Note : Les descriptions sont présentées dans la langue officielle dans laquelle elles ont été soumises.
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.
., ',~ ~;.
~Z57~
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
:'
. .
3125
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)
CH3
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~
;.7~
(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
14
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
17
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.
~Z
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,
23
~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) ,~
NIIC0 CHS02
-(CH2)~ Cla
(2)
- (CH2 )3 ~NlIC0- CIIS02~ c1-13
C 12~1 25
(3)
-~CH2)3~;~NH~0-CIIS02~ oocH3
C,lH~
24
~ j79~28
(4)
- (CH~ )3 ~NIICO~CI12 S
(5)
-(C1~2)" ~tlllCOCllG~3C51~ttl t)
I
C2115
; (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.
28
~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
~C
0 C)
~a
... ~
~ 3 P o o oo ~
~ J O ~a~ o ~ Q a~l Q
a~
~1 a~ M
E-l M
.. ~
_ _ _ ,_ _ _
-1 ~ ~I N 1` ~ ~ O
,0~
a~ a
M ~1
~ Q.
h t)
~ ~ O O O O O O
O ~
C~ ~ O
~ ,~
O
C) U~
. -
a~
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
N C7H15
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.
31
- ~!.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~
~2~;i7~8
. . . ... ___ . _
U~
.
u~ I` Ln 1` ~D ~r
O~
~
. .
~.~ O ~ CO t` O ~
. ':P .. ~ ~ ~ ~ ~ ~
_ . .. . _
,
C~
. ~ o ~ ~ o ~ u~
.,1.,~) o In ~ o a~ o ~ a~
t`~ Q
~ t~O ~
~1 ~ r~ ~f` ~ ~ O
O
a
:: to
:: ~ P~ ,~
h O
: ~ o
Q~ ~ . . . .
O O O O O O
Z t~l N ~`1 ~1 ~
34
~ 5~
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
W-1
1Q ~ I > N ~ q(t)
C~lq(t)
W-2
~ I > N ~ ~......... s~J,(t3
CsH~l(~)
*Y-couplers
Y-1
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~
.'~ ,.
~L2~;;7
C-3
0~1 3
tC~jH~g ~NHCO~
tC~3~ ONH
~ ' C~
ClH~3
.
. .
c-4
Q~
~C d6~,3 c~ C4
3'~
-
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h
o
m R a) ~ h E~
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. u~ .. ...__ . _ .,
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,~ r~ o t~ ') ~ ~ ~ ~ N
- M ~ ~ 0 CO 01 0 ~) ~D a) CO
. . . .. __.. _ .__ .
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'~ æ~ ~ ~ N ~ .
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U -rl ~ ~I rl ~1 ~1 ~~1
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~ ~ ~1 ~1~ ~1 ~ ~ ~ ~ ~r ,~~
O l ll l l l l l l l l
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_ _ _ . . . ___ . _
1~ ~0 ~ ~0
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a) ~ ~ o-,
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