CA1266394A - Silver halide color photographic material - Google Patents

Abstract

Abstract of the Disclosure A silver halide color photographic material is dis-closed which has at least one silver halide emulsion layer on a support, said silver halide emulsion layer containing at least one magenta coupler having the follow-ing formula:

Description

663~

SILVER HALIDE COLOR PHOTOGR~PHIC
TA~

~ield of the Invention~
The present invention relates to a silver halide color photographic material that contains a magenta coupler ~apable o~ effective color formation and which forms a magenta dye image having improved keeping quality, par-ticularly in terms of light fastness. More specifically, the invention relates to a silver halide color photographic material containing a novel lH,pyrazolo~3,2-c}S-triazole derived magenta coupler.

Back~round of the Invention:
The formation of dye images in most silver halide color photographic materials~:depends on the reduc~ion of exposed 5ilver halide grains with an aroma~ic primary amine color developing agent and the subsequent coupling of the resultant oxidation 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, i5 relatively low~

3~

~ vari e ~y of 1 H-~yrazol oE3,2-c~-S-trlazole derived magenra couplers have been procos~d to overcome these problems of the conventional pyra~.olone type couplers.
Reference should be had to U.S0 Patent No. 3,725,067, as well as British Patent NosO 1,252,418 and 1,334,515.
The compounds disclosed in these patents avoid the problem of secondary absorption but the improvement is inadequate in terms of resistance to fo.rmalin gas and is insignificant in respect of the production of a light-fast magenta dye image. The compound disclosed in Research Disclosure Mo. 12443 has no commercial value because o~ its low color formation. The lH-pyrazolor3r2-c]-S-triazole type magenta coupler disclosed in Unexamined Published Japanese Patent Applioation No. ~2045tl983 feature~ signifiaant improve-ments in ~ormalin 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. 99437/1984 and 125732/1984 but the dye images produced by these couplers are still low in light fastness. The coupler disclosed in U~examined 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 ~

:
~, ' , -:
.. , i3~

No~ 19 in Unexa~ined Published ~apanese Patent Applica-tion No. 1~5732/1984 produce~ a dye image having ~lightly ilm~roved 7 ight fastness but the improvement is far from b~ing satisfactoryO
In short, the lH-pyrazolo[3,2-c]-S-triazole derived magenta couplers that have been considered useful because of the absence of secondary absorption and their high resistance to -~ormalin gas fall far short of satisfying the requirement for providing dye images with improved light fastness.

Summary of the Invention:
.
The primary object, therefore, of the present in-vention is to provide a silver halide color photographic material that contains a magenta coupler capable of ef-fective color formation and which forms a magenta dye image having improved light fastness and resistance to formalin gas.
This object of the invention is achieved by a silver halide color photographic material tha-t 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

Il--N I~R2 :~663~L

wherein Rl is a tertiary alkyl group, R2 is a secondary or tertiary alkyl group9 X is a leaving grollp other than a hydrogen atom that leaves upon reaction with the oxidation product of a color developing agent.
As a result o~ various studies made to achieve the stated object/ the inventors ha~e found a l~-pyra2010-[3,2-c3-S-triazole derived magenta coupler that exhibits effective color formation and which provides a magenta dye image having improved formalin resistance and light ~astness.

Detailed Description o~ 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 l~-pyrazolo[3,2~c]-S-triazole nucleus, by an aryl ~e.g. phenyl) or an alkoxy. A cyclic ring including the tertiary carbon is also included wi~hin the meaning o~ the "tertiary alkyl group". In short, Rl represents all alkyl groups wherein the tertiary carbon is bonded to anything but hydrogen. ~he alkyl bonded to the tertiary carbon may have a substituen-t such as halogen or alkoxy.
Typical examples o the tertiary alkyl as Rl include t-butyl, l,l-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, 3~

