are reha:Logenating agents such as alkali or ammonium halides (e.g. potassium bromide, sodium bromide, sodium chloride and ammonium bromide), metal salt~ and chelating agent~. ~ny other additives that are conventionally incorporated in bleaching baths may also be used and they include p~ buffers (e.g. borate, oxalate, acetate, carbonate and phosphate salts), alkyl-amines and polyethylene oxides.
The fixing bath and bleach-fixing hath may also con-tain one or more pH buffers that are selected from among sulfites (e.g. ammnium sulfite, potassium sulfite, ammonium bisulfite, potassium bisulfite, sodium bisulfite, ammonium metabisulfite, pota~sium metabisulfite, and sodium metabisulfite), and a variety of acids or salts ~e.g.
boric acid, borax, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, acetic acid, sodium acetate and ammonium hydroxide).
Tf the photographic material of the present invention is processed in a bleach-fixing bath as it is supplied - 25 with a blix replenisher, thiosulfakes, thiocyanates, ~25~

sul~ites or other 3alts may be incorporated either in the bleach-~ixing bath or in the repleni~her that i3 ~ed to said blix bath.
In order to increase the activity of the bleach-fixing bath used in processing the photographic material of the present invention, air or oxygen may be blown into a tank containing the bleach~fixing bath or its replenisher. Alternatively, a suitable oxidant ~uch as hydrogen peroxide, bromate or persulfate may be added into the tank.
In the magenta coupler of the present invention, when Rl in the above-mentioned formula represents a t-butyl group and X represents a chlorine atom, R2 is preferably a group other than the following six groups:

(1) ,~

-(CH2)~ Cla (2) - (CH2 )3 ~NlIC0- CIIS02~ c1-13 C 12~1 25 (3) -~CH2)3~;~NH~0-CIIS02~ oocH3 C,lH~

~ j79~28

(4) - (CH~ )3 ~NIICO~CI12 S

(5) -(C1~2)" ~tlllCOCllG~3C51~ttl t) I

; (6) Cs~ll(t) -(cu2)3~N~lcocHo~3~sH~l(t~
C2Hs :
The following examples are provided for furthar illustration of the claimed photographic material but are no~ to be construed as limiting the inventlon.
Example 1 One tenth of a mole, per mole of silver, of one of the magenta couplers listed in Table 1 (which follows) was mixed with an equal weight of tricresyl phosphate and three times the coupler's weight of ethyl acetate, and -the mixture was heated to 60C to Eorm a complete solution. The solu-tion was then mixed with 1,200 ml of 5 % aqueous gelatin solution containing 120 ml of a 5 % aqueous solution of Alkanol B (trade name of du Pont for alkylnaphthalene sulfonate). The mixture was Pmulsified with an ultrasonic disperser and the dispersion obtained was added to 4 kg of a green-sensitive sil~er iodobrom:ide emulsion (containlng ~5~ 8

6 mol% AgI). To the mixture, 120 ml of a 2 ~ solution (water:methanol = 1:1) of 1~2-bis(vinylsulfonyl)-ethane was added as a hardener, and the 50 prepared coating solution was applied to a subbed transparent polyester base, and the web was dried to provide a sc~mple of color photographic material (with silver deposit of 20 mg/100 cm ), The other samples were prepared by the same pxocedure.
Each of the samples thus prepared was subjected to exposure through an optical wedge as in the conventional process and subsequently processed by the following scherne.
The results of such photographic processing are shown in Table 1 below.

Processing scheme Steps TemE~ __C Tirne Color development 38 3 min, 15 sec ~leaching 38 4 mln, 20 sec Washing 38 3 min, 15 sec Fixing 38 4 min, 20 sec Washing 38 3 min, 15 sec Stabilizing 38 1 min, 30 sec Drying 47 to 5516 min, 30 sec.

The foumulation oi each of the processing solutions used is indicated below.

Color developer , ~

Potassium carbonate 30 g sodi~m hydrogencarbonate 2.5 g potassium sulfite 5 g sodium bromide 1.3 g po~assium iodide 2 mg hydroxylami.ne sulfate 2,5 g sodium chloride 0.6 g diethylenetriaminepentaacetic 2 5 acld sodium salt . g 4-amino-3-methyl-N-ethyl-N~ 8 g hydroxyethyl)aniline sulfate potassium hydroxide 1.2 g water to make 1,000 ml pH adjusted to 10.06 by addition of potassium hydroxlde or 20 ~ H2SO~.
Bleaching bath - Ethylenediaminetetraacetic acid ixon 100 g ammonium salt Ethylenediaminetetraacetic acid 10 g Ammonium hromide 150 g Glacial acetic acid 40 ml Sodium bromate 10 g water to make 1,000 ml pH adjusted to 3.5 by addition of ammonia water or glacial acetic acid.
Fixing bath:
Ammonium thiosulfate 180 g ~7 ~25~ B

Anhydrous ~odium ~ul1te12 g So~llum metabi~ul ite 2 . 5 g ~thylone~ a~etraaoatla aaiâ0 5 g dl~odlum salt Sodi~n carbonate 10 g water to make 1, 000 ml _a bl li ~b~h Formalln (37 %aq. sol. )2 ml Konidax ~product of Konishiroku 5 ml Photo Industry Co., Ltd. ) water to make 1 ,000 ml.