171-dimethyl-butyl, l-ethyl-l-methyl-propyl and adamantyl.
The secondary alkyl group as R2 is an alkyl having one hydrogen atom bonded to the carbon atom directly coupled to the lH-pyrazolo[3,2-c]-S-triazole nucleus.
The tertiary alkyl group as R2 is an alkyl having no hydrogen bonded to such carbon atom.
The seconaary or tertiary alkyl group represented by R2 may be substituted by aryl, hetero ring, halogen, cyano, a group that is bonded by carbonyl (e.g. alkoxy-carbonyl, acyl or carbamoyl), or a group that is bondedby a hetero atom (e.g. nitro, alkoxy, alkylthio, arylthio, alkylsulfonyl, arylsulfonyl, alkylsul~inyl, arylsulfinyl or dialkylamino). Particularly pre~erred substituents are alkylthio, arylthio, alkylsulfonyl, arylsulfonyl, alkylsulfinyl and arylsulfinyl.
If the heterocyclic group is a lH-pyrazolo[3,2-c~-S-triazole-3-yl compound, a bis type lH-pyrazol[3,2-c]-S-triazole compound is formed and this is of course a magenta coupler included within the scope of the present invention.
~ The leaving group represented by X is either a halogen or an organic group that is bonded to the coupling site by an oxygen, nitrogen or sulfur atom.
Illustragive leaving groups that are bonded to the coupling site by an oxygen atom include alkoxy, aryloxy, ,: ' ~ , ;.

~2~3~

acyloxy and heterocyclic oxy; exemplary leaving groups that ~re bonded to the coupling site by a nitrogen atom include acylamino, diacylamino, sulfonamido, 5- or 6-membered heterocyclic groups containing that nitrogen atom; and illustrative leaving groups that are bonded to the coupling site by a sulfur atom include thiocyano, alkylthio~ arylthio, heterocyclic thio, arylsulfonyl and alkylsulfonyl.
The lH-pyrazolo[3,2-c]-S-triazole derived mayenta couplers in accordance with the present invention are illustrated by, but by no means limited, to the following compounds.

~1) (,~.e (g jC4 Hq ~ N~N
~ ~ ~ CH CH2~2 C~ 8 ~13 l~s , i;3~

~o ~o~
(~C,~
N - N CH CltI~ ~0,~ Cl8Ha~

(3 ~5~ C~
~8~17~ ' -N C --C~13 ~41 ~H
(t) C~ Hq~ C~ H ,, N--N CH<
C~ ~3 (5) C~

CH~
~H ,3 (6) C~ dr C~ C~ ~ t ~s H
C~ .N ~ j HI
~q '. '~

3~

17~ ce ~
~t) C~ Hq ~ ~a 0~ C'1~ H3.
~L8 ~8) ~0 ~8 ¢4~ q~N
N N C--CH~! SO~ Cls~

~9) 0 ~3 0 2 CH~s (g~ C~ C~3 N N (~! ~H 2 ~3 2 C~l8 ~H~

NH~3 ~t~
(t) C~Hq~
N~ N CH CHr~ 8 ~311 bH3 ~6 "
~ 8 --~ .

I ~ C~ H

,c3~l-e ~ 1 --N C~ 2 ~CIB~g7 ~9 ~3) ~J
}i ~tj C~3H" ~N~
N N Il--CJ~
C6 ~ l3 , C~ ~1 (t) ~ L H~, lhl--:N i--f3--C ~ H 37 ~H3 ~15j C ~ lH
(t)C~H~'~
N N CH~o2~30 Cl2H2 s ~6J

H
3LCh< Iq C6~13 _ g ; . ~

3~

(t~ C4Hq ~N~
N--N I --C~2H2s OC4~q (t)C~Hq ~ `N C~H
N--N--L <~HI3 ~ .

G~ H
(~) C~ Hq .~J~N ~
<C6 1~ ,3 ~ .
~3 .
(t)C, Hq ~_ C~I, N--N L;,--CH~ SO2C 18~3 ': C~

., :: ., . .,.. ; ` ~:
. ~ . . .....

(t)C,~ }lq f~.2~
I~N~ CE1~
~HS \~<C 5H

(2~ ~)aH3 H
C ,I Ho ~ a H 3 N -- N a-- OH2~o2Ct~,H33 (23~
~,CJ3H~7 C~H,l o~Y

N N 1 o-- O ~ G"H~7(t) a 4 H9 . ' ~
''~ ' ~2~3~

(24) ~O~ HI7 (t) 0 4 H,~
S
(tlC~ HD ~N"N
N-- N----a~ (t~

~5 ce H

(t) ~ H9 ~
CHOCH2CH20C~H5 (~1 2 25 ':., ' ' ,'' ~ ' ' ''" :
. ~',,,, ......... ~' - ~
', - ~

The methods for synthesizing several of the compounds listed are described belowO The general reference was to Research Disclosure No. 12443~ UOS. Patent No. 3,725,067 and Unexamined Published Japanese Patent Appli.cation No. 99437/
1984.
Synthesis of_col~ound (1):
The reaction scheme is shown below:

N~2N~ NH NH2~C~ 3~2~ ~2CH ~ ~OH
~ C~

N - M
H ~1N ~ CH CH2SO~C
NH~ C~1J tl) CH
J ,~ ~ ~`N
(l) tCH3 Cl~coc~Br ~ N ~ ~ L IC CH2S~2C18 (t)C~H4 ~ ~ C~ CH2~cl8 H3q (111) (t)C4 ~ ~ N ~

N - N C~ C~SO~C~ 3q (l~) C~13 '` Synth2sis of compound ~
~ mixture or 1-methyl-2-octadecylsulfonyl-propior.ic a^-d (70 g~ and thiocar'Dohvdra~ide (lO g) W2S refluxed ~or 3 hours in methyl Cellosolve . After cooling the mixture, the resulting crystal was recovered by filtration and recrystallized from a mixed solvent of alcohol/
water to obtain the end compoundO
l2) Synthesis of compound (II):
A mixture of 8.8 g of compound (I) and 3.6 g of t-butyl-bromomethyl ketone was boiled in alcohol ~200 ml) for 6 hours under agitation. The reaction mLxture was cooled and the resulting crystal was recovered by filtra-tion. The recovered crystal was dissolved in methanol and adjusted to a pH of 8 by addition of 10 ~ sodium carbonate. The resulting crystal was recovered by filtra~
tion and thoroughly washed with water. The washed crystal was recrystallized from alcohol containing a small amount of water, thereby obtaining the end compound.
(3) Synthesis of compound (III):
Six grams of compound (II) was dispersed in 500 ml of n-dodecane and the dispersion was boiled under agita-tion for 3 hours with a nitrogen gas blown into the dis-persion. After leaving the dispersion to cool down, the solid crystal was recovered by filtration and recrys-tallized from acetonitrile.
* Trademark , .

' i3~

~4~ Synthesis of compound ~IV3~
r~hree grams of compoun.d ~III) was dissolved in chloroform and; ~o the solution, an equ~valent amount of N-chlorosuccinimide was added. The mixture was held at 20C for 30 minutes to perform reaction. The reac-tion mixture was then washed with dilute alkali to remove the resulting succinimide. The chloroform was distilled off and the residue was purified by column chromatography on silica gel using benzene-acetone as a solvent. The purified reqidue was identified as the end compound (IV) or compound (1) by NMR spectrum, As for other compounds, the lH-pyrazolo[3,2-c]-S-triazole nucleus free of the leaving group X was synthesized by the method used in the production of compound ~1).

Synthe_is_of compound (2):
Compound (III) prepared as an intermediate for the production of compound (1) was brominated by, for example, the method described in Example 49 of U.S. Patent No.
3,725,067, and the resulting bromine-substituted product was reacted with a silver salt of methanesulfonic acid.
Compounds (4) r (10), (17), (18) and (19) were synthesized by referring to the general method described in Unexamined Published Japanese Patent Application No. 39437/1984.
The silver halide color photographic material of the present invention may contain conventional dye forming ,, .

.~, -:, ................ ..

3~L

~ple~s D
Xnown open-chain ketomethylene couplers may be used as yellow-forming couplers~ Ben~oylacetani.liae and pivaloylacetani7~de compounds are par~iculclrly useful.
Specific examples of the usable yellow forming couplers are described in U~S. Patent Nos. 2,875,057, 3,265,506, 3;408,194, 3~551~155, 3/582~3227 3772S,072, and 3,891,445;
German Patent No. 1,547,868, German Patent Application (OLS) Nos. 2,219l917, 2,261,361 and 2,414,006; British.
Patent No. 1,425,020; Japanese Patent Publication No.
10783/1976, Unexamined Published Japanese Patent Applica-tion Nos. 26133/1972, 73147/1983, 102036/1976, 5341/1975, 123342/1975, 130442/1975, 21827/1976, 87650/1975, 82424/1977 and 115219/1977O
Usable cyan forming couplers are phenolic and naphtholic compounds. Specific examples are found in U.S. Patent Nos. 2,369,92g, 2,434,272, 2,474,293, 2,521,908, 2,895l826 3,034,892, 3,311,476, 3,458,315, 3l476,563, 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, 26034/1976, 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 - 16 ~

., ~ . .
. .