~L~5~2~3 __ - -- -M
~D C~ U~ In ~ ~ In ~D ~D ~ ~ ~D ~ ~

_~ __ ____ _~, . ._ t~
, o o~
E3, ,~ ~ ~cn a~ ~ cn a~ OQ
O M
F4 a) . _ , _ ~ ~a~
~rl M~DN
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0 C) ~a ... ~

~ 3 P o o oo ~
~ J O ~a~ o ~ Q a~l Q
a~
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E-l M
.. ~
_ _ _ ,_ _ _ -1 ~ ~I N 1` ~ ~ O
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a~ a M ~1 ~ Q.
h t) ~ ~ O O O O O O
O ~
C~ ~ O
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O
C) U~
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R~ ~ ,1 ~ ~ ~ ~n ~ 1` c~~ o ~ ~ ~
IU Z
U~

~r~
., ~3 ~5~7~2~

Notes: 1) The specific sensitivity is expressed as the reciprocal of the exposure that provides a fog plus 0.1 density, with t:he value for sample No. 11 (using comparative coupler 1) being taken as 100.
2) A sample was subjected to color development after it was held for 3 days in a sealed container of 0.9% aqueous formalin (6 ml) conditioned at 30C and 62% ~.H. An untreated sample was al~o color developed. The formalin resi~tance of the first sample was calculated by the following formula:

Formalin Color density of the treated sample x 100 (%) resistance Color density of the untreated sample 3) A color-developed sample was illuminated in a xenon fadeometer for 5 days and the percentage ~ ~ ~ re idual dye for the ini~ial density (D) of 1.0 :~ was calculated to determine the lightfastness of the image:
; 20 Light Density after 5-day illumination fastness in xenon fadeometer x 100 (%) ~.:25'7~1L28 Compara_ive coupler 1 CQ H
CH3~d~N~N

Comparative coupler 2 tC4Hg ~ N

7Hl5 The data in Table 1 show that the couplers prepared in accordance with the present in~ention satisfied all the requirements for high color density and the produc~ion of formalin-resistant and light-fast dye images.

Example 2 Sample Nos. 21 to 28 as prepared in Example 1 were exposed through an optical wedge and subsequently processed by the following scheme. The results are shown in Table 2.
The specific sensitivity and light fastness were measured by the same methods as used in Example 1.

- ~!.2~;'7~

Processinq scheme:
Color development38C 3 min, 30 sec Bleach-~ixing 33C 1 min, 30 sec Stabilizing or 25 - 30C 3 min Drying 75 - 80C ca. 2 min.

The solutions used in this scheme had the following formulations.

Color developer Benzyl alcohol 15 ml Ethyl~ne glycol 15 ml Potassium sulfite 2.0 g Potassium bromide 0.7 g Sodium chloride 0.2 g Potassium carbonate 30.0 g Hydroxylamine sulfat~ 3.0 g Tripolyphosphoric acid ITPPS) 2.5 g 3-Methyl-4-amino-N-ethyl-N~
methanesulfonamidoethyl)aniline 5.5 g sulfate 20 Brightener (4,4'-diaminostilbenzo- 1.0 g sulfonic acid derivative) Potassium hydroxide 2,0 g Wat4er to make 1,000 ml pH adjusted to 10.20 3~

~LZ~ 8 Bleach-fixing bath Ethylenediaminetetraacetic acid iron (III) ammonium dihydrate salt 60 g Ethylenediaminetetraacetic acid 3 g ~mmonium thiosulfate (70~ aq. sol.) lO0 ml Ammonium sulfite (40~ aq. sol.) 27.5 ml pH adjusted to 7.l by addition of potassium carbonate or glacial acetic acid Water to make l,000 ml Stabilizing bath 5-Chloro-2-methyl-4-isothiazolin-3-onel.0 g Ethylene glycol lO g Water to make 1,000 ml.

3~

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As the data in Table 2 show, the samples co~taining the magenta couplers prepared in accordance with the present lnvention were superior to those containing the compaxatlve couplers ln respect to sensi.tivity, color denslty and the productlon of llght-~ast: dye lmages.