. . . ~ . . .
'~ '`' . - `
.
..

may be used ~hey may also be used in combination with ~nown rn.agen~a coup]ers such as pvra3010ne compounds, indazo1o~c compound , cyanoacetyl compounds~ pyrazo1ino-ben~ mida~o1e compounds and pyrazolotriazole compounds.
It should however be emphasized that at least one of the magenta couplers incorporated in the silver halide color photographic material of -the present invention must be the coupler defined in accordance with the invention.
The coupler of the present invention 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 U.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 diocty1butyl phosphate), citrate esters (e.g. tributyl acetylcitrate), benzoate esters ~.gO octyl benzoat~)0 alky~amides ~eOg. diethyl lauryl-amide), aliphatic acid esters ie.gO dibutoxyethyl succinate and dioctyl azelate) and trimesic acid esters (e.g. tri-butyl trimesate3O The low-boiling organic solvents are those which boil at between about 30C and 150C r and examples are lower alkyl acetates te.g. ethyl acetate and butyl acetate), ethyl propionate, secondary butyl alcohol, methyl isobutyl ketone, ~-e~hoxyethyl acetate and methyl cellosolve acetate. The high~boiling organic solvents may be used in combination with the low-boiling organic solvents.
Dispersion rnethods using polymers may also be used and such methods are described in Japanese Patent Publica-tion No. 39853/1976 and Unaxamined Published Japanese Patent Application No. 59943/1976.
The magenta coupler of the present invention is incorporated in a silver halide emulsion layer usually in the amount o~ 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 fastness may be obtained by using an anti-fading agent or by overlaying the emulsion layer of interest with a layer containing an ultraviolet absorber.
Illustrative anti-~ading agenks include hydroquinone 1 ~ -' ' ., ~

. .
: ' .. . ..
: :
" .,.
,: .' ~;~i3~

aer~vatives of ~e type described i n UOSO Patent Nos.
~3S0,290~ 2y418~613~ 2~673~314, 2,701~97, 2,704,713,

2,728,659~ 2~732~300, 2~735~765y 2,710,801 and 2r816,028, as well as British Patent No. 1,363~921; gallic acid derivati~es as describded in UOS. Patent Nos. 3~457r079 and 3,069,262; p-alkoxyphenols of the type described in U S. Patent ~os. 2,735,765 and 3,698,909, as well as Japanese Patent Publication No. 20977/1974 and 6623/
1977; p-oxyphenol derivatives of the type described in U.S. Patent Nos. 3,432,300, 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.
lS 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. Patant Nos. 3,314,794 and 3,352,681), benzophenone compounds (as described in Unexamined Published Japanese Patent Application No. 2784/1971), cinnar,lic acid ester compounds (as described in U.S. Patent Nos.
3,705,805 and 3,707,375), butadiene compounds (as described in U.S. Paten~ 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~ 3~4999762 and Unexamined Published Japanese Patent ~ppli~ation No~ 48535/1979 Any of 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 iodobromidel 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 dyes. Vsable dyes include cyanine, merocyanine, complex cyanine, complex merocyanine, holopolar cyanine, hemicyanine, styryl and hemioxonole dyes.
Useful sensitizing dyes are described in, for example, German Patent No. 929,080, U.SO Patent Nos. 2,231,658, 2,493,748, 2,503,776, 2,519,001, 2,912,329, 3,656,959, 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 24844/1977.
These sensitizing dyes may be used either individually or in combination. Combined sensitizing dyes are often used for the purpose of supersensitization, as typioally described in U.S. Patent Nos. 2,688,545, 2,977,229, 3,397,06~, 3,522,052, 3,527,641, 3,617,293, 3,628,964, 3,666,480, 3,672,898, 3,679,428, 3,703,377, 3,769,301, ,.

. ' , . ' 3~

3~814,609~ 3,837,862 and 4,026,707; British Patent Nos~
~344,~8l and 19 507,803; 3apa~ese Pa~ent Publication ~osv 4936/~968 and 12375~1978; and Unexamined Published Japanese Patent Application ~osO 110618/1977 and 109925/1977.
The silver halide emulsion used in the present in-vention ~lay incorpora~e a variety of known photogxaphic additives such as ~hose described in Research ~isGlosure No. 17643.
The 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 paperl baryta paper and synthetic paper.
The silver halide color photographic material o~
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 extensive:Ly used in various color photographic processes. Such developing agents include aminophenolic and p-phenylenediamine derivatives. These compounds are generally used in salt forms~ such as hydrochlorides or sulfates~ which are s ablex than the free state.
These compounds are used in concentrations that generally range from about 0~1 to about 30 g, preferably from about 1 g to about 1.5 g, per liter of the color developer.
Illustrative aminophenolic developing agents include o-aminophenol, p-aminophenol, 5-amino-2-oxytoluene, ~-amino-3-oxytoluene, and 2-oxy-3-amino-1,4-dimethyl~enzene.
Particularly useful primary aromatic amino color developing agents are N,N'-dialkyl-p-phenylenediamine compounds wherein the alkyl or phenyl group may have a suitable substituent. ~mong 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-S-(N-ethyl-N-dodecylamino) toluene, N-ethyl-N-~-methanesulfonamidoethyl-3-methyI-4-aminoaniline sulfate, N-ethyl-N-~-hydxoxyethylaminoaniline, 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 presen-t invention may contain a veriety o~ additives that are commonly incorporated in color developers and such additives in-~'' '- :

... . .

3~

clude alkali agents (e.gO sodium hydroxide, sodium carbonate and potassium carbonate) D al~ali metal sulfites7 alkali metal bisulfites, alkali metal thiocyanates, alkali metal halides, benzyl alcohol, water softeners and thickeners. The pH of the color developer is usually at least 7 and most generally ranges from about 10 to about 13.
After color development, the photographic material of the present invention 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. rrhis metal complex salt has the ability not only to oxidize metallic silver (i.e., formed as a result of development) 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 coppex. The organic acids most preferred for use in forming metal complex salts are polycarboxylic acids or aminopolycarboxylic acids. The polycaxboxylic acids or aminopolycarboxylic acids may be in the form of alkali metal salts, ammonium salts or . . ~

' :

3~

water-soluble salts.
Tvp~cal examples of polycarboxylic acids or amino-polvcarbo~ylic acids are listed below~
~l) ethylenediaminetetraacetic acid;
(2) diethylenetriaminepentaace-tic acid;
(3) ethylenediamine-N-(~-oxyethyl)-N/N',N'-triacetic acid;
~43 propylenediaminetetraacetic acid;
~5) nitrilotriacetic acid;
(6) cyclohexanediaminetetraacetic acid;
(7) iminodiacetic acid;
(8) dihydroxyethylglycincitric acid (or tartaric acid);
(9) ethyletherdiaminetetraaceti.c acid;
(10) glycoletherdiaminetetraacetic acid;
(11) ethylenediaminetetrapropionic acid;
(12) phenylenediaminetetraacetic acid;
(13) ethylenediaminetetraacetic acid disodium salt;
(14j ethylenediaminetetraacetic acid tetra(trimethyl-ammonium) salt;
(15) ethylenediaminetetraacetic acid tetrasodium salt;
(16) diethylenetriaminepentaacetic acid pentasodium salt;
~17) ethylenediamine-N-(~-oxyethyl)-N,N',N'-triacetic acid sodium salt;
(18) propylenediaminetetraacetic acid sodium salt;
119) nitrilotriacetic acid sodium salt; and 2~ (20) cyclohexanediaminetetraacetic acid sodium salt.

., 3~

Tn addition ~o m~tal complex salts of ihese organic acids which are used as bleaching agents, the bleaching bath used in processing the color photographic material of the present invention may contain a variety of ad-ditives, and preferred additives are rehalogenating agentssuch as alkali or ammonium halides (e.g. potassium bromide, sodium bromide, sodium chloride and ammonium bromide), metal salts and chelating agents. Any other additives thak are conventionally incorporated in bleaching baths may also be used and they include pH buffers (e.g. borate, oxalate, acetate, carbonate and phosphate salts), alkyl-~amines and polyethylene oxides.
The fixing bath and bleach-9ixing bath 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, potassium 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).
If the photographic material of the present invention is processed in a bleach-fixing bath as it is supplied with a blix replenisher, thiosulfates, thiocyanates, i3~

sulfite.s or other salts may be incorporated either in the bleach-fixing bath or in the replenisher that is fed 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 such as hydrogen peroxide, bromate or persulfate may be added into the tank.
The following examples are provided for further illustration of the claimed photographic material but are not to be construed as limiting the invention.
Example l One tenth of a mole, per mole of silver, of ~ne of the magenta couplers listed in Table l (which follow) 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 form 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 so~ution o Alkanol B (trade name of du Pont for alkylnaphthalene sulfonate~. The mixture was emulsified with an ultrasonic disperser and the dispersion obtained was added to 4 kg of a green-sensitive silver iodobromide emulsion (containing ~6~3~

S mol% AgT~ To the mixture7 120 ml of a 2 % solution ~W2ter methanol = 1:1 ) Of 1~ 2-bis(vinylsulfonyl~-ethane was added as a hardener ~ and the so prepared coating solution was applied to a su~ed iransparent polyester base, and the web was dried to provide a sample of color photographic material (with silver deposit of 20 mg/100 cm2). The other samples were prepared by the same procedure.
Each of the samples thus prepared was subjected ~o exposure through an optical wedge as in the conventional process and subsequently processed by the following scheme The results o~ such photographic processing are shown in Table 1 below.