~ s~nple of s~lver halide color photographic material was prepaxed by coating the followlng layers in sequence on a support made of polyethylene coated paper contain-ing anatase type TiO2. The ~mounts of the additives incorporated in each of the layers descrlbed below are based on an area o~ 100 cm2-(1~ Layer contalning 20 mg of gelatin, 5 mg in ~erms of sllver of a blue~sensitive silver chlorobromide emul-sion, and 3 mg o~ dloctyl phthalate coupler solvent having dlssolved therein 8 mg of Y-coupler and 0.1 mg of 2,5-di-t-octylhydroquinone:
: (2) Interlayer containing 12 mg of gelatin, and 2 mg of dibutyl phthalate W absorber solvent having P.5 mg of 2,5-di-t-octylhydroquinone and 4 mg of W absorber dissolved therein:
~3) hayer containing 18 mg of gelatin, 4 mg in terms of silver of a green-sensitive silver chlorobromide emulsion, and 2.5 mg of dioctyl phthalate coupler solvent having dissolved therein 5 mg of M-coupler , \
~z~

2 mg of antioxidant* and 0.2 mg of 2,5-di-t-octylhydroquinone:
(4) Interlayer having the same composition as (2):
(5) Layer containing 16 mg of gelatin, 4 mg in terms of silver of a red-sensitive silver chlorobromide emulsion, and 2.0 mg of tricresyl phosphate couplex solvent having dissolved therein 3.5 mg of C-coupler*
and 0.1 mg of 2,5-di-t-octylhydroquinone:
(6) Gelatin protective layer containing 9 mg of gelatin.
Æach of the layers (1~ to [6) also contained a coating aid, while layers (4) to (6) further contained a gelatin crosslinking agent. The ultraviolet absorber used in each of the layers (2) and ~4) was a mixture of UV-l and UV-2 having the structures shown below. The antioxidant incorporated in layer (3) was di-t-pentylhydroquinone-di-octyl ether.
Samples of multi-layered photographic material were prepared as above and each was processed as in Example 2.
The specific types of the Y-coupler, M-coupler and C-coupler used, and the results of the photographic processing are shown in Table 3 below. Each of the samples was checked for its magenta density after exposure to white light.

3~

The data in Table 3 show the improve~ light fastness o~
the dye images produ~ed by using the magenta couplers prepar~d in aacordance with the present invention. It was also clear that t~e llght ~astness o~ the images could be further improved by uslng W ab~orbers in aom-blna~ion with the mag~nta couplexs.
'~Itr- ~let a~orb~r 1Q ~ I > N ~ q(t) C~lq(t) ~ I > N ~ ~......... s~J,(t3 CsH~l(~) *Y-couplers C~
~ d ~co c~ co ~H ~ t ~ HII
bH ~ I ~ NH CO(CH2)3 O ~ tC

~ N-CH~

~2X~

CHJ
C~ ~ C1:1 CH CO~
~N~1CC~ 3 t C~HII
o.~,, N ~o - b C2 ~SIr~N ~H2~3 . ~ .
.
*C-coupler~ -C l 14H t CS~3J
C~-NHCO CH(~,3t C5H~I
CHJ~ b"~l~
~ .
~5 ' :- ~ c-~

ce,~NHC09HO~tCs~
C~HS ~ ~S
C~

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~L2~;;7 0~1 3 tC~jH~g ~NHCO~
tC~3~ ONH
~ ' C~
ClH~3 .

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c-4 Q~

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qO

Claims (6)

The embodiments of the invention in which an exclusive property or privilege is claimed are defined as follows:

1. A silver halide color photographic material that has at least one silver halide emulsion layer on a support, said silver halide emulsion layer containing at least one magenta coupler having the following formula:

wherein R1 is a tertiary alkyl group; R2 is a primary alkyl group; and X is a halogen atom, with the proviso that R2 may not be substituted by an alkylsulfonyl, arylsulfonyl, alkylsulfinyl or arylsulfinyl group.

2. A silver halide color photographic material according to claim 1, wherein R1 in said formula is a group selected from among t-butyl, 1,1-dimethyl-2-methoxy-ethyl, 1,1-dimethyl-2-chloro-ethyl, 1-methyl-1-methoxy-ethyl, 1-methyl-1-phenyl-ethyl, 1,1-di-n-amyl-hexyl, 7,7-dimethyl norbornan-1-yl, 1,1-dimethyl-butyl, 1-ethyl-1-methyl-propyl and adamantyl groups.

3. A silver halide color photographic material according to claim 1, wherein R2 in said formula is a primary alkyl group having 1 to 30 carbon atoms.

4. A silver halide color photographic material according to claim 1, wherein R2 in said formula is a primary alkyl group having 1. to 20 carbon atoms.

5. A silver halide color photographic material according to claim 1, wherein said magenta coupler is a compound having the following structure:

6. A silver halide color photographic material according to claim 1, wherein, when R1 in said formula represents a t-butyl group and X represents a chlorine atom, R2 represents a primary alkyl group other than the following groups:

(1) (2) (3) (4) (5) (6)