Processing scheme StepsTemperature, C Time Color development 38 3 min, 15 sec Bleaching 38 4 min, 20 sec Washlng 38 3 min, 15 sec Fixing 38 4 min, 20 ~ec Washing 38 3 min, 15 sec Stabilizing 38 1 min, 30 sec Drying 47 to 55 16 min, 30 sec The foumulation of each of the processing solutions used is indicated below.

Color developer I

" ,. .,; ~
.

3~

Pot2ssium carbonate 30 g sodi~m hYdrogencarbonate 2.5 g potassium sulf~te 5 g sodium bromide 1.3 g potassium iodide 2 mg hydroxylamine sulfate 2.5 g sodium chloride 0,6 g diethylenetriaminepentaacetic 2 5 g acid sodium salt

4-amino-3-methyl-N-ethyl-N-(~- 4 8 hydroxyethyl)aniline sulfate g potassium hydroxlde 1.2 g water to make 1,000 ml pH adjusted to 10.06 by addition o potassium hydroxlde or 20 ~ H2SO4.
leaching bath Ethylenediaminetetraacetlc acld ixon . 100 g ammonium salt Ethylenediaminetetraacetlc acid 10 g Ammonium bromide 150 g Glacial acetic acid 40 ml Sodium bromate 10 g water to make 1,030 ml pH adjusted to 3.5 by addition of ammonia water or glacial acetic acid.

Ammonium thiosulfate 180 g 3~

~hyd~^us sod~um sulfite 12 g Sodi~m metabis~lrite 2.5 g ~thyleredi~minetetrââcetic acid disodium salt 0~5 g Sodium carbonate 10 g water to make 1,000 ml Sta~ilizin~ bath Formalin (37 %aq. sol.) 2 ml Konidax*(product of Konishiroku 5 m~
Photo Industry Co., Ltd.) water to make 1,000 ml.

Table Sample ¦ Coupler used Specific 1) ~Yimum Fbrmalin 2) Li~ht No. ¦ sensitivity density resistance fastness . .
1-11 Comparakive 100 1.30 50 26 ~ coupler 1 1-12 Ccmparative 95 1.29 49 67 ooupler 2 1-13 Comparative 222 2.64 91 35 coupler 3 1-14 Ccmparative 188 2.32 92 56 coupler 4 1-15 Ccmparative 217 2.63 92 32 coupler 5 1-16 Coupler (4) 206 2.52 90 67 of-the in-vention 1-17 Coupler (5) 226 2.82 89 69 of the in-vention * Trademark ' , ~

~i63~

1--18 Couplex (163 215 ¦ 2.64 92 64 of the in-vention 1-19 Coupler (7) 228 2O85 93 76 of the in-vention 1-20 Coupler (8) 213 2.50 91 76 of the in-vention 1-21 I Coupler (19) 203 2.54 91 74 of the in-vention 1-22 Coupler (20) 222 2~70 94 67 of the in-vention _ . . ~ ~ . _ _ Notes: 1) The specific sensitivity is expressed as the reciprocal of the exposure that provides a fog plus 0.1 density, with the value for sarnple 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 30~C and 62 % r.h. An untreated sample was also color developed. The formalin resistance of the first sample was calculated by the follow-ing formul~a:

' ':
:' ~

3~2663~L

rmalin Cc~lo~ dc~it~ ~ tbu treated sample x 100 (%~
resistar.ce Color density of the untreated 5amp~

3) A color-developed ample was illuminated ln a xenon fadeometer or 8 days and the percentage residual dye for the initial density ~D) of 1.0 was calculated to determine the lightfaqtness of the image-Density after 8-day illumination Light fa~tness - in_xenon fadeometer _ - x 100 (%) 1 ,0 Comparative coupler 1 C~
. N--N C ,~H3, co~ 2 , tC~4 ~ ~
N N ~ CH ~ ~6~ 3 , :

:~2~639~

C~ H
r~8 N - N ~ - C H2~2 Cls H
CH~

~e~b~ ' See Exampl~ 19 of Unexamined Published Japanese Patent Application No. 99437 j1984 N ~ C~

~N ~ ( CH, ) ~ 0 ~. ~

CH J~
~ ~ N ~'CHcH2sO2c18H37 The data in Table 1 show tha~ ~he couplers prepared Z5 in accordance with the present invention satisfied all , .. ~

: ;:

3~L

th~ reauirements for high color density and the produc-~or. of formal ' n-resistant and ~ig~t~fast dye lmag2s.

Example Sample Nos. 1-11 to 1-25 prepared in E`xample 1 were exposed through an optical wedge and subse~uently processed by the following scheme. The results are shown in Table 2~ The specific sensitivity and light fastness were meas-ured by the same methods as used in Example 1.
Processin~ scheme:

Colox development 38C 3 min, 30 sec bleach-fixing33C 1 mln, 30 sec stabilizing or25 - 30C 3 min washing drying75 - 80C ca. 2 min.

The solutions used in this scheme had the following formulations.

co~E~g~
Benzyl alcohol15 ml Ethylene glycol 15 ml Potassium sulfite 2.0 g Potassium bromide 0.7 g Sodium chloride 0.2 g Potassium carbonate 30O0 g Hydroxylamine sulfate 3.0 g ~2~39~

Tripolyphosphoric acid (TPPS~2 . 5 g 3rMethtl-4-amino-N-ethyl-N-(~-methane5.5 g sulfonamidoethyl)aniline sulfate Brightener t4,4l~diaminostilhenzosulfonic 1.0 g acid derivative) Potassium hydroxide 2.0 g Water to make 1,000 ml pH adjusted to 10,20 Bleach-fixing bath Ethylenediaminetetraacetic acid iron 60 g (III) ammonium dihydrate salt E~hylenediaminetetraacetic acid~3 g Ammonium thiosulfate (70% aq. sol.) 100 ml Ammonlum sulfite ~40% aq. 901. )27.5 ml pH adjusted to 7.1 by additlon of potas-sium carbonate or glacia1 acetic acid Water to make 1,000 ml.

5-Chloro-2-methyl-4-isothiaæolin-3-one1O0 g Ethylene glycol 10 g .
1-Hydroxyethylidene-1,1'-diphosphonic acid 2.5 g Bi~muth chloride 0. 2 g Magneslum chloride 0.1 g Ammonium hydroxide ~28% a~. sol.)2.0 g Sodium nitrilotriacetate 1.0 g Water to make 1,000 ml '.

;3~

pH adjusted to 7O0 by addition of anunonium hydroxide or sulfuric acid.
Table 2 ... ~ .... _ _ . ............. . __ Sa~pIe Cbupler used Specific Maximum Iight ~ sensitivity density fastness : _ . _ .
2-11 Cbmparative 100 1c30 22.
.coup_e~ 1 .
2-12 Cb~paxative 114 1.36 66 coupler 2 .
10 2-13 Ccmparative 212 2.40 35 . ooupler 3 2-14 Ccmparative 170 2.30 54 ooupler 4 2-15 Ccmparative 204 2.43 35 ooupler 5 2-16 Coupler (4) of 202 2.27 65 the invention :
2-17 ooupler (5) of 234 2.44 65 :
: ..the invention 2-18ooupler (16) of 223 2.44 67 the invention .
2-19Cbupler (7) of 212 2.38 75 the invention . 2-20Coupler (8) of 210 2.40 76 the invention 2-21Cbupler (19) of 204 2.24 75 the inwention 2-22Ooupler (20) of 208 2.39 66 ~: ____=
.

,, :: :

~. .

' ~
. ' 3~4 As the data in Table 2 show~ the samples containing the magenta couplers prepared in accordance with the present invention were superior to those containing the comparative couplers in respect to sensltivity, color density and the production of light-Fast dye images.

A sample of silver halide color photographic material was prepared by coating the following layers in sequence on a support made of polyethylene coated paper contain-ing anatase type TiO2. The amounts of the additives lncorporated in each of the layers described below are based on an area of 100 cm~-l1) Layer containing 20 mg of gelatin, 5 mg in terms of silver of a blue-sensitive silver chlorobromide emul-sion, and 3 mg of dioctyl phthalate coupler solvent having dissolved therein.8 mg of Y coupler and 0.1 mg of 2,5-di-t-octylhydro~uinone:
(2) Interlayer containing 12 mg of gelatin, and 2 my of dibutyl phthalate W absorber solvent having ~.5 mg of 2,5 di-t=octylhydroquinone and 4 mg of W absorber dissolved therein:
(33 Layex 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 dissol~ed therein 5 mg of M-CQUP1er, ';

~ mg of antioxidant and 0.2 mg of 2,5 di-t-octylhydroquinone O

~4~ ~nterlay having the same composition as ~2):

(5) Layer containing 16 mg of gelatin, 4 mg in terms of silver of a red-sensitive silver chloxobromide emul-sion, and 2.0 mg of tricresyl phosphate coupler 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.

Each of the layers (1) to (6) also contained a coating aid, whlle layers (4) to (6) further contained a yelatin crosslin]cing agent. The ultraviolet absorber used in each of the layers (2) and (4) was a mixture of W-1 and W-2 having the structures shown below. The antioxidant incorporated in layer (3) was di-t-pentyl-hydroquinone-di-octyl ether.
Eleven samples of multi-layered photographlc 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 checkef for its magenta density after exposure to white light. The specific sensitivity and light fastness were measured by the same methods as used in Example 1.

,: :

6~3~

The data in Table 3 show the improved light fastness of the dye images produced by using the magenta couplers prepared in accordance with the present inventionO It was also clear that the light fastness of the images could be further impro~ed by usi~g W absorbers ln com-blnation with the magenta couplers.

*Vltraviolet absorber W-l -~ I>N~C,~(t) C4 Hq~t) 0~ 1 >~ ~C, ~ H~ l(t) - ~5H1I(t) *Y-couplers CH~--C~O ClH CO NH ~ t N~ o N~ CO ~H2330 ~ tC

0~N~H~3 ,' , .

3~

Y~
.

C~Is~--CO C~C~ON~ t~ 3 = <N~lCOCHO~ t C~H~
~ N
C2 H~N ~H

*c couplers (;~H t CsH~
C~-N~ CO CH(}~t Cs H~
CHD ~ ~ 15 C~ . . .

. . .

(;)H t~
Ce~,NH Ct) IHo~tcsH
C,~Hs~ (~2 Hs C~

' ' ' , :.
-.

: ' - , .

.

:~6 c--3 t CsHu ~HC~F
t CsHIg~OC~I CONH~
C~

c-4 ~ Ç)H
l~rN~ CO~
tCt~l"~CHCONH~ ce - ~0 -.

. ~ .
, ~ ~ - - - ~ ~

- -~
~-~ ~ o o c~ 7 N .-- O S:~ u7 ~, ~`, N ~ N ~J N 1~i ~`I 1~i ~Y ~`i ('`i ~ _ ._ _ _ ,0 ~ Oo .-,In __ _ __ ~' ~ .
E~ ~ ~
î~, ~ :
~ ~ .
~ -- '' ~ `I N ~') ~ ~ ~ _ Y- I I I I I I I I . I I I I I
~ O U ~ U ~1 U U U U U U U
: , , ~1 ~P l l l l l l l l l l l l l ~ . _ __ _ _ _ _ _ . ~-.

, - - ' . : --' :

Claims (7)

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 secondary or tertiary alkyl group; X is a leaving group other than a hydrogen atom that leaves upon reaction with the oxidation product of a color developing agent, with the proviso that when R2 is a secondary alkyl group, it is not substituted by an alkylsulfonyl, arylsulfonyl, alkylsulfinyl or arylsulfinyl group.

2. A silver halide color photographic material according to claim 1 wherein X is a halogen atom.

3. A silver halide color photographic material according to claim 1 wherein the tertiary alkyl group represented by R1 has 3 to 6 carbon atoms.

4. A silver halide color photographic material according to claim 1, wherein the tertiary alkyl group represented by R1 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-dimethylnorbornan-1-yl, 1,1-dimethyl-butyl, 1-ethyl-1-methyl-propyl and adamantyl groups.

5. A silver halide color photographic material according to claim 1, wherein the secondary or tertiary alkyl group represented by R2 has 2 to 30 carbon atoms.

6. A silver halide color photographic material according to claim 1, wherein the secondary or tertiary alkyl group represented by R2 is substituted with an alkylthio or arylthio.

7. A silver halide color photographic material according to claim 1, wherein said magenta coupler is one represented by the following formula: