Note: Descriptions are shown in the official language in which they were submitted.
l(~S3~58
* * * -^ ,...... .
This invention relates to a silver halide photosensi-
tive material for color photography which has improved sen-
sitivity, resolving power and color reproducibility. ~-
Silver halide photosensitive materials for colo; photo-
graplly comprise three silver halide emulsion layers formed
on a support. These layers are sensitized to blue, green
an~ red rays, respectively. For e~ample, in a color nega-
tive film, blue-sensitive, green-sensitive and red-sensitive
emulsion layers are generally formèd in this order from the
/0 exposure side, and a bleachable yellow filter layer is
formed between the blue-sensitive and green sensitive emul-
sion layers to absorb blue rays passing through the blue-
sensitive emulsion layer. Further, intermediate layers
having special properties are provided between every two
emulsion layers and a protective layer is formed over the
outermost layer.
In the case of a color printing paper, red-sensitive,
green-sensitive and blue sensitive emulsion layers are gen-
erally formed in this order from the exposure side, a.,d as
~0 in ~lle case of the color n~gative ~ilm, intermediate la~ers
such as
`
- ~S3~ 5~ -
an ultraviolet absorbing layer, as well as a protective layer
are formed for specific purposes similar to the color negative
film. It is known that the emulsion layers can be disposed
in an order differen~ from that mentioned above. Although
one layer is generally formed as each of the three emulsion
layers differing in the sensitive region, it is known to
su~stitute two emulsion layers,which together are sensitive
to the same wavelength range as one of the three layer~ for
that layer.
lo A yellow coupler for forming a yellow dye image, a magenta
coupler for forming a magenta dye imag~ and a cyan coupler for
forming a cyan dye image are incorporated in the a~ove blue-
sensitive, green-sensitive and red sensitive emulsion layers,
respectively. These color-fonming couplers are divided into
two groups; that is, 4 equivalent couplers and 2 equivalent
couplers. In order to form one molecule of a dye from the
4 equivalent couplers, four molecules of the silver halide must
be developed; on the other handg only two molecules of the
silver halide must be developed for forming one molecule
20 of a dye from the 2 equivalent couplers. These two kinds of
couplers are appropriately chosen an, used depending on the
intendS~d purpose.
In general, couplers are selected in view of the folLow-
ing conditions and requirements:
.
, . ' ' , , ~ s . . . : ,
~5 3~ ~8
In development by a color developing solution comprising,
as the main ingredient, a color developing agent such as a
p-phenylene diamine derivative, couplers are required to react
with an oxidation product of the color developing agent to
form a dye as quickly as possible. In other words, the couplers
should have a color couplin~ rate as high as possible. Further,
dyes formed by this coupling reaction are required to have
good hue and good stability to light, heat, moisture and the
like. Moreover, the couplers should cause deterioration of
~0 the photographic properties of the silver halide photosensitive
material by its interaction with photographic additives present
in the silver halide photosensitive material, such as a
sensitizing dye and the like. It is also required that the
couplers have good storage stability and be easily synthesized
at a low cost.
However, it is very difficult to selec~ couplers meeting
81~ of the above requirements. Although photosensitive emulsion
layers having a yellow coupler, a magenta coupler or a cyan
co~pler (which layers are relatively satisactory when used
; 20 singly are known) it is very difficult to find photosensitive
emulsion layers meeting the above requirements when combined
wlth other phtosensitive layers to form silver halide photo-
.
sansitive materials for color photography.
Among the above requirements~ the color coupling rate is
desired to be as high as possible. ~owever, if the color
.
' ~
....... ,~7
. .
~ 53~58
coupling rate is too high,.the upper layer is developed
before the lower layer because of the difference in
permeation of the liquid developer into the photosensitive
materialj and hence, the developing effect becomes uneven.
Accordingly, it is desired that each of couplers of
respective photosensitive emulsion layers has a color
coupling rate which is high but also is such that development
. o all layers is completed at the same time. However, since
the couplers of the respective emulsion layers exhibit diffe-
10 rent coupling rates, it is quite difficult to find a combina-
tion of yellow coupler, a magenta coupler and a cyan coupler,
all of which exhibit substantially the same coupling rates in
respective ph~tosensitive emulsion layers and can mee~ the
othex requirements mentioned above.
In a silver halide photosensitive material for color
photography in which coloring coupling rates of couplers in
respective photosensitive emulsion layers are different~ an`
. oxidation product of the color developing agent is diffused
into other photosensitive emulsion layers so that the quantity
20 of the resulting dye is insu~ficient in the photosensitive
emNlsion layer from which the oxidation product diffuses,
which an undesira~le excessive amount of dye is formed in
the other photosensitive.emulsion layer. As a result, color
turbidity is caused and color balance is lost in the resulting
image. Accordingly, in such canventional silver halide
: . . : .. . :
1, ..
1~53~5E~
photosensitive materials for color photography, respective
photosensitive emulsion layers cannot be disposed directly
adjacent one another, and intermediate layers are needed
so as to prevent the undesirable diffusion of an oxidation
product of the color developing agent from layer to layer
and thus maintain good color balance in the resulting colored
image.
In order to attain this object satisfactorily, it is
necessary to provide an intermediate layer having a considerable
thlckness, for example, in excess of I ~. Since such thick
intermediate layers are provided, the total thickness of
photosensitive coatings of the silver halide photosensitive
material for color photography is naturally increased and this
results in reduction o~ the sensitivity and resolving power.
Further, permeation of the li~uid developer is inhibited to
somè extent by provision of such thick layer, and therefore,
most of the conventional silver-halide photosensitive materials .
for color photography are not suitable for the quick development
treatment.
2~ It is therefore desired to provide a novel silver halide
photo~ensitive material for color photography which comprises
yellow, magenta and cyan couplers having substantially the
same high color coupling rate in respective photosensitive
emulsion layers and which is substantiaIly improved in sensi-
tivity, resolving power; image color sharpness, color repro-
ducibility, storage stability and other properties.
,
- ~.
,
11~5~0S8 `;
`,~ ~.
As mentioned in detail in u.s. patent 4,026,706 it has been
found that the above object can be attained by incorporating at
least one yellow coupler represented by the formula I into a blue-
sensitive silver halide emulsion layer, at least one magenta coupler :-
represented by the formula II into a green-sensitive silver -.
halide emulsion layer, and at least one cyan coupler represented
by the formula III into a red-sensitive silver halide emulsion
layer.
General Formula I
10RI -COIH _ R2
: . N
',, Yi\C=O ''.
Wherein Rl stands for a substituted or unsubstituted alkyl,
alkenyl, aryl or heterocyclic group, ~ stands for a cyano or
N-phenylcarbamyl group which can have a substituent or substituents,
Y is -CO-, -SO2o, nitrogen, sulfur, oxygen or carbon not double
bonded to oxygen, and Z is a non-metallic atomic group necessary
for formation of a 4- 9 5- or 6-membered nitrogen-containing
heterocyclic ring,
' General Formula II
.
.
Cl ~ < N-- I--NH
Cl ~ -CH~ .
.
` '
~ 6 - .
'~ .
11~53(:~58
Wherein R3 stands for hydrogen~ halogen, nitro, alkyl,
alkoxy or acylamino and R4 stands for hydrogen, halogen or
a mono-valent organic residue such as nitro, alkyl, alkoxy,
acylamino and optionally substituted carbamoyl, sulfamoyl,
alkylsuccinimide~ alkoxycarboamide, alkoxycarboalkylamino,
aralkoxycarboalkylamino, alkylaminocarboalkylamino,
arylaminocarboalkylamino and aralkylaminocarboalkylamino.
General Formula III
OH
R5 ~ NHCOcHo ~ 8
X IO
. . . .
,
1~ Wherein R5, R6 and R7 individually stand for hydrogen,
halogen, alkyl, aryl or alkoxy, R8 and Rg individually stand
for hydrogen, alkyl or alkoxy~ Rlo is hydrogen or alkyl3 and
X designates an atom or group spitta~le upon coupling.
A silver halide photosensitive material including these
couplers in combination is characterized in that each of
. couplers in a different photosensitive emulsion layers has a
high and well balanced color coupling rate. Therefore, in
the silver halide photosensitive material, the color coupling
reaction proceeds simultaneously at substantially the same
rate in alL of the photosensitive emulsion layers~ and hence,
the thickness of the intenmediate layer for~ed to avoid the
diffusion of the oxidation product of the color developing
~gent into an adjacent layer or layers can be greatly reduced.
.
~ ,
' , , '' : .'
53~58
In certain appropriate rombinations of the yellow, magenta
and cyan couplers, the intermediate layer can even be omitted.
Further~ since each coupler has a sufEiciently high color
coupling rate, the coupling reaction proceeds substantially
simultaneously in the respective layers, regardless of their
order of lamination.
Accordingly, in the silver halide photosensitive material,
it is possible to form a blue-sensitive emulsion layer~ a
green-sensitive layer and a red-sensitive layer on a support
1~ in an optional order. It is also possible to construct one
photosensitive emulsion layer by employing two photosensitive
emulsion layers having a photosensitivity in substantially
the same wavelength region. An intermediate layer of a suitable
thickness may optionally be provided for purposes other than
prevention of diffusion of the oxidation product of the color
dev~eloping agent. It is also possible to provide other layers
customarily used in photosensitive materials, such as ultra-
violet absorbing and protective layers. As a result, good
sensitivity, resolving power and color reproducibility can
2~ be attained regardless of the layer structure in the photo-
~ensitive material and the order of the layers. The fact
that such desirable results can be obtained in this invention
i8 owing to the combined use of the above-mentioned three
specific couplers.
~ ,
. - .. , ~
.
~0S 3~ S ~
As an improvement on the color photographic material
disclosed in u.S. Patent 4,026,706, it has
been found that the presence in at least one oE the layer
elements such as a silver halide emulsion layer, an inter-
mediate layer, a filter layer, and a protective layer, at
least one compound represented by formulas IV, V and VI provides
excellent storage stability of dye images and therefore is
free from changing and/or fading even when stored in darkness.
Formulas IV, V and VI are as follows^
A-cHcoocH2 (CF2CF2 )n
CH2coocH2(cF2cF2)n2H
wherein nl and n2 are individually a positive integer
~ not more than 5; A is -SO3Ml (Ml is a cation) or -O(CH2CH2O)ml~B
: in which B is hydrogen, -COCH2CH2COOMl or -COCH=CH-COOM
(Ml is a cation) which ml is 1 to 1005
H(cF2cF2)n3cH2ocH2lHcH2
OS03M2
wherein Rll is alkyl, su~stituted or unsubstituted aryl or
-CH2(CF2CF~)m2H (m2 is a positive integer not more than 5); M2
is hydrogen or a cation; and n3 is a positive integer not more
than 5; and
2n
-
- 9 -
. t
~; ' .
:~'
t
" ~53~58
M303S~CH-COO(CH2CH~O)m3CH2(CF2CF2)n4H VI
CH2COOR12
wherein R12 is a substituted or unsubstituted hydrocarbon
residue having carbon atoms not more than 18; m3 is zero or a
positive integer not more than 3; n4 is a positive integer
not more than 7; and M3 is a cation.
In other word, this invention relates to a silver halide
color photosensitive material comprising a support and a
plurality
,
-' ' ' '' , - ' ~, .
c
' ' .
, , , ~ 1
S3~58
of layer elements, said elements comprising a blue-sensitive
silver halide emulsion layer containing a yellow coupler of
formula I, a green-sensitive silver halide emulsion layer .
containing a magenta coupler of formula II, and a red-
sensltive silver halide emulsion layer containing a cyan
coupler of gerLeral formula III, at least one of said elements
comprising a compound represented by general fonmula IV, V
or VI.
Couplers used in this in~ention, namely a yellow coupler
lo represented by the formula I, a magenta coupler represented
by the fonmula II and a cyan coupler represented by the
fonmula III, are incorporated in the silver halide photo-
sensitive material for color photography so that each coupler
is prevented from diffusing into other layers. Incorporation
of such couplers into a silYer halide emulsion is accomplished
by dissolving the coupler in an organic solvent having a boiling
point higher than 175C., such as tricresyl phosphate and
dibutyl phthalate9 or a low-boiling-point organic solvent such
as ~thyl acetate and butyl propionate; or mixtures thereof.
2n The resulting solution is mixed with an aqueous solution of
gelatin containing a surface active agent and their emulsified
and dispersed by a high speed rotary mixer or a colloid mill.
- .The resulting dlspersion is incorporated into the silver .
halide emulsion directly or after setting of the dispersion9
' .
" ' . , ' .
,. 10
.' '
'
,
: -
': ' ' .' ~ . ' ` ' ' ~';. .
~053~
... ..
and the set dispersion is finely divided and the low-boiling-
point solvent removed by water was~ing or the like. It is
preferred that the coupler be incorporated in the silver
halide emulslon in an amount of lO to 300 g per mole of the
silver halide, but needless to say, the amount of the coupler
can be varied widely depending on the kind of coupler~ the
intended use and other factors.
As typical examples of the yellow coupler represented
by Formula l, the following compounds can be mentioned:
(Y-lj
~H3 GC
. .
0~3-C-OOCHCON~ ~ ¢5~
. . C~ ~N~ N~C0(~2.)30 ~ Cs~ t)
--l I-- ., .
. . - ~2C - ~2
.. ; . _ .
.-
~,
', ''
., '
~ '
~ . . i
53~5~
t ~--2 ) ~ . :
. . - . . !.
c~ aoc~o~
, ~ CE13 N~ . . .
o~ a=o
- ~2 --CH
4H29 ..
.
3 )
. .
a OONa
' 012EI250~COC}laON~
~ ¢ O ON R
: ~ ' O--C C--O ' ''
.. I I
a--c:g ,
~3 . ' - ~r
. - . .
...
- - ~[3 . ¢~ .
a~ 3--¢--C O G H O O N~ Cs ~ (t3
-. aEl~N~ 21HOOt C ~2)~0~5~11(t)
. 0=0 0--O
! -. ,~a--c~ -
~2~ . ~G~2 .
~7a--¢~
- ~
., , . :
! . . ~ .
' I
:- '~ ~ ,' . I
, . ,, . ,''. ' .,
.... . . . . . . .
~; ~ s - : ~
`, ~053~5~3 . .;
: . .
. .
g~--.s ) ' ~ . .
.
a~3 aE~3
0~3--O COCHCO~I~ 2
.t a~3 ~ C~
O--~ C = O ' '
3~C--C~ , '
~a~--0~2--~C~
a--C:E1
a,E~ ~ - ' ' ' '
OP 3--O--C O C :E~ C O N~ ~ C5 }~ t)
o o( a H2 ) 3 O ~C~ t ~t)
0--0 C=~ - ~
' ' ~ ' - ~. `~
'''' ','-'- .' ..... ',' - ~.
~y_7 )
~iL c ocH¢ oNH~ 1¢5~ (t)
,~ , , ~ ~1}~0 0 ~ ~ E 2 )3 0 ~C5
\ ' ~)~ 11~ 0 o O
~ ' ,' , -'.
. . . . . . .. ..
' - ' . : ' . - . . ', ' , ' ~
i ' " ' '. . ' ' ' ', '', ' , .'. . t' ' '
~3
- . . .. --~ ~ . . .
t
dt
_ _ _ _ _ ____ ___ _ ___,_, . , ,.. ..... J,
' '` ' _ , , ' , '
' ' " ' ' ' '
. ~ . . I
: ` ~
~53058,
.
t Y~
05}I11 (t)
5t~ 5 ~ O C }I O O N E~ ~2 o a
- ~` C2~5 OO~ICONH~
o--C a--o
2a- C}12
Y~
a~3 1
O~I 3- C - C 0~:}3 ¢ Ol~
. ~3 ~N~ ¢oo7~Ecooc~2~I25
` O = C ,~C--o C~3
C3 E7 C~; ~17
. ~. . . . .. I`
--.f O ) - '
- 0¢~13
- C~3- l -aoc~oo~ o5~11 (t)
¢ O CIIO ~ G5 E~ t (t~
~i ~ , zO~ ~o a2~s .
' - ' ,' ~3 '', '' -' ,`''
'- : . : - . . i
Lf ' '~
,' - ' ' , ' ' ~ . '
, . ... , . ,. : .
- ' . , ~ '
. . , . ~ .
~ ', , ' , ~
' ! .
., ~ . !-
.. . . I
~. . ... .... ~ . .. .. . . . .. . .. . . . . ~
-- - . ' ' ; ' !
.
~, . . .
- ~53~5
.
.
~Y // ~ ` . ,
`:
OH~, 0 CH3
,~ ~ a~3--O--COC~ICON~I~ C5H11 (~)
d~N~ ~El C O G~o~ C5H11 ~t)
O= C~O
~6 C2~5
~< , . ` '
C~
t ~/2 3
a~3 ~O~I3
O~I3 -COOHCON}I~ ~C~ L~
.. . , \ 802~ . . . .
o= c~a =o ~a ~.~H37 (n)
~ ' ' .
.
(f~/3~ r
~ 3 N~2~5)2 ~:sE~
f -COC~C0~1~802
a~ ~ 2 ~
o--a - ~o
. ~ ¢0¢gB.
' ' ', -~
.
.', ~ ' ' ' '
' ' - ~,
.
.
' ' ~ ' ' , ,
.
~53~58
,' ` , ~
,
I 3 . a2~5
-~C:E3--C--a OC~ICON~
.~ CE[~ ~N~ oooc14E29(n)
- O--t~ C=O
I I
~IC ~ C~
6~ ~S)
OO~I~
~ '', ~ .
. aE~3 ¢ 0 C HC ON~
802N
o--a f=o G18~37
~El2¢--C~2
- r
.. .. . ~ .. .
'17~35 C O CJ~IC ONll~
11~ OOO¢H~ . `
'' ` 0=~ O
- ~ / , .
ao2~
' . ': ' ' 5 '
- /G ~ , .
- , ~_
,
; ' ' ' '. ' .' ' -
., ' ' '1. ~ ,.
- -
.
., I
.
.. .
_,
~QS3058 ` ' , `
.
t Y--/ 7 3 ~ , :
OC'H3
a~3 a oc~c ONH ~ ` `
.,~
~N~ ~ ~'`02N
a o - o 18~7
~,~ . . . ..
:BF
~2¢ lS~
~C~I¢OC:~CO~ C~2~ (t)
~N~ I~ICOCE20~C5H1 1 (t) ~'
~' 0~0 C=o . , : `
~'' I
;'` ` . ~2~ 1_C2}~5
.
9) ,-~` ` `, ~Ir
¦ ~C ~ ~ O O E C ON H~
- i ~12C
~1~ OC}~O~ C5~1 t ~t)
:: - ` t)=O C--Q I .
I` `' I e2~5 '
a~ ~C~2 , . .
. ~2 " ` ` . - : i
.
' ~ .
. .
'
'
; - !
.`., . . :'-
- . . .; s ~. !
, . . ~
- '-,.
~53058
(~-20) " , j,
~2--(~H2 0 ~
`' ' . f :E120~ C H C O C ~ C O NH ~ C5 ~1 1 (t)
aH2- a~2 ' I
NIIC OCH20~C5~ (t)
o--a c--o
~2 C--C
- . g ~--2/ )
OE~ CE= C~I5 O CHC ON~ .
~h~ L
o--¢ CO
, . -- ~ I . .
~ ~2 ¢ ~ '
1 8 3 7
`. . . -. . . _u
':
- . '.
o~3--1 _ COO~OON~ 8 02N
~. . ." ~ , .
o--a' `~=o
: .. -. . I I . . ..
- ~2~
at BF~37 . .
:, , . , , . . :i ;
. . . - , .
'- `i8
. - ' , . ~ - ;
- ,, .
~ . . . .. . . . .
.
., . ` I .
.. ' I '.
- ' ` . ,~
~~ ~ ' ' ~ ' ' ' ~ ~ ~ ' ~ ~ '' ' ' ~ ' ' ~:n~
' ''. ~ '` ' ' ' ~ ' ' ,;,
. 1 [)5;305B - `
~Y--23 )
. ¢1~I3 C~ .:
C ~ 3--IC--O O O ~I O O N$~ O .C
CEt3 ~N~
~=C~ C=O '
C5~I~1 (t)
N~IC00~I2 0~ C5H1 1 (t)
~-2~
~2--C:EE2
/ 1 3 \ ` O~
--a --c--C O CHC O N ~
\ a~3 / ~1~ NHC3)~2)30~o5}I11 (t)
CH2--O~I2 O=C a=o
~ - r~
25 )
.. .. : . . .
(~)C4 }~ ~0 C O O CH C O~E~ - . 0 5 ~ (t1
o ~3t)2~ O~C5
~a--c~
.. . . . - -. . ~ :
Q
'
,' . ' I
,:
'', .
.' - ,
., ' I .
,- I
!
1C~530
6 )
. .
7~3 /C 4 H 9
OE13--~--OOCHCONH~N~ICOCE~2a~[2N
CH~ "N ~ . a a 15 H3 1
O=C C~O . - .
Ob~ C~C ' ' - ''' '
ao o~
(~ 27)
S' C ,, ~ ;,
c~--a--o o o ~ c O N X~ f:l5 ~It 1 (t) i~
~N~ 8O21~ 2 )3~ C5~11 (t)
2 ~ "G~ 2 r
2 ' ~i
g~-28~ . ``'
I
c~ a
f -aoc~coN~ - ,, , -
a~B ,~ IO O ¢ II 2
O;QO C=O
. t 8 = ~ . ~15~31 ~n)
I
,2
"" - - ' ' ~ . '
.. . . . . . .
.; ' . . ' ' ' '
,
,, . - I .
S~S8
' ' ' ' , ' , , ,
~
a~l3--Cl--00 1 }ICONH~ ,~,CE[3
O=C C--O C18H~7
. ~o30)
C}~3 C~ ~
C O C X C O NH ~ C j5 H1 1 ~t) L
~` 0=0 C=O C ON~I~ CH2 )4 O~C5~ t)
~C~ \
~2a3}I7(~) r
o3t ) ~ I
` .
23NHco~3N~IaoG~Ico(cE2)3coc~IcoN~ooNE!¢1~H33
' ` o=~ \c=o o=c C~O
- I I I I . ' ' ''
~2¢--CH2 ~2C--~2
~' - . ,
.", - . . . .. ... ~ . . - . . . . .
'' . ' ' . ' ''
f
. '
~,
- . 1.
.. ..
" ~ '
_, , '. .' ; '; ' ~ ' 4.,
~L05~5~3 `
,
~ Y-32 ) ` .,
¢~3
Ci~3 COa~[aON~ N~COC~lOOaH3
' /~\ oa~3
O:=CI C=O O=C C=O
I
- ~2c f~ ~c_c~ ~ ~
C~8H37 ¢18K37
S ~-33 ) ` - :
CH3 C~ .
~ . .. ..
CE~5 ~ . L~
~1~ N~laOa15 E~31
o=a c=o
,~ ' ' ~ ' ' ' ' ' ' '
O=G~ ~0=0 - r
o~i~3 ~ O
OE~3 7 C~C~CON~ 1
~3 I~HCOi~15H31
3*) . - . `-
. ~ 3 . ¢~C .
O~EI 3 ~ C O CH C O N~ 5 ~j ~
"N~ ~HCO(CH~)30~C~ (t)
o=a ¢-o
a: - ~ a~
~ .
.
- : ~
- ~ l
i
_ _____,,_ ___,,,,_ _,,,,_, ,, ,_ ,_,_,_ ,,, ~, ,_, ,_,, ~ ~,, , ,_ ,,_ _ ,,,,,_, _,,.,.___.. ,_. - ---- ' ---------'---'-''' Dl-~J
-~Q530S~
.
( ~--3~
.
'' C~5 ¢ ~ ' ' ; ' `
~ ,
0~3--C--COC~CONX ~ ~16~33
.` C~; ~N~ N~COCEl
~7 ~ o \80~H
~2 N--CX2C~IC~:~9
C2~5
--3~
11 (t)
(t)C5~11~ O C~C ONH~ OC~
a2}15 CO¢~ N~
. o~c~N\O=O
JI2~ --N ~3 r
(~--37) .. . ., .
C~
~COt~OONH~ ;--
C O ~IC~ O OC1~!~2
` ' ' ' ' 0~=1~ C=O ~` ' .
~12~ CoGE~ a~
.
- .
i
.
~053~:15g ! ;
( Y--3~
f~3 c~
a H 3--C--C O C :EI C O N X~ C5 iI1 1 (t)
, C~3 N N~ICO~0~2)30~C5~11 (t~
0~--0 C~O
¢~3~C--~1~¢~
` ~3
37 )
~00
a~ 7 o~ c oc~c oN~ -
L
O O OE
' C=O
N~
:r
OX 2 ~ C~ H 3
3 C4~ ~¢4II9
_
a~ o--OOC~ICONH--~ J ~NH¢OC~C~I2N
-@~3 ~N~ 4O015
. ., ~ ~=0
~ 2 }I 5
' . ..... , ~ ,
,
,
.. ~ ~ .. . , .
-, ' ' . ' -' ' ':
. . - ,, .~ . ~ ' ., ,, I .
_ ~ _~ _ _ _ _ _ _, ... . .... . ... . ... ..... ... ...... .. ...... ..... . ... ...... . ... ... . . . . ..... .. . ....
~ILo5;~S8 ,
'' , . ' `
(~/) , ' ~'
OE~ C ~ "" , . .
I ~ .
3 ~ 0--a O CH C ONH~ . ,.
CE13 ~,N~ 4
'' ' O=~ C=O ,- , ..
:E~2 C -- N
~a--Nl~ .
' O=:C C=O
- ~ 3 I C~ .
o~- a - ~OC~CO~H~ `
- ~ aL ~,
~2)
~3 ~ 4
¢~I 3 - 1 _ O OO ~lC 0~ C5~l 1 (t)
aEI3 ~ oC~ ~C5~ (t3
o=t~ c=o . I . l
I I a2~s , , . ,,~, 5--C--~
C1~2C:EI20a2H5
~ Y-~3 ) " ,
.- ~ I ~ -!
¢~ 3--0--a O C ~[ C O N ~ (t)
! . ~O~ ~C=O ~I~CO~¢}I2~3 0~5 ~1~ (t~
.
O ~ NE
OE~ 7S `'
: '
. ~
- ~ ' ' ' ' ,
:
.
. ., , , ~;, : ` e
' ' _,
53~58
. (~ 44~ , . , :
. . :.
c~3 C
`.t OH3--~C--C OCHC ON:H~
; C}~3 ~N~ NECOCHO~
o=a
C~3~ a2~5 C15H31 (n)
¢.~3
.
4~ )
. .
a~3 a~
` O:E~3-l-COC~CONE~ C5~ ) L
3 ~N~ l~ao(c~2)30~C5~
: " ~f ,
E[O N~ J
E . r
6 )
~3 oa~ ~
C~3- ¢ - aoa~aoN~ ¢5~11 (t) - `
CE~3 ~ I¢OC~O~C5~1`1 (t)
- . Ha~ 2~5
` " ' ' , , ' ~ ,' ~ '
' ` . , ~ ~
. _.. .. .
: . . .
. . .: ~
', j
.
.
~053~58 ` '`
.
( ~7 ) ~. :
., ' ' , ' '. aH3 0 C~?3
OEI 3--a ~ C O¢~IC ON~l~ C5~t 1 tt~
3 ~N~ ~co~Ho~c5E
~N ---- N~ C: 2 ~5
.
~OOC~ICONH~ ¢5X11 tt) :
COa~IO~C5~1~ tt)
~f l=Q C2~s , L
~ ` ~ C~2 ~0 4~ ~ (t) . . . .
,. . c~2
.
r4~(t) - r
.~
(Y~
` ~ 3 ,~C
- o~ C--C O C~C ONll~ C~ t 1 ~t)
O(a}~2 )3 0~C5~ t)
- . ~ O=C ¢=O . . . .
- `~D L~2~ : ` :
, , , , , ' 2.1 ' ' ' ' " ' ;
. ~ ~,
. . .
. - :
.. .. . . . . .
.
. .
. . .
. . . I
. 1
.
.
3058 - . .
.
--so ) . ~.
C OOR~
C:121E~250~COC~CON~
~N~ (~001~ ;
.~ .'~` 0=~ ¢=0 . , ,-
H 3
aE~ ,
~ y_5/ )
1 3 ~ aL
aE~3- f - coc~c o~ C5~1 l (t) ~,_
o=a c=o ~T~I 0 05 O:EI2 ~3 o~C5 ~1 1 (t)
~" I I , . .: N--N
; a~D ~~ ~ 'r
' ' ,- I ~ ' ' ' - ~,
f-~:OC~ICOII~ C5~11 (t)
o2N~ 3~¢5 ~ t) . ~
COOE~3 . ; i
~
"
.' ' ~ '
, , ' ' ,' - ~ :
.
.- I .
_ . _ _ ____ _~ _~ _ _ . , ... . . . . ,.. _ . .. . _ . .... . ..... .. .... .
: , ~ . ., . I
s
3~SF~
., . , , , "', ~
,
3 )
C~ ' ': '' '
, ~ ~OOC~lCON~ C5~11 (t)
~ N~C O~C :~12 3~ O~C5 ~1 t (t)
- O=C ' ~--O
t I , C~ A
O b 3 2 ~r
`' " ~D ;
,
~ ~--S4~
C5~l 1 (t) oa~;
(t)c5H1
., C2~Z
`' .: . O=C G~)
~' . . I I
C l~--C~ 3
I ~-SS ) - - - ` l
~ - j .
a~3
a~ a - c oc~o o
GE~ ~ aOOC~I2COOC12~25 (~
; ~ ~f, - ~
oaia--~-- 12 }~2 5 (D~
,
. .
., , , - ,
.. . . . . . .. .. . . .. .
.. .. ~,_ ' '.
. ,- ', . .
, ' - ' ' '' ' : ' ^ ' '' '
. , ' , ' , , ;
.
~ . . . . .
,
j,
',
.. .. ,
''' ' ' ' ' ' . .
;~
- . l~S30S8
--S6 )
a15~31 CON~ OC~3
O O O ~3: C O N~ ~ .
~N~ a OOE
O:~C oco
N ~O C H 3
--57J : '
~ 3 ¢~ -
a~I3--C - CO~C ON~I~ 05H1 1(~)
QH3 1~ N~ICO~C~I2)30~C5H11 (t)
` .' 0~1:~ C--O
.
.' ' . '' . .. , ~ .
(~-s8)
l 3 c~
o oc~ c o~ OH3
aooaaooa12~2s (~
o l l -
, 3 ~
.
~ ' ' ' ' '' . ' .
.. ' - '
. ~ ' ' - ' j .
= . . . _ . .. _ _ .,, . _.. , ,. . , . . ... , . ., _ .... , .. , .. _ , . --. .. , . . _ , ,.. _ . .. ....... .. .
, .. _ .. _ .. .. . _ . . . .... , . 9~". ,.,~
.
. . , , . .. ,.
`
.
- ~53~5~3 . -
. . . ' , i
Y--S ~
C~l3 C~C ` '
._~ rall3--a--oocHao~lH~ 5E~11 (t)
O--C C=O N~t~Olc~2 )3 ~C51~1 1 (t)
o _f~ -
a~3,
(~--60)
CE~3
¢~3--~--COCHOON~I~ . ,
- a~3~I\ h
o--C C=O
O--C--C--C4 ~9 (n)
~E3
~-6/ )
¢5~11 tt)
~` S~t~CslIl~OC~¢o~o~3
2~5~:OCHOONE~
0~7 ~3 ' '''
,,, ,, 3~
'' j ' ' '' ' ' '' ' , ' . ' ' '
'
.
: `
~Q~i3(~5~3 -
~--62) - ~ - .
~ 5 C~ " . ~ ~"
U }~ 3--f a O C H C O ~ ¢5 H1 1 (~)
aE~3 ~N~ . N}lCO(CH2)30~C5E11 (t)
, ,' 0=0 ¢=0
o f~
t~2
- ~D - - - '. ' ' ,
~ ~-63 j ~ ..
. .
a~I3 G ~ ~ .
t)}~3- 1-aOO~[CON~I~ 0~5~ t)
o=a ~--O ~c~(~H2)~o~cs~
t
o--¢
6~
a~3 C,C
~I3- 1 -~OC~ICO~ 5
~o~U~ ~}IOO~¢H2);0~05Htl ~t)
~2~ eE{2
~o~
.- . , 32~ ,
,~, .
` . - , '
~' . ' .
_
. . `:
- . ,
.. . .
., .' ' ' ' ' ' ' . ' ~ '
.
-
~053(~58
~Y--6S) . ` '
a~3 C~ .
O~I 3--C--C O a }I C O N~ C5 ~ (t)
, C~3 ~N~ N~IOOfCH2~30~C5~11 (~)
O=C C30 , ~ ,'
.''' -~D - ., s ,
Y--6 6 )
~3 ~ ~ `
0E~30 ¢--C O C9~C O~H~ ~_(t) . ~_
Il}ICO~C~2 )3 5}I11 ~t~
` ~=0 C=O
1~--OH
. ' ' , " ~D , . . - ' , `'' : ` ~
--67)
aoo~
~18~37Q~OC~CONE~
` C~OOE
`.', ." ' ' ' ', ,,, ~ ' ' ;
;` , . , - ,. ~ ~
' . ~ . ' .''.
~................... , ~
.... . . .
- ,
I ~ .
I .
~ .. _.. __.. ___ ___,_ ____ _ .. _____ .. ._.__ _ . _ _ .. _ . . - - . _- -- - - - -' ' ' ' ~ ~:~''.bJ
. ' ' ' ' ` ' ' ` ~ ' ` : ' ' '` ' ' . ' ` ,
s~
IX--6&')
. .
I 3 ao
a~ 3--C--C O CH C ONH~ ~5 ~11 (t)
~3 ~,N~ NHCO(C~2)30~C5~11 ttJ
: 1 3
~--aE{
~ .
~ Y~
$~ cæ
a~5- ~ -OOC~CON~ a~ t) L
N ~ NH C O (C :EI2 )3 o~C5 ~1 1 (t
2 ~ 0=o
aL .
Y-70 )
, . . ,~
I 3. .C -.
~ C OO}ICON~ C5:E~11 (t)
~ N~Ioo~2)3o~c5a11 ~t)
- `` . 0 2 B C=S)
- ~ ~ 2 ~ ~ 2
,, ' ~ ' - , ' ' '.
. , .. .
. . , - ` 3 7 ` ~ - .
. . . ~ , . .
.. ,
.
. .
- l :
'' -'' ' , -
!
. , . , , . ,,;, . .. . .. . .
. .
~L053~58 ,
.
--7/ )
O¢~I3 : `
018H370~ C!OCHCONH~
2 ~ C=O ,
021~50 ~NHCONl~
72 )
. . ,
5
(t)G5~11~0C:EICON~I OCH3 . h~
02II5 ~ ~ OC~HC ON}I~
' ~N~
02~3~ ~a--o
c2~ 02H5 r
~-73 )
OC~3 OL
' ~COC~I¢O~
,,"11~' COI~ 2 C ~ O C 1 2~ 2~, , .
2~ ~ '
", ' '' ,.
3~ ~
.. _. ~_ ' .,
','-- .
`;
. .- ,
I .
.,, ~ I
, - ' ;-'
~ . r i
- :
~053~8
. . .
( Y-74 ) ; , ~ :
c~
~ c o a ~a o N~
" ~ ~, /o--C~I--¢ t8~37
~N~ . N
2 e~¢-o \c - C~2
~OC~[3 o
OC~I3
Y--7S )
:E[coN~æo2Nl~2 -
,"N~
t~2~ C=O
)` ' ~ . ' .' ` .
~13~27 0 0 NII . .
t r
. . . . .
7;6 ) " ` .
C~3 C~
- O H s ~C O C ~L O O N ~ ~ . . C5 ~1 1 (t)
3 ~,N o ~r ~ a o ( ¢ H2 ) 3 O ~ C 5 ~1 1 (t)
, . '. ~ `'' ' .'
~, ' ' ' ' . ,
,
... . . . . . . . . . .
. .. , ~ ~, . .
.
' . ~
.. . .
- ' ' ,
,~
. - ' ,
'' '.
.. _______~__~___,_ ,____ .. . ... , .. .. . . . ... , .. ............ ........ ... .. .. ...... _ _ . ._ . _ .. _ .. _.. _ . ... _ . .
. ... ... ~",,,~. ",J
.
. .
~ .
~53~S8
-- . . .
(~--77~ ~ .
. .
a4
.~ !''~ ~CO¢HCONl~
~N~O COO¢HCOOc12H25(~)
Br
~r
7~ ) .
-
. 1 3` C~
OH~-C-COC~CON~ ¢s~ (t) L~
C~3 ,;N N~co(c~2 )3 o~as~1 g (t)
,~ ' U~ `' '' '
¢
.~ . . . '
. i , . .
i Y-7~ ) ~ .
- , . 1 -
. Ot~:EE3 , .
~NEOOCHCO ~ t~51I19 (t)
,N~fs; O N ~IC O CH O ~Cs ~1 1 (t
'
~ . . . .. .. . .. . ... . . . ~
- ~ .- -i . :-
' ` ' ' ' ' ' , '
_.. ... . . :. .. . . .. . ..
,
,,` ' i
_ _ , ... ,, . , . . .. .. . ... . .. . . , .. .. .. .... . .. .. .... . _ . .... ... ..
;
~0530s8
o
c~ c ~ . .
O ~ C--O 0 C H C O N :~ ~ C5 :E~1 1 (t)
, ~ 3 N~ o NH a O ( C ~l2 ) 3 0 ~C 5 H1 1 (t)
,~
a~ . `
l y~
` ~C~3
N}IC OCEC O~ aS~I1 1 (t)
0 N IIC O C ~ 05 H1 ~ ~t) ~-
~2~5
,
--8'2 )
` . CE~3 C~ ` - '.
~,
0}~3--a--a OC~I C ONH~ - 05 11 (~
00(~2)30~C5~ t)
o~
. ' ~' ' '. ,, :
3 8
_. ~ , . .
.
.' ' '' , ' ' ' ' :
', '
- ''
. .
, . , !. , ~ .:. : i
i' .: ' .
3~S St
-~
--~3)
(n) 1 8H 37 NH C O~NH ~ o 2 -~L
~o C OCHCN
'~ ' ~.
- C
( ~--8'4 )
~3
OH~--a--C OCHC t~NH ~ L
~ - ..
.
. . - . - 1,1',
--8~ ~ :
,. ~ - .
- . - . . .
~3--C--OOC}IOONH~ $E11 (t~ ;
acc(~21~0~c5~11(t)
,~ ' . ' ' ". .
. '.' ' ' ' ' -, ~ , ''''
- ;' -~ .,
.
,
.. . .. . i
.~ . . .
' ' ~ ' ' i'
11
~L~5305~ ' ~
'
6 )
1 3
aE3--f COCHCONH~
3 ~o N~CO~OH2)30~3C5Hl1 (t)
.. .
(Y--~7~ .
C~ '' , . .i
0C~C ONH~
~ ¢OOCHCOOa 12~125(n)
ClE~3 ~_
~ ' ' . ' ' '' ' .
~ a~
. , tS~13- C~ -COC~CO~ C5~1 (t) - ; r
~3 ~ N ~ O .. N ~I O O ~ C~ 2)3 0~cs ~ (t~
C1~ 3
C~ C--aOC~CONH~ C5 1 i ~t)
3 ~ {CO~C~2~30~:5~1~(t)
a~3 . , . ,,~ .
~ 53~5~ -
. .
(Y--~O)
~1~?3 a ~
a~3--C--COCHCON~
C~3 ~ O N;EICOCHO~
~CH~ ~2H5 ¢15H3~ (rS)
EI 3
CX3 C 4
C--sC O C H C O N EI~ ,
¢~3 L~ N~ C O C H O~
~3 C2~[5 C151I~1 (n)
' ~ . . ' ~:
"~
C ~ . . .
, I ~0~ , ; ".
C~3--C--coaElc ON~ ~5~11 ~t) r'
~ , N~C~2)30~as~11(tj " ~,
-.... , 0~
~~5'3 )
~ 0 ~ ' ' . -
- ,' . ` I ~ .i
- O~--O--C O¢:EIC ONII~ C5~Z1 1 (t)
3 ~o ~2ICO~OE~2)30~CsHql (t)
. 1~ ~ . ,' ' , , . ' .
,
. . . ,' . , . - , . . .
' ' ' . ' ~ .: ,
-- . .
.
~ '' p~"rt
: , - , . , ... ... , .. , . ,, ,~;,
1~530~
,, . ;, .
_ .
C~I3 ~
., ,~ C H 3--C--C O O EI C O N~ C5 H11 lt)
CE[3 N~O NH C O ~ C H2 ) 3 O~C5 EI1 1 (t~
@~6 . '
,
(Y--9~)
a~
~¢ O C H C O N~ ;
N_"O COOCHCOOC12EI25(nJ
CH3 N CH3 ~Q
.. : `` ' . . . .
: ~ y~
~ ~ a4
~OOcxaoNH~ r
cooaHcooc12}~2s(~)
- ` OII3 ¢}~3
, . , ~ .
9;~' ) ' -
~3 C ~ .
- 0~3--G--OOCHaON~ 5H11 ~t)
a~3 N N~lC:O~aH2 )~jO~C~jH1 1 (t)
S~2
- ; , , :
- . ,
:; ' ,
_~ . - - . : . .
.. . i
:`, . ~ . ,~
.
- ., ,. ^;. ~ ' ' ' l',
s3~s~ ~ l
t~ 9~) ` . .
~3
OH ~--a--c o c ~ c ONE~
S~3 ~ -O C
' ~' ; - . .
9ts~t ~
c
- 1 - c~a~co~
, 0 N~ C O C }I O~ ~,
--O a2~5 C15~31 (n)
,`- ' ' I~ ~
,
~joO) . r
~ G J
11~3--O--QOCIl~ON~
~ ~G oc~o~
15 ~
1~ 3 : -
~D : , - .
' ' ' ' ' - - .
- 4 - ~
' , ' ' . Ot
.. . . ....
~ _ .. ~ ... . . . .. . .
. . ' . 1,
.. ~ . . . - .
~Q5;~5~ . ~
C~
.... . . _ .
~ C O C H C O NH
.` 11 o C.C
Il .. .. .
~I N
,~
`'
a~ :
Y--~ 02 )
aæ
' ~COCHOONII~
.'", ' ~ V~ , . .
- o~ N~N~O C~
N .
j. .
a~-~03 ) - . - - .
c -c oo~aoN~
~ ~ o ~oo~xo~
~2~5 Cl51I31
' ' - ~ '
- , . ' . .
''
- ,~ `
- :
,
.`.. ~' . ' ' ' ~
- ,
.
,
, .. , ... . ........ ... . . ... . . . .... .-- --, . ` . ._.. V
: - -! `
: . ~ . . . .
.
~53().
' ( Y-/O~ ) . ' , , , 1 l .
CH~ C ~ . . .
0~3--O--OOOHOON~ a5~11 (~)
3 N~ O N~tOO(C~2)3 O~CsH11 (t)
~_0 '' '. ' ," ',
'
/OS ~ .
~ C~ .
CE13
OH3--O--C OClIC ONH~ C~5~11 (t)
CH~ ¦ NHCOtCH2)30~C5H11 (t)
N O
i~ E~ . . . . .
. ( ~ 06 ) . - `
.` . ' o}~ ' .'~,~, . . .
`~ - OII3--C--ooaHooN
OHs ! ~? E C O ~ H O ~
¢ N a21I5 C15 ~31 (n)
~D2 ; ~
. ' , . , ,, , i,
4s _ ~ :
. ' . .' . '.... . ' I '.
~- , ' ., ~
~L~S3058
O OOHCON~I~
OH3--N' ~ Ol)OO~COOC12~E25(n) .
.. ,~ I I . I . ..
~H3 . ! :
I~X3 .
( ~--/ 0~ )
3 ~ . .
~3 f aocHcoNH~
OlEI3 N O C4 .
t3~I 3 C ONEI:~C
--J 09 )
C~3 C
o ~ ~--c--a o CH CO NH~ 05 ~t 1 (t) r--
CE~ o,~ ~ N~I¢O~o~I2)3o~c5~1l (t) . ' !
0 ) , , ~ ~ /
a~3-- o - a oo~ao
aE~ o C ~ -
. . ~ ' ' '
!:
., l
- , . ~ ~ .
: :
.
' t', ,~ _
;. .
3~51~ .
. , -
t ~
a~3- a - a oa~a oNH~ . . - .
" a~ ~o c~ .
N
ICOC~3
/2 ) oE[ a~ :
a~--o--c OCHC ON~
~ C~3~c) C~
l~ , ' , .
N~I C O CH 3
3 )
" : ~; C
a~; f ¢OC~Co~E~ 05H1'1 (t)
aE13 ~o ~ NIIGO(C~2)30~C5~11 (t~ ~ r
- - ; .
J~r4) ~
a}~aoN~
¢~3 . ;.. .
.
~7
.
. .
:
.. . - ' ' ' ' ' ,
j
:. ,
. . . 1,
.
.
- ~ ;
~(~S3~)58
s) . ~ , ,
C ~
~C OCHC ONE[~
` N~2~N~ C.C . . ' .
, ` ,
N C H~S
/6 )
1~ a~ . :
C~3~ ~:--COCHC ONH~
~3 1 O~C :
~ ~ - L
.
/7 ) a~
~O O O H C O N ~ ¢5 El t ~t) ~ r
~0 - NH~Ol~ ~2 ~3O~c5 EI11 (t) . i
C~S OH3
a~aoN~ G6E11 (t)
CO~C~I233o~cs~ t)
i
. , _ ~11 ' -.
" ' '
`
.
. ' ' ' . ' 1.
..
1 '
r
~L~5305~
(Y--/t~ ) ;, . . .
C~ ¢~
a~I3- la - aocHa ON~I~ ' `
_~ v a~3N ~f~ o
~ N~
OC8E{1 7 (n~
--f20)
. } C~II3 C
C~I3--C--COCECONH.~4
a~3 N ~ O C .C , ``
~N ---N
~-.
. i2~ 3 ¢-
C~3--C--C OCHC ONH~ ~5~ 3
C~ o N~ o(cH2)30~csEl19 (t)
:, . t~ C~ ' '
''~,' ~, . -.
5~-/22) CE~3 cæ ~ ; `
0~--C--OOCHOONl~ C5}3~ t)
OE~5 ,N o N~ICOt~:}I2)3û~G5H19 (t)
" 1~ 8 . :'
~,~. ' . ' '. ~. .
.
,,
.... .. , .. , . ; . . ~ . . .
.
.` ' - ' ' ~
.
i
___ . _ ._ _ _ ._ ._. __._. _____ _ __ . . .. _ _ _. ... _.. _ ._,._ ._ ; .. _ __ .. . ~ ._~, . ...... _ _._._._ __ .__ _._ . ... __._ ,
~, ` . , .: .` ~ ;. ` ` . `
`
:
r
. ~Lo53~5~3 :
.
~-/23 )
C~3 C~
C~3--C--COC~lCONH~ C5H11 (t)
C~3 N o N~I¢OlC~2)30~c5B1 1 (t)
--/2~ )
I 3 a~
GH3--C--GOC~CON}~ : C5~I11 (t)
~ ~ o NEiOO~C~I2)31~C5~11 (t)
~= N
' , ' " ~ ': ''- ' ''
--/2~ ) , -
` ~3 GL
,,
O~ C--OOCHCONH~ (~5~11 (t~ ;
~CO/C~2)30~05~1~(t) .;I,
11 ' , , ',''
OH
26 )
a~3
a~3--O--COO~ICON~
3 ~ O P~CO~}~
- 11~0~ 02~E[5 G~31 (n)
~S~3
' 50
~ -- - . . .
- . . ' ` ;
- ,
.
.
', ' . , i ~
: - - . J
: :
., ,. . ' S . ' . !
_,
. . .
S~OS~
. .
Y--/27 )
0~0E : !.
a1 8~I 37 ~o oc~C ONII~ . '
N ~o ~~ :
0
'
-
2~
aEI3
- c~ c--aoc~c ON~I~
- I I - .
G~ ~N~
o=a c~o ~._
I ,
.- - 17--N
~ ` ~ I I . .
}~2C~ ~o~
. o~ ~ r
~ I
- ~ 2g~
- . ,
' ~ool~o~
OOCHCOOC14H29(D~ - i
- o~a ~=o 3
. ~ - ; 3 ~113 ~ ~ ,
~2~ ,~2 - - . -.
~3 CE3
- .
~,~ . ..
~ .
.. ..
- - ;
'
.
' - . , ' , ~- ~
- , .
.
.- . -
. .
~ . . . . .
_j
~(~S3058
These yellow couplers can be synthesized according to
methods disclosed in West Germany laid-open applications
No. 2,057,941 and No. 2,163,812; Japanese laid-open patent
applications No. 26,133/72 and No. 29,432/73; Canadian
patent 1,018,175; Canadian application Serial No. 183,597,
U.S. Patent 3,900,483; U.S. Patent 4,008,086 and Japanese
laid-open application No. 28834/75.
As typical examples of the magenta couplers represented by
Formula II, the following compounds can be mentioned:
,C~". ' ,.:,
N = C-2
~--N
. . ~ ~ OoNHc12~25(n)
a.~ Il~CH2
,;
~c--.2 ) ' ' '` ' ' '
. ' ' C~
C -N~
.
- 52 -
~1 .
- , ., - . . . ,: ~. , ~ ' . ;
.
)53~58
M--3 )
C~ ` ' , i
C4 ~
~N=C--NH~ a5~11(~)
~ C--¢~2 CoN~c~2 )i~ a 5~11(t)
.` C~
' C~ .
C--N H~
. . ~ \O--C~2 CON
04 ll C B
'- ' ~.,
' , '-, . . . .
S ) . cæ - ~ `
C--N~l~
H 2 t~ O N ( 0 ~ 2 ¢ }I C 4 ~ 9 J 2
o 2~5 ` - .
.
;; ( ~l-6 ) : ; -
. - . ¢~ . :
cr ~ N~ ~ C~H~7(tJ
N~ I CO~
,,, , , ~ a~2 \ '' ''
- O.C 11 C~2~s -
:~ : ,' ' O
~i ~3
,: ' , . ,'.' ' ~, . ,, ' ' ' '.~ '
, . . .
- .
- -- - - . .. -- . ` - . . . . ..
:, . . .
~ . . .
,
- : I
~ . . ~
~LID530513
7 )
04
a.c ~
/ N~ O--N~
a~N ¦ ~Y~o--0~--¢12--~I25(
~ ~ ~ \a c~ CONH(0~2)3--N
-
ce
c~
2 E2
C~ 7 C~ 2 C ~ c o c 4~ 9(~ .
O ~2 ~2
~l--5i' ) ' ' '.
C~ ~000
~ ~N--C--N~NHC O O~I 2 a:EI
a~N ~ 8~37(Il) r
C~2 ~ noc~(C~3)2 ~ ~
o
-
O) ' ~ ' ' '
- a~ a ON~C1 ~ ~25~1
J ~11--G--N~I~N~ICO~OOO~I -
. ~ . 0~
' ~¢~ a'--~H2 ~OC~
O ' : ' :
.
s~
;~
- l
os3Q58 ~ l
M~
0.~ , 3 !
a~
a L~N ¦ ~
\¢~-CH2 8o2~Ha:~2cHc4H9
,t ac ll , C2~s
i ~--f 2 ) JL
0~ ~ ' .
N=C--N~
~` O-- ~ 2 ~ 0 2 N H~3
. o OC 1 8~37(
" (~ J3) .
- )L
- ~ ~N=C--N~I~ 05H11tt) , , r-
~ \0 ~ o2N~c:~2~4~)~c~iHl1 ~t) ' ¦ `
.~
- a~ ,
a~2~e~ 3
~N ¦ ~ ~C--~ 12~25(~)
OII2 ~1021l~C~2)~
B - ` ~
:. . . . . . .. ~ ,.
.~ ~ . .
.. .. . . ~
.
- ~.
.. . .
. ' '- ' ', ' : .
. . . -
l .
? :`
i . - . . .
~(:)53~:)58- `
. . I .
s
~;;L\~ o2U~a~2oooo12~5(~
t ~--/6
o~ ..
C~
~N=C--N}I~
~ \O--O}I 2 ~ICl~ 2 O O OEl C 6E 1 3(n)
., ¢.~ Il I .
O OX3 .
- h~
. o4 ~
a 4~ ~ c ~ a o o c ~ 2 H 2 5(n) . '~ r
- 0~3
' . . . .
t g
o~
,N=~S--N~
C~ 11 N El~ C EO ON~I O 4 ~I 9(n)
~ 12~25 .
S~
' : . ' ~ ' ' " '
.
' ~ , ' . ' : '
... , . ,, -. j .
- ' ' . ' . ' . '~ .
.
, , , . : : ., :
531:~5~3
- ; ;
. t
N~O--N~
;. C~-~N ¦ ~ ~C--CU--018H37 (n)
.~ a4 11 ~-c~2
O. 11,
o ~ ~ .
20 ~ o
C ~C--¢~I--C12 ~25 (~)
,~ ~N--C--~IH~ ¦
C ~ N ~ C ~ 2
a ~ C H 2 o
.. . o . . 1~.~
C~
a ~N~ C--O ~I--( C ~2) 3C ~E-- ~ 1 7 (n3
C4 ~ aE~2 ~ ¦
` B - ~ ~
l Jl--22 )
- C~ ~
la=~--N~
E=C~{01 6~33 (
C-C~
,. . .. . . :
', ~ `
,' ~ . 5~ ' ' ' -' :
~ ' . ~ ' , '
:'
- ... . ' ._' : ,
.
'-
'' I
.
. .
.
' ' ' . , ' . : .
)53(~
.
. - .
~-23) ~ `
/¢ ~ --C 12 ~ 25(n)
N--C--N~N
oL~ kN 5 o~2
\ ~ 0-01~2 . O
O
.
--2~ )
a4
~=0--N H~ ¦¦
~ / w~ C--C:El--C}I 2--8--t~ 4 H29 (n)
.- C~_ ~N . /
¢--aH 2
O a-a~ 2 Ld
.
--2~ )
O ..
~N--C~N~ ¦¦
\C--I ~I2 N ¦ .
c~ 1l H-~[2 `!:
` . . - . -
.
(1[-26)
C--N~I~N~IC O 1 7 ~ 35(n)
~ ~ O , . ;
- . , : .
- - ' --
.
.
_, _ , . ,, , _ _ _ ., _,,,,,, ,,, , , , . _ _, _ _ ... .. ... . . ..... _ .. ... _ _ . _ _ ... - - -- .. _ . -- . -- -- - -- -- -- --
- -- -- --- - - --- - - -- -- - ' ' ' -- ' -- ' ' ' ' ' ' ' ' ' ' ~ F ~ '-- '~ (
~ L O 5 3 0 5 8
.
27 )
., a4
a 4~ ~N=O--N:~N~Ic oc ~Io 1 g H 3s(n)
~~ ~ \C--OH~ OH2 CO OH
C ~
', - - .
(ll-2~ ) -
. . . ¢,~ .
, ~ ~N=a--~I~NHCOC~C16~33(n)
~a~C C-~2 ~33
O
1;~ _
. . (1~ 25') :
C~{ 3 - -
o~N\ I Nl~OOO~
O
--30 )
o~3 ' ::
~ ~a--G}l 2 ~ C~ 2
~ H
, . . : .
, . ' ~ ~ . ' ' ,
'' " ' ' ', O~
, ' ' ~ ' ' , . ' .
'
. . ' 1'
. '" ' ' . '
.
"' , ' ~:
, ~ . ' . I ' ., .... '`. ~. ' .
.`:
~Si3Q5~ .
.
3~ )
CiI3 ;
a~ ~, .-. j.
N~C ~N~I~
o ~N\ ¦ , C ~ ,
\a~ ~2
o . . .~ . . . ;.
32 )
O CH~ .
/N=C--N~ -
\C--0~2 N ~
.. o . , ~,
(~--33 )
Cl~,, N=Ci--N~
\ ¢--I;H 2 N O 2
G 11
o , .. i... .
34~ j . . ; ; i
~L
.e, ~=a '
~=~f ~N=Oi--N~l~N~Ii iCiO~
0 4~"~N ¦
~C--Ol~
' . .. C.C U . . . ~' '
O
`
~ O
.
.
.
'. ' ,. ,,, ' ,.
.... . . . , , ~ . , ,
; , , , - , _ ,
.
;
'
. . I
,, , . 1.
<~;
: ~ ~53~58 .
~ g
.
3S ) N H C O ¢ :~ 3
~N=C--NH~
C 4~N ¦
C--C1~ 2
O
.
36 )
C4
~N=C--NH~NE C O~
O--CH2
a~ 8 r
( )l--37 ) ~ OO~I
` ' ~lHC OC H 2 C H
~1=9--NH~ \N~C ~2H25(n3
C~l,~N~ ¦
- \ ¢--C~ 2
. ', . O ' . ' . - ~
~ ~ ' ' . . ' " ' , ' , ' ' ' , .
38' ) ~al~3 .
~N=C--Nll~ . . .
C~ 2 ~I}I C O C ~I 2 C E{
a ~N~C12E25(~).
Gl COGE~3
: ` . ' . ' , .
'~
, -
.
;, ' . ,
. . . . . .. .
.~ , . . . , . :
- .
. : .. . .
,, ~ ., .
~ '
.
l~S3~
.
.
(~39)
¢~, ' .,
~ jN=C--NH~ /C O OH
", '~ \¢--C~2 N~COC~2C:EI ' '
~a12~2s(n)
oocH3
t ~0 ) ' . ' ' . ` '
c~ . :
C ~ N ¦ ~ ~C 4 ~19 (t~
~ \C--C~2 ~HCOCHO~O~I
', ' O ' a12~25(~ '
. , ' , ' ~;~':
~æ o4~9(t)
. ~ ~N=C--N ~ C O C H O ~ O ~1
¢~ I - oE2 - ~1 2}I25(n) r
.. . O . .. i
C~
- , , ~ ~ '- 0~; C18~37(~.) ' '
. . ~ .. .
.
. ~ .. . . ..
... .~ ........ .. . ~ . ; . .; .
... . ... . . . . . . . .. ... . ... .
~ os3~s~3
' ` '' ' ', '' ' ,' ' . " . '' ' ;'
~ 3J ~.
... , . a~3 ~ ....
. . ~ ~N=C-N~
.~ C~ ll 2 a~7~C1~H25(
. .. ,': ' ., ' ' ' ;:
, {~ ~, ' ' ,
~ /~=C-N~ ~ - a5~11(t)
C~ 11 C~2 N~CO(C~I2~30 ~ C5~1(t)
O
.. . .
These magenta couplers can be synthesized according
to methods disclosed in U.S.P. 3,684,514, British Patent
1,183,515, Japanese Patent Publications No. 6031165
No. 6,035/65, and No. 15,754/69 and Japanese laid-open . ,
Applications No. 29,639/1974; No. 117034/1974; No. 53437/1974
and No. 123023/1974. -
As typical examples of the cyan coupler represented by
FonmulaIII the following compounds can be mentioned:
-
- 63 - .
. ~ , .
.. , _ .. .......... .
., , ' . ', . ~. .
~s~0s~
, OH
~NHCOC~0~0 4~9~t)
- C~
~a-2)
, o~
~N}IC OC:~O~C 5
C~I3~ 1 .
G2~5 ,
.
~3) . -
c
~ I ~ r
~a~) ' ''
.. ~ . ~ .. . .
8~E~ . . .
~N ~I C O C ~ o ~ C 5 l~E 1 1 (~J
OJ ~2~5
- ' '-
' t'-
.~. . ": .
,` ' , . . .
.
'
.
____ ,_.. _.. ______.______ ._.. _ _._ .. ~ . ~ .~ _.~.. _.__ _.,, .. _~ _, _ __ ,.,,._ _, - __ _ _,,, ---- _ - ~.".. " ~,_,
( c-s ) ~53058
~N~ICCCEIO~C5~11(t)
. .
..
t¢-6)
o~ , ` .
,_~N~ C O C H 0 ~ C 5 H t 1 (t~
c~ ,
~' '. ' . ' ~ .
o--7 )
oa8~17(~ -
OE~ . ~ ,
`0L~N~COI~O~ - r
¢4 .
'. .
(a-8? : - -
14~29 ~ ;
' 0~
alc
G5 ` ~ .
, ~ :
`- .. . ,.
: ` . . ' ` -
-
.. .. . . . . , ` .
"- - . ' - ; ~
..... . .
. :
`
:
~ .
. ~
~lS3(~
~ O --9 ) . :
"~ ~ OE C5~11(t)
~N ~I C O C ~ O~ C 5 H 1 1 (t)
~3 ¢2~5 ~ ,
aL
--/ 0 )
OII
--N H C O C ~ o--Q
a 2~5 a 15H3t(~)
- ' . . ' '
~ !/)
., o~ , . ~ . .
C00 o~5~ (t) ;
'-,
- . . ; '
O-J2 )
0
N~ C O C }I 0~ ~ 5E1 1 t (~
.. a~ ~2~5
.
6~
. ,..
.
' . - ' . -
,
.
.
.
)
1053~513
o--/ 3 )
O E~ a 5 H1 1 ~
J~ * a-'C~D-N~ICOCH20-~-C5~ (e)
.C}~3
t C~
0}~ 05H11~t)
` O~ COC~20~5~ t)
a~
~ ~ I c~
a 5~11 (t)
000o~3~5~--(t) r
..
6)
$~. ,
~N H C O ~ 10
1~; Z~{5
OG12~25(~
' ' , :~1' , .. .
, ' , '. ,', '' ', ' , ' .. `
_..... . ' ' . ' ' ' ' '. ..
.
- . !
.
.:
.r ,. . .
105~)5
(o--/7)
o~ ~:
~N ~ C o o H o
~C~3 :2 5 ¢15~I31(~
( 0~
OE
G4~NECoC~:2o~
C~ OC 12~I25(n)
, ., ' ' ' . ~':
l a-t ~
co ~0~ - ~ , r
~E3 2 H5 . O t: t 4 ~ 29 ~)
- :
1~-20)
- . 0~ 4 ~ 9 ~B~ ;
~JII C O C X 0~ 0 4 H 9(~)
}. ~ C 2~5 .
. GY
. . ' ~ . ' . .,
. . . : . . .. .
. .
.
.'
.. ~ .. . . . . , ~ . . ... .
: - :
~ (~53~5t3
a-2~ J
O H G 5 ~I 1 1 (t)
cæ ~N~C OC~I2 O~C 5~11 (t)
. ` a~ .
- . . :.
C--2~ )
'
0
¢~ ~NHCOCHO~
a2~5
o~ oc12~2s(~) - L
o-æ3 ).` .
o~
,
c ~OOcl2~cls~ - r
.
C--2~ )
- ~ C 4~9(~
C~N~COC~IO~C 4~I9(~
~ 2 ~3[5 - `
0~ , :
.:; .. - ` . ~:
G9
~ "i~ -
. .
' ' ~
- -
, , , !
.~ '
. ' ' ' ' ~ ' i
: . !
,
'1~)53
. ~a-2S)
OH
? ~N H ¢ O ¢ ~[ 2
a~ O~t 2H2~
( ~--26 )
o~ t 5~1 1(t)
h~NHCOCHO~C 5~I11 (t)
C~30~V a2~5
I~.C ' -
~..
~ ~, c-2i )
.~ . - , .
5
o n ~ o~
a~ - a~5~3~
. :
a-2
o~ , . .
a~ coc~o~ -
a~o 2~Ei
G~ 1~¢ ~6E33(n)
' ~
' - , ~() '
.: _, --.-- .
. , ' - , :
-: . . . . :: ',
:
:................... , . , ~ . .
~0~3~58 ~ ~ ~
:~l(cF2clT232o~I2ocEI2cElc~2oo16E~3~(n)
-- O,~O~E
V--/O)
H~cF2o@2)2cH2ocH?c~c}~2
O~O~Na C~
(V--/J )
~I~CF2CF2~2C~I20CH2CHOE[20~
0,$03Na OCH3
2 ) t
~1( CF2C~2) 2cH2ocx2c~c~2o~c 8~17
OB0
--/3 1
, . }I~¢F2cF2~3c~2oc~2c~c~o~c8~7(t) 1¦ .
. 0803~a
--,4~ , , .
~I(cF2cF~)5c~I2ocH~c~cH2o~c8~I17(
0 8 0 3 N,~
`
~g¢F2¢F2)2C}i200~2C}~ 2'~
080~Na ~ ~ `
' .' . ' ', ' . . . 'i '
. ;...... .. .. .
.6V. ~6.) . ;'
~(O~?CF2)3c~20cE~2o~c~2o~ ~ I
0 5B O ~ N a ~
t
. - ~ . i
- 8
... ,.. . ... ., . . . . ,.. . . . .. . . . .. . .. , . .. . . . . .. _ .. ......
., , ,, . . ::
.
~ ~ 3~
The following ompounds are typical examples of compounds
represented by Fonmula Vl and can be according to synthetic
processes disclosed in Japanese laid-open Application 32322/1976.
NaO3S-CIHCOOcll2(cF2c~2)2~l
. C~12COOcH2c~20c8~l7(n)
NaO3S-CH-COOCH2 ( CF2CF2 ) 2H
CH2COOClOH21(n)
NaO3S-CH-COOC~l2(CF2CF2~2H
CH2COOcH2cH20c8Hl7(n)
., - ',
NaO3$-CH-COOCH2(CF2CF2)2H
CH2-COOCH2cH2 ~ ,
,
- NaO3S-CH-COOCH2CH20CH2(CF2CF2)3H
CH2-CoOCH2cH20c~12cF2cF2~1
.
NaO3S-IH_cOOcH2(cF2cF2)3H
CH2-COOCHzCHClCH2Cl
' ~', ~ ' ~ ~ ' ~ .
`' ' ' ' ',
~ ' .- ' . : .
., ~ ~1 , , , ' .
_ .~" _
.
. ~ . ..
~.j .
~ . ~,
' : - ' ' . ' , ' , ' ' . '; .
~L05~0~i8
In order to incorporate compounds of genexal fonmulas
IV, V and VI into the layer elements of a silver halide photo-
sensitive material, such as a silver halide emulsion layer,
an undercoating layer, an intermediate layer, a filter layer,
an anti-halation layer, a protective layer etc., the compound
is added directly into the cuating li~uid used to fonm the
l~yer. An alternative is to add the compound to water and/or
an organic solvent such as methanol, ethanol, acetone, and the
like9 or a mixture thereof and then to add the resulting solution
~ tO the coating liquid for the layer.
The quantity of the compound used in the silver halide
photosensitive material can be varied according to the compound,
the layer into which it is incorpora~ed, etc. However, it is
generally preferred that the compound be used in an amount of
O~Ol-lOgg more preferably 0.1-3g, per kg of a coating liquid
to which the compound is added.
In this inventiong a combination of two or more compounds
of general fonmulas IV, V and VI can be advantageously used.
The compound can be incorporated into the photosensitive material
20 at any stage in manufacturing the material~ It is~ however,
preferred that the compound is added into a silver halide
emulsio~ after the completio~ of th ripening of the emulsion
but before its cQati~g.
Am~g the dyes formed from couplers of general fonmula
I~ II and III, cyan dyes are mos sensitive and tend to change
8l ~
,
,. . ~ ~ ' ,.
' '. ~ ,
.
~53~5!3
and/or fade in color more Pasily than the o~hPrs. Yellow
dyes are nex~ and magenta dyes have the least tendency.
l~erefore, it is prefçrred in this invention that the compound
i8 incorporated into the red-sensitive ~ilver halide emulsion
layer in which the cyan dyes are formed.
Hydrophilic colloids advantageously used for a photo-
~ensitive emulsion of the silver halide photosensitive material
for color pho~ography according to this invention include
gelatin, colloidal albumin, agar, gum arabic, alginic acid,
lo cellulose derivatives such as cellulose acetate hydrolyzed
up to an acetyl content of 19 to 26%, acrylamide, imidated
polyacrylamide, z~in, urethanecarboxylic-or cyanoacetyl- ;
group-containing vinyl alcohol polymers such as vinyl alcohol
vinyl cyanoacetate copolymer, polyvinyl alcohol, polyvinylpy-
rroiidone~ hydrolyzed polyvinyl acetate, polymers obtained
by polymerizing protein-or saturated acyl-modified protein
with a vinyl group-containing monomer, and the like.
Any o silver halides ordinarily u~ed or siLver halide
photographic e~ulsions can be used in this invention. For
e~alple, ~here can be employed silver bromide, silver chlori-
de, sil~er idobromide, silver chlorobromide, ~ilver chloroio-
dobromide and the like.
Th~ silver halide emulsion to be used for -the silver
., .. ~ ;
halide photosensitive material for color photography according
to this invention can be prepared according to any o various
~ustomary methods and k~own methods. For instance, methods
a~
.. ~ .
;- ~
~ 3(~5~
..
(C-2~) " '
0~1 ' - . . .
OR 3--~N H C O C E 2 0~
0~114II29(D~ -
a~ . . .
-
--3~7) - ' -
E a 5 ~ n)
0~3~ COORO~C5E111(n)
2~5
o~ - L
.
(¢--3~ )
OE
-
t ¢-32 ~
o~ - ~5E~1(t)
C~ N~GO~:ElO~¢ 5}Itl(t) .
3 ~
, ~3~ ,,, ", , ~,
7~
- ..
'............... ' -' ' ' . ~
. . . .
. , ~
.
... . .. . . . . . . . . . ..... .. . .. . .
~ ` . ' . `;
. : .
105;~058
t ¢ -33 )
, o~ C5E~11(t) ' ~ ;~
- OH30~NROOcH20~3c5~11(t)
` C:.C, ' .
,
~0--34~ ` !
OH C5H91(t)
a~ ~ o ~NH C O C H O~ C 5 ~ 1 1 (t~
~3H7
a4
ta-3s~ -
OE[
130~N~COCHo~3
o~, ~cs12~I25(n) ,i I .
' ' ~
36 )
' OEl ` ,
0~I 3 0 ~ 1 G O CH O~
~2~E~5a15~31
... .....
-- - , . .
, 7~
' ' , ', ` -
.. . .. . . . . .
.
.
.,
.. . . .. . .. . . .. .
.. . . . .. ..
105~(~58
0-3~ ) . .
OH a4~9(~) -. . `
0.~ H c o c E~ 2 o~ a 4 ~ 9t~
OH3 0 . - ~ . '
' 0~ . . ..
38 )
0~ C5~11(t),
~NHCOCHO~C5~11(t)
C~I3 0 G 2H5
L.
-39)
OE
a~ COc~O~ f~
CH30 C2~5 12~25
' , ' ' .` -,
- . 0~ . - .
~N~C O C~ 0~ ~ .
. . ~1 C2~5 0151EI31(D)
_
- - . i3
.
.... . . .. . , '
.
,
,
' ' . ' ' '
., ,
, ''~ ' ` ' ' . , _ `
'' ' : '; S .
.
lOS~ 8 . ;.
a~/ ) `
~E[ a s~~
-~ " ~ Coc~!~o~os~11(t~ , ~
( a-Y2 3
¢ 5 ~ 1 ~ (t)
~ ~N}IOOO~O~C 51I1 1(t)
' C~ ¢ ~ 7
O~. , ~
.' ' . ' , ,
` ~¢~3)
- ~s
.o~
~ ~NECOC~O~ r
0 ~ C 2 1I 5 0 C 14 ~ 2s (~ `
.. . ~,. . . . . .
.. . .
,~, . . - ~, .
0~ a4~
~I!J El C O C H O ~ C 4 ~1 9 (B)
- $ ~I C 2E5 ..
~F, , . . . ::
, , , ,, ' ' s
,, ~ .,
.,, ~4~ ., ` .
'~
.
,
. . .
.. ,. ~ . .. . .
, ,. . . '
, . . . .
~053~
.
(C-~5)
o~ 05~I11(t)
~-N~C o c H o~ c 5~ (t)
N - H
~/ 11 -.
.' , [~ ~ .
( C--~
' :
OH
~N }I C O C R 2 $~ ~
N - ~ OC12~s(n)
~ </ 1, , ,
N - N
5These cyan couplers can be synthesized according to
such methods as disclosed in U.S.P, 2,423,730, - .
. . ~ .
U.S.P. 2,801,171, and U.S.P. 3,737,318. ~
~ ~'
`,' ' ~ .
.
,. ~
., .
. .
, ' . .
, ' ~
75- :
` 1 .
,, .
compounds of general formulas IV and V are kinds of surfactants,
they also function as surfactants in manufacturing the photo-
sensitive material, On the other hand, typical and very well-
known surfactants such as sodium dodecylbenzene sulfonate and
di-2-ethylhexyl-sodium sulfo-succinate are not effective to
improve the dye image storability.
The following compounds are typical examples of compounds
represented by Formula IV and c~n be produced according to
synthetic processes disclosed in Japanese laid-open
Application No. 46733/1974.
(IV-l) -
~aO3a--CHCOOC~I2 (CF2CF2 )~E~
~Cooc~2(cF2cF2~3
' ~ .
(IV-2
~(~C~2C~2)22. o-C~ooocH2(cF2c~23~
- G~2COOC~2~CF2c~2)2~
.'::
(IV-3)
.
C~CO(OC~2CH2 ~ 64ocElcoocH2cF2cF
O~lCO,O~ 2~oocH2cF2c~2
. , _ ..... .
- 77 -
~ .
.
:' : :,, ' ' '
~53~58
In this invention, the silver halide color photosensitive
material comprises a compound of general formula IV and V in
at least one layer element ~hereof. These elements comprise
various layers of photosensitive material; for example, a
silver halide emulsion iayer, a protective layer, a filter
layer, an intermediate layer, an anti-halation layer, and an
undercoating layer. The compound of general formula IV and V
can be incorporated into any of the layer elements. However,
in order to obtain the most advantageous results; that is,
the most effective prevention of color ch~nging and/or fading
of dye images~ it is most preferred that the compound be incor-
porated into a silver halide emulsion layer or layers in which
dye images are formed. It is also very effective if the
- compound is incorporated into a layer or layers adjacent the
silver halide layer or layers if the compound is diffusa~le
enough to move into the adjacent silver halide layer or layers.
The compounds of general formula IV and ~ are kinds of
surfactants. It is well-known that various surfactants can
be used in layer elements of a silver halide photosensitive
æo material for the purpose of improving coating or anti-static
characterisitics, etc. The use of the surfartants is especially
~mportant to obtain uniform layers. As a matter of fact,
uniform coating is impossible in phtographic maufacturing
without them. The same is true here. However, since the
76
.. _ _. .... __ .. _.. .... , . . - , F r ~
~ `~
~053~5~ ~
(IV~
,o}l2aO(OOH2C~I2 ) 1~.2ocHcooc~l2cF2cF2
a~COON~ C~I2COOCH2 ~ CF2 CF2 ) 2
.
(IV-5)
~OCH2C~I2 )~o~5ocHcoocH2(cF2c~2)5H
CH2ooocH2~cF2cF2)sH
'.
The following compounds are typical of compounds represented
by formula V and can be produced according to syntheses disclosed
in Japanese laid-open Application No. 16525/1975.
.
'': ,
2CP2)~0H20c~12c~c~I2~c~2(cP~2cF2)2
O~lO~Nh
,`~ '
~ ` ' ' ' ~"'
_ 78 -
. .
,_ . .
.-
; . -
53~S~
.' - ' " ,
(V--2 )
2o~F2)3cH2ocH2c~lcH2ocH2cF2cp~2l~, , . "
0803Na , ' ' . j
,.~
(V--3 )
~I(CF2CF?)2CH20C~I2CHCH20CH2~C:~2c~2)
0~03El
gV-Y)
, h(cF2cF2)2cH2oc~I2aHc~2oc~2(c}~2cpl2)2H
0~3
I V~
~( CF20F2)2¢}3i~0C~12C~iC~[20C~2 I CF2C~2)2~, . . .
080
'( V.- ~!; ) ' - , , ,
}I(aF2CF2)3c~20c~2cHiO}[2oc~2 ( cp~2~2~3~
080~1a -
( V~ 7 )
~F2cF2)2cE~2oo~i2c~Ic~2oc8~I17(3~
- . ` 08 0 ~lla
8 ~
2C~2 )Sc~2oC~ a~2oc8~7(~) . - ,...... ..
0803Na
,~,
19
.' ' '' ' ' .'' ' ' . ' . . ' .
.... . .. .. . . . . . . :
. '. .
.' ,-' ' -, ' . . . i,
. . , . :-
~ - - . ~ ;
lOS~5~ -
such as disclosed in Japanese Patent Publication No. 7772/71
and methods such as disclosed in the specification of U.S.
Patent No. 2,592,250. More specifically, there can be
adopted a method for preparing so called conversion emulsions
by forming an em~lsion of particles o~ silver salts including
at least one silver salt having a solubili~y higher than
that of silver bromide and converting at least a par~ of the
particles to silver bromide or silver iodobromide, and a
method for preparing Lippmann emulsions including a finely
~ divided silver halide having an average particle size not
exceeding O.I~.
Such emulsions can be sensitized by chemical sensitizers,
~uch as sulfur-sensitizers, e.g. allylthiocarbamide, thiourea,
allyl isocyanate and cysteine;- active or inactive selenium
sensitizers; noble metal sensitizers such as gold compounds,
~-g-~5 potassium chloroaurate, auric trichloride, potassium
auric thiocyanate and 2-aurosulfobenzo~hiazole methochloride;
palla~umrompounds, e.g., ammonium chloropalladate and sodium
chloropalladite; platinum compounds, e.g., potassium chloro-
platinate; ruthenium compounds; rhodium compounds and iridium
co¢p~u~ds, and the like. The chemical sensitization càn also
be accomplised by employing two or more of these sensitizers
in combination. In addition to the chemical sensitization,
reduction sensitization using a reducing agent can be applied
to ~he emulsion of thi~ mvention.
~ ~5 3~ ~
Further, the emulsion of this invention can be stabili~ed
by triazoles, imidazoles, azoindenes, benzothiazonium compounds,
zinc compounds, cadmium compounds, mercaptans and mixtures
thereof. It is also possible to incorporate into the emulsion
o~ this inve~tion a sensitizing compound of the thioether,
quaternary ammonium salt, or polyalkylene oxide type. Further,
wetting agents, plasticizers and fiLm property-improving agents
su~h as dihydroxyalkanes, e.g., glycerin and 1~5-pentanediol,
ethylene-bis-glycolic acid ester, bis-ethoxydiethyleneglycol
succinate9 and water-dispersible, finely divided granular
macromolecular compounds, can be incorporated into the emulsion
of this invention. Moreover, various photographic additives,
for example, film-hardening agents such as ethylene-imine
compounds, dioxane derivatives, hydroxy polysaccharides,
dicarbo~ylic chlorides and diesters of methanesulfonic acid~
fluorescent whitening agents, antistatic agents and anti-
sta~ing agents can also be included. Furthermore, coating
a~ tance or surfactants other than the compounds of ~his
invPntion can be employed in the silver halide color photo-
s0~sitive material insofar as the quality of the photosensitive
.
material is maintainPd.
Blue-se~sitive, green-sensitive and red-se~sitive ~mulsions
to be used for a silver halide color photosensitive mater~al
: . : - I
, ` ' ~ . -.. ..
. .
5~513
are optically sensitized to the desired wavelength regions
by employing suitable sensitizing dyes. Various sensitizing
dyes can be used for this purpose, and two or more sensitlzing
dyes can be used in combination. Sensitizing dyes advantageously
used in this invention will now be described.
Typical Pxamples of the sensitizing dyes used for the
blue-sensitive emulsion include cyanine~ merocyanine and
composite cyanine dyes such as disclosed in U.S. Patents
No. 2,108,485 and No. 2,161,331 and British Patens No. 424,559
~LO and No. 2,1613331, and cyanine dyes such as shown below:
~. 5 / 5
(CH2)3S03~ ' ~C~2)3so3
. .
~3~ H~ S~O~H3
(~ H2)3S03H (S:~2~3$03~ ......
: . - ,
--
@~S ~ ~H ~G ;~
e2~5 . C~2c}~2l:~cH2~:H
,
.
9~
. .
~os~:s~
' ~c~.~3~,~ '
C~3 ~233S0
.~C~33So3~ (C~2~3S03~3
.
; N ~
(o~2)21 S03~ (CH2)2~ ~3
. ~H3 CH3
As typical examples of the sensitizing dye for thegreen-sensitive emulsion, there can be mentioned cyanine,
merocyanine and composite cyanine dyes such as disclosed in
U.S. Patents No. 1,939,201, No. 2,072,908, No. 2,739,149
and No. 2,945,763 and Bristish Patent No. 505,979. As
typical instances of the sensiti~ing dye for the red-
sensitive emulsion, there can be mentioned cyanine,
merocynine and composite cyanine dyes such as disclosed in
U.S. Patents No. 2,2693234~ No. 2,270,378, No. 2,4429710,
No. 2,454,629 and ~o. 2~776~2800 Furthermore, cyanine,
~L~53C~S8
merocyanine and composite cyanine dyes such as disclosed in
U.S. Patents No. 2,213~995, No. 2,493,748 and No. 2,519,001
and West German Patent No. 929,080 are also advantageously
used for a blue-sensitive, green-sensitive or red-sensitlve
emulsions.
A coupler or couplers other than the above-mentioned
couplers of this invention can be incorporated, according
to need, into the silver halide color photosensitive material of
this invention in order to attain special objects. In this
o case, the coupling rate of the other coupler or couplers -~ ;
should be the same as or as close as possible to those of -
- the three couplers of this invention. For example, a magenta
coupler can also be employed in the green-sensitive emulsion
layer for masking. A suitable coupler is selected depending
on the intended purpose from various couplers capable of
releasing a development inhibitor in correspondence with
the image density at the development step. Such are disclosed
in British Patent No. 953,454, and can be incorporated into
any of photosensitive layers or a layer adjacent thereto.
It is possible to use, instead of such development inhibitor-
releasing couplerj7 a development inhibitor-releasing compound
hsving no coupling activity. As such a compound, there can
` be mentioned compounds disc~osed in Japanese Patent Publication
No. 22514/71 and, Japanese laid-open Applications No.
77635/1974 and No. 104630/1974 e~c.
- 87 -
'
~L053~S8
I~ case such development inhibitor-releasing coupler
or compoun~ is incorporated in a photosensitive emul~ion
layer, the development inhibitor is released in correspondence
with the image density at the development step and hence
controls the development in said layer in correspondence
with the image density. This exhibits so called intra-image
effects such as control of the image tone, reduction of the
image particle size and improvement of the image sharpness.
On the other hand, in case the released development inhibitor
1~ diffuses into another layer, ie exhibits so called inter-
image effects such as masking action of inhibiting the
development in said other layer in correspondence with the
image density in the layer from which the inhibi~or has been
released and improvemcnt of the color by controlling the de-
velopment in said other leayer in the case of monochromatic
exposure.
The silver halide photosensitive material for color
phoèography according to this invention is prepared by coating
blue-sensitive, green-sensitive and red-sensitive emulsion
layers incorporated with various photographic additives
mentioned above as needed on a corona discharge-treated,
fl2me-treated or ultraviolet-irradiated support optionally
through undercoat and intermedlate layers.
A~ the support advantageously used in this invention,
there can be ~entloned, for example~ baryta paper, polyethylene-
coated paper, polypropylene artificial paper, glass sheet,
cellulose acetate, ~elluiose nitrate; polyester fi~ms such
8~ !
`
.. _ _. _ .. . _ . _ _ _ .. , .. _ .. _ _ . _ _ ,, .. . _.. _ ... _ . _ . . . - . _ . _ . _ .. . ._ _ . . . ~qw~ ~~ ~
~ ~1
~5305~3 :
as polyethylene terephthalate polyamide, polycarbonate, poly-
styrene and the like. A suitable support is selected depending
on the intended use of the silver halide photosensitive material
for color photography. In watever order the photosensitive
layers may be laminated, the benefits of this inv~ntion can
be satisfactorily obtained. However, in the case of printing
photographic photosensitive material, it is desired to form
blue-sensitive, green-sensitive and red-sensitive emulsion
layers in this order from inside to outside.
In the silver halide photosensitive material for color
photography according tc this invention, a sufficient effect
can be obtained even if the thickness of an intermediate layer
provided for preventing diffusion of an oxidation product of
the coloring developing agent is very small, and in some cascs
provision of such intermediate layer can be omit~ed. Of course~
it is possible to form an intermediate layer of a suitable
thickness optionally for other purposes. Further, such layers
as a filter layer, curl-preventive layer an an anti-halation
layer can be combined as structural layers with the photo~
~ sensitive emulsion layers. Hydrophilic coll~ids suc~ as
mentioned above with respect to the photosensitive emulsion
layers can be incorporated as binders in these structural
layers. It is also possible to incorporate various photographic
additives such as mcntioned above into these structural layers~
.
,
,
.. . _ _ ... ... . ... . .
~53~ S~
It is advantageous that the silver halide pho~osensitive
material for color photography according to this invention is
sub~ected to color development according to the usual method
for development of ordinary coupler-in-emulsion type silver
halide photographic photosensitive ma~erials. In the reversal
type, the photosensitive material is first developed with a
liquid developer for black-white negatives, subjected to white
light exposure or the treatment with a bath containing a fogging
agent, and then developed with an alkali liquid developer
containing a color developing agent. After the color development,
the developed photosensitive material is bleached with a bleaching
agent comprising, as an oxidant, ferricyanide or a ferric salt
of an aminopolycarboxylic acid, and then subjected to the fixing
treatment with a fixing liquid containing a solvent or silver
salts, such as a thiosulfate, to remove the silver image and
residual silver halide while leaving a dye image. It is possible
to conduct the bleach-fixing treatment by employing a bleach-
fixing solution of the one-bath type containing an oxidant
~uch as a ferric salt of an aminopolycarboxylic acid and a
20 ~olvent for silver salts such as a thiosulfate instead of the
above-mentioned bleach and fixing solutions. Such treatments
as washing, stopping and stabilizing treatments can be combined
with the above color developing~ bleaching, fixing or bleach-
q~
.
';;
~l~S30S8
fixing treatment. The development process which can beadvantageously adopted for development according to this
invention includes, for example, the color developing
step, optionally the washing step, the bleach-fixing step,
the washing step, optionally the stabilizing step and the
drying step. This trea~ing process can be accomplished
- at a temperature not lower than 30~C in a very short time.
Typical instances of the treating process and each of
treating liquids are described below:
10 Treating Step (30C~ Treatin~_Time
Color development 3 minutes and 30 seconds
Bieach-fixing 1 minute and 30 seconds
Washing - 2 minutes
Stabilization l minute
Drying
: ' :
: ., .
i3~)58
.
B nzyl alcohol 5.0 ml
~odiu~ hex~met~phosph~te 2.~S g
AIIhydrou3 sodi~ sulfite l.9 g
$odi~ bromide 1.4 g
i~ot~lsg~um bromlde oo5 8
Bor~x ( N~2B407 IOH20 ) 39. I g
N~ethyl~N~- methan~-sulonam1doo 5.0 g
athyl-4-~mino-~nill~e Yulfate
1 0
~ot~l . I liter
Th2 pH iY ad~usted to I0.30 by additio~ o~ ~odium hy-
droxide.
~ror~ amnonium ethylenedi~ c- 6I.0 g
t~t~a-~cee~te
~am~onlum ethylenedi~ e- S.0 g
tetr~cetate
~no~ium thio~ulfate I24.5 g
~odi~m metabi~ul~ite I3~3 8
~nbydrous sodium ~t~lf ite 2 ,, 7 g
~ater balaace
- ~tal I l~ter
The p~ iL8 ~d~u~ted to 6.5 by addi~io~ of ~queou~ o~
.
.
.~ ' ' q~
1 ' ' , . .
~ f - r
r~_.~- ~.---- ---_----.. --__._ -.---__.__.__.. __._____ _._.. ____.. _.. _.. _.. _.. _.. _.. _ _.__.. __.. _. ___.. ,.__.. _. _.. __. __.. _ .. _._._. _.. _.. __
_.. _._.. _.. ,.. , .. ~j~,~,~
~ ~5~ 58
. ~ .
G1ACia1 ~cetic ~cld 20 ml
~er. 800 m1
The pEI of the solu~lon i~ ad~usted to 3.5 to ~.0! ~nd
water i~ further ~dd~d to th~ ~olutlon ~o make I ~ of ~he
~olutio~.
Primary phenylPnediamine~ and der~atlYe~ thereof cnn b~
~d~antsgeously used aq color developing ~ge~t~ for color deve-
lopment of the ~ilver hal~e photvs~n~itiv~ materIal for color
- 10 photography ~ccording to ~h~-~ inYentlon. As typi~al i~ta~ces
of such color developin~ agent, there can be men~io~ed N, ~-
dimethyl-p-phenylenedi~miney N, ~-diethyl-p~phe~yle~edlamine,
N-carbamidomethyl-N-methyl-p-ph~ylenedlamine, N-cQrb~midom~-
~hyl-N-tetrahydro~urfuryl-2-~ethyl-p-ph~nylenediAmine, N-
et~yl~N-c~rboxymethyl-2-~e~hyl p-phe~yl~di~mine9 ~car ~ i-
dam~thylN-ethyl 2-methyl~p-phenylensdlami~e, ~-cthyl~N-t~tr~
I hydrourf~ry1~2-methyl-p ami~ophe~vl9 3-~cetylamino~4-aml~odl-
j ~¢thylanil~9 N-ethyl-N-~ -m~th~ul~o~a~ido~thyl-4-amino~n~-
, N-et~yl~ e has~sulfoRa~ldo~t~1-3-~ethyl~4-Rm~no-
~ ne, N~meth~l~N ~ lfoe~ylp-p~e~len~di~e sodiu~
lt~ and the like.
I~ c~e a bleach-fi~i~g solutlo~ co~tal~i~g a f~rr~c alt
of a~ ami~opolycarbo~yllc ~cid asd n ~hl~lfste iig used ~
! t~e trea~en~ of th~ i~llv~r ~ de phot~en~tlve material f~r
I ~ ~olor photography accord~g ~o thL~ entio~ order not eo
c~use a problem of ~nv$ro~me~al pollutlo~, ~t ~prQferred ~o
- ..
~-q3
. . ..
- r
. . ~ . ,' .
~ ' ' , :. " ~, ' ';' '
3L05;~058 `
use the bleaching-fixing liquid repeatedly by recovering the
active portions of the liquid used so as to make it re-usable
while reducing the amount discharged of the liquid to as low
a level as possible.
The liquid can be regenerated by contacting the used
liquid with steel wool to remove at least part o~ the silver
ions formed at the treatment step, and simulatenously or sub-
sequently blowing oxygen or an oxygen-containing gas into the
liquid and thus contacting the liquid with oxygen to convert
lQ ferrous ions formed by reduction of the ferric aminopolycarboxylate
to ferric ions, there~y-restoring the oxidation potential of
the liquid without decomposition of the thiosulfate. In
conducting such regeneration treatment, ~o further improve the
effeet of recovering the active portions of the liquid, it is
pre~erred to add a regenerating composition such as disclosed
ln the specification of U.S. Patent No. 3,700,450.
This invention will now be described in more detail by
referPnce to the following Examples:
Example 1
Layers 1 to 6 as set forth hereinafter were coated on poly-
ethylene-coated paper in the order set forth starting with the
support. The dry thicknesses of layers 2 and 4 were ~u, 2~,
~ and 0. ~ in su~cessive tests and the foux kinds of pho~o-
sensitive materials w~e~sed as samples 1 to 4, respectively.
.
- ' : :
., : . '' . . . :'.:.
~ i3058
Layer I:
A yellow coupler-containing, blue-sensitive silver
halide emulsion (an emulsion of silver chloroiodobromide
including 1 mole % of silver iodide and 80 mole % of silver
bromide, which contained 400 g of gelatin per mole of the
silver halide and was sensitized by the following sensitiz-
ing dye:
U3C~ ~ ~ CH ~ Sc ~ OC~3
(CH2)3S03H (CH2)3S03
in an amount of 2.5 x 10 4 mole per mole of the silver
10. halide, an~ in which the coupler Y-34 was dispersed in the
state dissolved in dibutyl phthalate in an amount of 2 x 10
mole per mole of the silver halide) was coated so that the
amount coated of silver was 400 mg/m2.
'
Layer 2:
Gelatin layer (intermediate layer).
Layer 3:
A magenta coupler-containing, green-sensitive silver
halide emulsion (an emulsion of silver chlorobromide includ-
ing 80 mole % of silver bromide, which contained 500 g of
-9.5- :
, ~,, . ' ~,
. ~ , . ;.- :
~ 53058
gelatin per mole of the silver halide and was sensitized by
the following sensitizing dye:
0
(CU2)3S03~1 (CH2)3S03 9 :~
in an amount of 2,5 x 10 4 mole per mole of the silver hal-
ide, and in which the coupler M-22 was dispersed in the state
dissolved in tricresyl phosphate in an amount of 2 x 10-1. . . .
mole per mole of the silver halide) was coated so that the
amount coated of silver was 500 mg/m2. :
','
Layer 4:
Gelatin layer (intermediate layer),
. .
Layer 5:
A cyan coupler-containing, red-sensitlve silver halide
emulsion (an emulsion of silver chlorobromide including 80
mole % of silver bromide, which contained 500 g of gelatin
per mole of the silver halide and was sensitized by the fol-
lowing sensitizing dye:
CU= CH -C~ ~--C2aS
C2H5 I ~3
in an amount of 2.5 x 10-4 mole per mole of the silver halide,
-96-
; . ' : ' .
:: . . . .
~053(~5~3
and in which the coupler C-9 was dispersed in the state dis-
solved in tricresyl phosphate in an amount of 2 x 10 1 mole
per mole o the silver halide) was coated so that the amount
coated of silver was 500 mg/g2.
Layer 6:
Gelatin layer (protective layer) having a dry thick-
ness of ly~.
Each silver halide emulsion used for formation of layers
1, 3 and 5 was prepared according to the method disclosed in
Japanese Patent Publication NoJ 772/71, and each emulsion was
chemically sensitized with sodium thiosulfate pentahydrate and
had incorporated therein 4-hydroxy-6-methyl-1, 3, 3a, 7-tetra-
azaindene sodium salt as a stabilizer, and bis-(vinylsulfonylmethyl)
ether as a film-hardening agent. In addition, each of the layers
contained compound IV-l in an amount of 0.5g per lkg of a coating
: liquid therefor.
4 kinds of photosensitive materials or color photography
difering in the intermediate layer thickness were prepared
by fonming the laminate structure in the same manner as in the
case of samples 1 to 4 and employing the following yellow
~oupler Yl instead of coupler Y-34, and they were used as
samples 5 to 8.
Yellow coupler Yl:
3 ~ '
C~3 -C -COCHCONH ~
C~3 ~l N~C0~2)30 ~ CsNII(e)
''' '-''''" -` ' ' ; C5RII(t~
, "" ", ~", ~, ~, ",,", :", , ~,
~ 53058 . ~
Then, another 4 kinds of photosensitive materials for
color photography differing in the intermediate layer thick-
ness were prepared by forming the laminate structure in the
same manner as in the case of samples 1 to 4 and employing
the following magenta coupler Ml instead of coupler M-22, .
and they were used as samples 9 to 12.
Magenta coupler Ml:
Cl ~ l N - C - ~CO ~ / C~ CH- CI?U25~3)
l ll 2 C- C~l2 ~:
Then, still another 4 kinds of photosensitive materials
for color photography differing in the intermediate layer
thickness were prepared by forming the laminate structure in
the same manner as in the case of samples 1 to 4 and employ-
ing the following cyan coupler Cl ins~ead of cyan coupler
C-9, and they were used as samples 13 to 16.
Cyan coupler Cl:
0~1
~I I ( t
~, .
Then, still another 4 kinds of photosensitive materials
for color photography differing in the intermediate layer
thickness were prepared by forming the laminate structure in
'
" '
-98-
.
, ~
'1~53~S8
the same manner as in the case of samples 1 to 4 by employing
yellow coupler Yl instead of coupler Y-34, magenta coupler Ml
instead of coupler M-22 and cyan coupler Cl instead of coupler
C-9, and they were used as samples 17 to 20.
Separately, comparative photosensitive materials were
prepared by forming only a layer 1 including coupler Y-34 or
yellow coupler Yl on a polyethylene-coated paper, and they
were used as samples 21 and 22. Further comparative photo-
~ensitive materials were prepared by forming only a làyer 3
including coupler M-22 or magenta coupler Ml on a polyethylene-
coated paper and they,were used as samples 23 and'24. Moreover,
comparative photosensitive materials were prepared by forming
only a layer 5 including coupler C-9 or coupler Cl on a poly-
ehtylene-coated paper, and they were used as samples 25 and 26.
Moreover, the preparation of sample 3 was repeated except
that di-2-ethylhexyl-sodium sulfo-succinate (comparative
' compound A) was employed in each of the layers in an amount
of 0.5g per kg of the coating liquid in place of compound IV-l.
~his sample is numbered as 27.
T~e preparation of sample 3 was'additionally repeated
except that a combination of co~pound (IV-l) and cOmparative
compound A was used in all layers respectively in an amount
of 0.5g per kg of the coating liquid instead of compound (IV-l)
alone in sample 3. This is sample 28. ~ '
9~9
.`
. :..... ~ .. . . . ..
.
53t~S8 `-
The aforementioned 28 samp~s were exposed to blue,
green and red light through light wedges by employing a
sensitometer (Model KS-7 manufactured by ~onishiroku Photo
Industry Co., Ltd.), and subjected to the color development
according to the following ~reatment steps:
Treatment Steps (31C);TPeat-~e~t Time
Color development 3 minutes
Bleach-fixing 1 ~inute
Washing 2 minutes
Stabilization 1 minute
Waahing 10 minutes
Drying ( b~low 95C.)
Compositions of treating solutions used at the above
steps are as f~llows :
Composition of Color Developing Solution:
N-ethyl-N- -methanesulfonamidoethyl- 4.0 g
3-methyl-4-aminoaniline sulfate
Hydro~ylamine 2.0 g
Potassium carbonate 2B.O g
Sodium chloride ~.I g
Sodium bromide 0.2 g
Anhydrous sodium sulfite 2.0 g
Benzyl alcohol 10.0 m
Polyethyleneglycol (average poly- ~3.0
merization degree)
Water balance
.
, Total 1 liter
The pH was adjusted to 10.0 by addition of sodium hy- -
, droxide.
:~ "' , ''
-100- ~ '
1~53C~5i3
Composition of Bleach-Fixing Solution:
Iron sodium ethylenediaminetetra-
acetate 60.0 g :
Ammonium thiosulfate 100.0 g
Sodium bisulfite 10.0 g t
Sodium metabisulfite 3.0 g
Water _ balance
Total 1 liter
The pH was adjusted to 6.6 by addition of aqueous
ammonia.
Composition of Stabilizing Solution:
Succinic acid 10.0 g
Formalin (37% aqueous solution)15Øml
Water 800 ml
The pH of the liquid was adjusted to 3.9 by addition ;
of sodium acetate, and water was further added thereto to ~ -
make 1 liter of a treating liquid. : ~:
Each of dye images formed on the foregoing samples was
tested with respect to the reflection density by employing
a photoelectric densitometer (Model PDA-60 manufactured by ~ -
?0 Konishiroku Photo Industry Co., Ltd.) according to the fol~
lowing method, to examine the degree of formation of color :
turbidity in each photosensitive emulsion layer caused by
the influence of the adjacent photosensitive emulsion layer
or layers. More specifically, in the yellow color-formed
area, the magenta denslty (DG) in the light-wedge e~posed
area coLresponding with the yellow density of 1.00 measured
- 1 0 1 -
~(~53~51~
: by a blue filter was measured by means of a green filter,
and in the magenta color-formed area, the yellow density (DB)
and c~an density (DR) in the light-wedge exposed area corres-
ponding with the magenta density of 1.00 measured by a green
S filter were measured by means of a blue filter and a red fil-
ter, respectively. In the cyan color-formed area, the ma-
gent,a density (DGl) in the light-wedge exposed area corres-
ponding with the cyan density of 1.00 measured by a red fil- .,.
, ter was measured by means of a green filter. Results are
shown in Table 1.
~. -102-
~1~53051~
_ . ~
C ~rJ~1 ~ ~ ~t ~ ~ ~ ~t U~ ~ ~t ~D C;~ ~) ~O cr~ O /~ I~ o~ ~ 00 00 ~'1 ~t
~ h Q~ ~') ~ ) ~) ~1 ~ ~') ~ ~ ~') ') ~) ~) ~ ~t ~ ~ ~ ~t C~l ~ ~) ~
~ ~OOOOOOOO.OOOOOOOOOOOO OOOO
E-l __ .~
rd~ t ~ 00 ~ ~t 1~ a~ oo O O O~ J
I I ~ ~ I I ~ ~
OOOOOOOOOOCOOOOOOOOO OO OO
U~ ~ ._ .. _ . - _ _ ''' ~ '
J- r~ t ~ ~ ~ ~ O ~ ~ 1
Z C o~ J ~, ~, ~f7 ~, ~ ~ ~ ~ ~ ~ ~ ~ ~ ~) ~) ~ ~ ~ ~t ~t
. t~l ~ ' 00000000000000000000 00 0,0
- _
~t ~t ~t U~ t ~t U~ ~ ~t ~t L/~ O 00 0 ~ ~ t ~t`
3 (~J ~ ~1 ~
~ COOOOOOOOOOOOOOOOOOOOO OO
.` ~ ~:'''''
~ _ ~_ __ _ _ .__
~ _~
~ ~ t . ,~
~ ~ ' :.
V~ :
a) o c~ c~ o o o ~ o o o ~ o o o ~ o o o ~ o o o ~ o o ~ -
~ ~ ~ ~ C; ~ ~--I O ~ ~ ~ O r~ ~ ~ O ~ C~l ~ O ~
.,1 ~ ~ . ' .
E~ ~ '.
_ _
h O~ ~ : .
,_1 ~ _ _ _ _ _ _ - - - - _ C ~ - _ _ - - _ _ I I I I I ~) I -
.. _ .__ ___ .... _.. . _ __
~J ~ ~ ~ ~ C~l ~ ~ '. '
P~ ~ ~ ~ _ _ _ _ _ - - ~ - - _ ~ - _ - ~ - _ - I I C~l ~ I I ~ _
,_~ ~_
c~ -- ---I -
~ ~ ~t ~ ~t ~ - -
__ ~ ~.,
_ C~ . , ,_._ . _ _ .
0 r~ ) ~t U~ O ~ ~ ~1 ~t U'l ~ r~ 00 Cl~ O ~ ~ t Ln ~ 00
E Z ~ ~ _I ~ ~ ~ ~ _~ ~ ~ ~ ~ C`J c~l ~ C~J ~ c~ C`J
. _ __ _ _ _ __
.
- -103-
~.
- -: . : . . . :,:
`
~ ~S 30 S~
With respect to samples 27 and 28, the quality of color
changing and¦or fading ( dye image stability) was tested
according to the following method after the samples were
exposed to light and then processed as mentioned before. The
samples were stored for two weeks at 65C and 70% Relative
Humidity (R.H.) in a constant temperature-humidity chamber.
Then, densities of parts of the samples were measured to see
the degree of color fading, the densities of which parts had
been 1.0 before the above treatment. Densities of unexposed
areas Gf the samples ~in wh W~ areas no dyes were expec~ed) were
also measured and compared with densities of the areas before
the above treatment in order to determine the degree of color
changing. The densities of each of the dye images were measured
through filters. A blue filter was used for measuring the
yell~w dye area, a green filter for the magenta dye are, and
a red filter for a cyan dye area. The unexposed area was
measured through a blue filter.
The results are shown in Table 2.
,
~)5305i~ -
T~IE 2
_ ~ , _
¦ DYE IMAGE S~ABILITY
Density after the
treatment at the
SAMPLE COMPOUND area of density 1~0 Density of
NO. USED before th~ treatment unexposed area
. Yellow ¦Magenta ~ Cyan ,Be~ore thelAfter the
__ . dye area dye areald~e arealltreatment treatment
3 Cpdo(N~ 0.97 0O95 0.99 ¦ 0O05 0.08
27 Cpd. A 0.79 0.56 0O05 0.27
28 ~pd.(N~ 0.91 0.84 0~O73 0O05 0.15
ComparO ¦ L~ ~_
/e~s~ .,
~ffS
.
~L~53~8
As is apparent from the results shown in Table 1, in
~amples 1 to 4 of this invention, formation of color turbidi-
ty was hardly observed in dye images formed in respective
photosensitive emulsion layers and clear color images could
be obtained even if the thickness of intermediate layers was
extremely reduced. In addition, as is apparent from Table 2,
the sample containing compound (IV-l) of this invention has
excellent dye image stability and hardly changes or fades in
color at all when compared with the samples not containing
the compound.
Example 2
On a polyethylene-coated paper, the following layers were
formed in order starting from the support side, toge~her with
two intermediate layers 2 and 4 having a dry thickness of 2~,
~ or 0.2~, to thereby form 3 kinds of photosensitive materials,
which were used as samples 29 to 31.
.. , . ,
L~yer I:
-A yellow coupler -contai~i~g, blue-sensitive ~il~er
- halide cmul~ion ~ a~ emuls~os~ of 3ilver chl~roiodobrom~ de in-
20 cludlng I mole % o~ gilver iodid~ ~d 80 mole ~ of.sil~er
bromide, whlch cont~ined 400 g o~ gelatln pe~ mole of ~che
~lver halide and was ~en~i~ized b~ the ollowing sensitizing
dye~
>~ C8
)3so3R ~ ~ B2~3~03
., IG~
... . . .. . ..
- ~53~S8
in an amount of 2.5 x 10-4 mole per mole of the silver hal-
ide, and in which the coupler Y-8 was dispersed in the state
dissolved in dibutyl phthalàte in an amount of 2 x 10~1 mole
per mole of the silver halide) was coated so that the amount
coated of silver was 400 mg/m2.
Layer 2: :
Gelatin layer (intermediate layer).
Layer 3:
A magenta coupler-containing, green-sensitive silver
halide emulsion (an emulsion of silver chlorobromide includ-
ing 80 mole % of silver bromide, which contained 500 g of
gelatin per mole of the silver halide and was sensitized by
empl`oying the following sensitizing dye:
C2~5 ~,.
CH- C- CH - 6
C2Hs SON C~5
in an amount of 2.5 x 10-4 mole per mole of the silver hal-
ide, and in which the coupler M-l was dispersed in the state
dissolved in tricresyl phosphate in an amount of 2 x 10-1
... ..
mole per mole of silver halide) was coated so that the
amount coated of silver was 500 mg¦m2.
Layer 4:l
Gelatin layer (intermediate layer).
107-
?5~58
Layer 5:
A cyan coupler-containing, red-sensltive silver halide ~-~
emulsion (an emulsion oE silver chlorobromide including 80
mole % of silver bromide, which contained 500 g of gelatin
per mole of the silver halide and was sensitized by employ-
ing the following sensitizing dye:
O- ~ N ~ ~ N ~
. C2~5 C2~5 S4C2~5
in an amount of 2.5 x 10-4 mole per mole of the silver hal-
ide, and in which the coupler C-41 was dispersed in the state
dissolved in tricresyl phosphate in an amount of 2 x 10~1
mole per mole of the silver hallde) was coated so that the
amount coated of silver was 500 mg/m2.
LAYER 6:
Gelatin layer (protectlve layer) having a dry thickness
of I~U.
Each of silver halide emulsions used for formation of
layers 1, 3 and 5 was prepared according to the method dis-
closed in Photographlc Chemistry, Vol. 1, Page 346 (written
by Grafkis [phonetic] and published by Fountain Press), and
,
each emulsion was chemically sensitized by using sodium ~hio-
sulfate pentahydrate and incorporated with 4-hydroxy-6-
methyl-I, ~, ~a, 7-tetra-azaindene sodium salt as a stabil-
izer, and l, 3-bis-(aziridinylsulfonyl)-propane as a filQ-
hardening agent. Each of the emulsion layers were incorpo-
25 , rated with compound V-6 in an amount of 0.58 per 1 kg of a
coating liquid therefor.
-108-
s~s~ :
Then, 3 kinds of photosensitive materials for color :
photography differing in the intermediate layer thickness
were prepared by forming the laminate structure as in the
case of samples 29 to 31 and employing the following yellow
coupler Y2 instead of coupler Y-8, and they were used as
samples 32 to 34.
Yellow Coupler Y2: :
C2Hs
(t)C5HII- ~ OC~OONH - ~ OC~3
S~II(t) COCHCO~H
Br
Then, another 3 kinds of photosensitive materials for
color photography differing in the intermediate layer thick-
ness were prepared by forming the laminate structure as in
the case of samples 29 to 31 and employing the following
magenta coupler ~I2 instead of coupler ~1-1, and they were : -
used as samples 35 to 37.
Magenta Coupler M2:
<C IH NUCOCU20~-C5~1I(~)
Then, still another 3 kinds of photosensitive materials
for color photography differing in the intermediate layer
thickness were prepared by forming the laminate structure
as in the case of samples 29 to 31 and employing the follow-
ing Fyan coupler C2
-109-
.. : ., . , ~ , : ... ~ ; . ,:,:
~S~ 5 ~
instead of coupler C-41, and they were used as samples 38
to 40.
Cyan Coupler C
OH
I6H33(~)
Cl
Separately, still ano~her 3 ki~ds of pho~os~ns~lve ~tex
~al~ ~or color phot~ra~hy di~er~ng in the intenmediate layer
thick~es~ were prepared by orming ~he laminate structurc as in
; the case of s~.lples 29 to 31 and ealploying yellow coupler Y2
instead o coupler Y-8, magenta coupler M2 instead of coupler
M-l and cyan coupler C2 instead of coupler C-41, and they were
used as samples 41 to 43.
Comparative photosensitive materials were prepared by or-
mining only a layer 1 including coupler Y-8 or yellow coupler
Y2 on a polyethylene-coat2d paper, and they we~e used as samples
44 and 45. Further eomparative photosensitive materials were
prepared by forming only a layer 3 including coupler M-l or
~agenta coupler M2 on a polyethylene-coated paper, and they
were used as samples 46 and 47. S~ urther comparati~e
photosensitive materials were prepared by fonming only a layer
5 ~ncluding coupler C~41 or coupler C2 on a polyethylene-coa~ed
paper, and they were used as samples 48 and 4g.
. Moreover, the method of producing sample 3~ as repeated
to obtain sample 50 except that sodium-9-hexadecylsulfonate
~comparative compourld Bj was used in an amount of 0.5g per kg
of the coating liquid in each of the layers in place of compound
~-6.
11
:;
~53()~8
..... .
a~ .
r~ ~ Ln `D O~ r~ cr o o ~ ~ ~ I~ ~ ~ oO 1
C~ ~ ~ ~ ~ ~ ~ ~ ~ ~ ~ C~l
~ ~, a ............... ,,,, ................. ..
~¢ooOoooooooooooo 000
_
E~ ~c~ ~ O ~ C~l
a~ ~~ ~ ~ ~ ~ ~ ~ ~ ~ ~ ~ ~ ~ ~ ~ ~ ~ ~
s~. ~ ............... I I .. I I . :
. coooooooooooooo oo o . .
U~ ~ _ ::
~d . , ''
. U CO CO O~ ~o ~ o ~ C~l 00 ~ O ~ O U~ O ~ 00 00 , ..
Z ~:: Q e`! C~
~) OOOOOOOOOOOOOOO OO O
~ ~ . : '
~ a)
~ ,
~a c~ : .
3 ~) C~) ~1 ~ ~ ~ --I C~! --1 ~ r-l ~1 ~ ~1 ~ ~--I C~l ~ ~1 ~J
O~ ~ ..................... III~-
~¢ OOOOOOOOOOOOOOOOO O
~ ~', '
_ . _
~t
U~
U~ ~ ~ ~ O ~ O O C~ O O C~l O O ~ O O ~ O
~; a)O~ ............... ~ .
E~ C`J ~ o c~l ~ o ~ ~ o ~ ~ o c~ ~ o ~
~ ~ SJ .'
' ~ ~ . ~ -
.'
. _ _ .,. . ":
. :,
~t ~ ~t~t
U~ ~ _ _ _ -- - - - _ ~ - - _ _ _ I ~ ~ I I C~ I
a ~ ~
~ I . .. .. _ : - ''
a~ ~ c~ ~ ~ ~
~ ~ X ~ X ~: .~ .
o ~
C~ s~ . .
--I 00C~l 00 ~ 00 ~ CO
~5 ~ I I I
.
aJ .
~O ~O~t~O~t~O
~t~t~t~t~t~t~t~t~
-112-
- . .: ,, ~. -
; . .
1~53051~ -
The aforementioned ~2 samples were exposed to blue,
red lights through light wedges by employing a sensitometer,
and the exposed samples were subjected to the color development
acco~ding to the same treatment steps as in Example 1 by using
the same treating liquids as used in Example 1. The reflection
density of each of dye images foxmed on these samples was
measured in the same manner as in Example 1 to examine the
color turbidity in each photosensitive emulsion layer caused
by the influence of the adjacent photosensitive emulsion
~0 layer. Results are shown in O le 3.
-
.. /1/
.
,
;' .,
~, ,'1 : '
'``; l :
10S;~58 ~ `
With respect to .samples 30 and 50, the dye image
stability was tested as mentioned in Example 1. The results
ar~ shown in Table 4. 1'
TABLE4
.,. ., _ '' ' 1~'''
¦ DYE I~GE STABILITY ~ -
. . I Density after the
¦ treatment at the 1'
SA`MPLE COMPOUND j area of density 1.0 ! Density of i~ -
NO. I USED before the treatment ~ unexPosed area ~ '
¦ Yellow I~Sagenta ¦ Cyan Before the¦After the
dye arealdye area dye area treatment Itrea~ment
Cpd.(V-6) ¦ 0.9~ j 0.97 j 0.98 1 0.05 0.10 l.
. 50 Compar. j 0.85 ¦ 0.85 1 0.52 1 o.o~ i
~ .'.
~ .... .
,, ~; .
~ '~". ~ ;... '
~..:
:, . ~ . ~
,~
:,. ..
.`'~':
- . ~
'~
,.,
,.,~
. . ~, . . . .
~.. . : .,
.
~ ~S30 S~
As is apparent from the results shown in.Table 2, in
saMples 29 to 31 of this invention, formation of color
turbidity was hardly observed in dye images formed in respective
photosensitive emulsion layers and a clear color image could
be obtained even if the thickness of intermediate layers
was extremely reduced. Furthermore, the sample containing
compound (V-6) of this invention hardly changer or faded in
color when compared with ~he sample not containing the compound
and has excellent dye image stability as is apparent from
Table 4.
.
Example 3
On a polyethylene terephthalate film, the.following
layers were formed in order from the support side. The thick-
ness of the intermediate layer was ~aried so that three kinds
of photosensitive materials were obtained having the inter-
mediate layer of 2~ or 002p in thickness respectively.
Those samples were respectively numbered as 51 to 53.
;
Layer 1-:
A cyan coupler-containing red-sensitive silver halide
emulsion (a highly sensitive emulsion of iodobromide containing
. 7 mole~h of silver iodide which emulsion contained 200g of
gelatin per mole of silver halide) was sensitized by the
following dye:
.
. . .
: ,, . ,,: ,
~5~ 5~
~ S ~2~ /S ~ ~1
cl S 2 3 3 (CH2~3S03~
in an amount of 2.5 x 10 4 mole per mole of the silver halide,
and inwhich emulsion the coupler C-ll was dispersed in the
state dissolved in a mixed solvent of tricresyl phosphate and
ethyl acetate in an amount of 0.7 x 10 1 mole per mole of the
silver halide) was coated so that the amount coated of silver
was 2000 mg/m2.
Layer 2
Gelatin layer (an intermediate layer).
Layer 3
A magenta coupler-containing, green-sensitive silver
halide emulsion (a highly sensitive emulsion of silver iodo-
bromide including 7 mole % of silveriodide, which emulsion
contained 200g o~ gelat~ ~ ~er mole of the silver halide
and was sensitized by the following sensitizing dye
H -C -C~
~ ~ N ' ~
~H2)3So3H (CH~)3So3G~ :
.
: 4 ~ ?
in an amount of 2.5 x 10 mole per mole of the silver hallde,
and in w~ich emulsion the coupler M-ll was dispersed in the state
-. disso~ved in a mixed solvent-of tricresyl phosphate and ethyl
,
scetate in an amount of 0.7 x 10 1 mole per mole of the silver
halide) was coated so tha~ the amount coated of silver was
2000 mg/m2.
11
.. ~ . , .
.. . ; , -
~6~53
Layer 4:
A yellow f~lter layer (~gelatin layer contai~lng a dye-
~rrier lpolymer having the guanidylketimine structure~and
the following yeilow dye .'
CH3 1 ~ CH ~ CR~
N ~O H ~ N
N N
,," , ~il ~3 " ' '
Sû3H S03H
in combinat~on ) h~v:5ng a dry thi~knes~ of 0.3~..
L~yer 5:
A yellow coupler-containing, blue-sensit~v~ ~ilver halide
em~lsion ( a highly 3ensitive emulsio~ of silver iodobromide
~cluding 7 mole % silver iodide9 wh~cl-emulslon contained 200 g of
gelatin per mole of th~ silver halide and ~n whlc~ emuIsion the`ooup~r
~?7 was dispersed i~-the state di~solved i~ a mixed ~olvent
o~ dibutyl phthalate and eehyl acetat i~ a~ amount of I.5 x
I0~ mole per mole of the silver hallde ~ w~s coated so that
~he smount coated of 5ilve~ wa~ IS00 mg/m2.
L~ 6:
G~laein layer ~a protect~Ye layer) having a d~y thickness
~f I ~Lo
EEICh of ~llver halide emulsion5 used for ~.~
layer~ ~,, 3 arld 5 was prepared by the neutral method', arlà
. .. ~ _ - ,
- llb
. ` ' -
.
_ . _ .. . .. .... . ~
:. ~ . ' , . .,......... : .
...
~ 0530 58
each e ~ lsion was chemically ~ensi~ized with pota~sium cholro-
nur~te and s~dlu~ thiosulfate pentahydrate a~d incorporated
with 4-hydroxy6-methyl-I, 3, ~a, 7-tetra-~zaindene sodium
8alt AS a 8tabilizer, and N, N', N"~triacryloyl-hexahydro-S-
triazine as a film-hardening agent. In additon, a combination
(1~1 by weight) of compound IV-5 and compound V-2 was incorporated
into each o~ the layers in an amount of 0.5g per kg of coating
liquid therefor.
Then, 3 kinds of photosensitive materials for color photo-
graphy differing in the intermediate layer thickness were pre-
pared by forming the laminate structure as in the case of sam
ples 51 to 53 and employing the following yellow coupler Y4
instead of coupler Y-77, and they were used as samples 54 to
56.
Yellow coupler Y4 - . ,
. . . _ . . .
. Cl
,~ coc~co~ -~ S r
~Sr ~00 ~E~COOCI2~2S(~) ~
. , . . . ~
GH~ ~
,~, ..
' `' . ' '- ~
The~, another 3 kind~ of photose~si~l~e ma'c~rlal~ for
¢~lor photography diering 1D the ~termediate layer ~hick-
. ~es3 were prepared by forming the lam~nate structure as ~ the
case of samples 51 to 53 and employing the follo~iDg magentacoupler M4 instead of coupler M-ll, and they were used as samples
57 to 59.
117
., ~ :
~ 53~58
Magenta Coupler M4:
Cl
~ Cl < ~ C -NHCO - ~
Then, still another 3 kinds of photosensitive mater-
ials for color photography differing in the in-termedlate
layer thickness were prepared by formlng the laminate struc-
ture as in the case of samples 51 to 53 and employing the
following cyan couplèr C4 instead of the coupler C-ll, and
they were used as samples 60 to 62.
Cyan Coupler C4:
OH C\5HII(t)
C~3 ~ N~3co(cH2)3o ~ C5HII(t) :
Cl
Then, still another 3 kinds of photosensitive mater-
ials for color photography differing in the intermediate
layer thickness were prepared by forming the laminate struc-
ture as in the case of samples 51 to 53 and employing the
yellow coupler.Y4 instead of coupler Y-77, the magenta
coupler M4 instead of the coupler M-ll, and as the cyan
coupler the cyan coupler C~ instead of the coupler C-ll,
and they were used as samples 63 to 65.
-118-
~'
~LOS3~58
Comparative photosensitive materials were prepared by
forming only a layer 5 including coupler Y-77 or yellow coupler
Y4 on a polyethylene terephthalate ilm, and they were used
as samples 66 and 67. Additional comparative photosensitive
materials were prepared by forming only a layer 3 including
coupler M-ll or magenta coupler M~ on a polyethylene tere-
phthalate film, and they were used as samples 68 and 69. Still
further comparative photosensitive materials were prepared
by forming on~y a layer I including coupler C-II or cyan
coupler C4 on a polyethylene terephthalate film, and they
were used as samples 70 and 71.
Moreover, the method for producing sample 52 was repea~ed
to obtain sample 72 except that sodium dodecyl benzene su~fonate
(comparative compound C) was used in each of the layers in
an amount of 0.5 g per kg of the coating liquid in place of the
combination of compounds :(IV-5) and (V-2). .
The aforementioned 22 samples were exposed to blue, green
and red lights through light wedge~ by employing a densitometer,~
~nd they were subjected to the color development according to
P0 the following treatment steps: - -
Treatment Steps (38C) Treatment ~ime
- Color development . 3 n~nutes and 15 seconds
~leach-fixing 6 m~nutes
; ~ashing 3 minutes and 15 seconds
Stabilization 1 mihute and 30 seconds
~rying (below 80C)
Compo~itions of treating liquids used at the above treating
- ~teps are as ~ollows: .
119
-
- ~ `
lOS31:)S8
Composition of Color Developing Solution:
N-methyl-N-~ -hydroxyethyi-3-methyl-
4-aminoaniline sulfate 5.0 g
Hydroxylamine sulfate 2.0 g
Anhydrous potassium carbonate 26~0 g
Anhydrous sodium bicarbonate 3,5 g
Potassium sulfite dihydrate 18.0 g
Potassium bromide 1.3 g
Sodium chloride 0.2 g
Sodium nitrilotriacetate monohydrate 2.0 g
Potassium hydroxide 0,4 g
Water balance
Total 1 liter
The pH of the liquid was adjusted to 10.5 by addition
of sodium hydroxide.
Composition of Bleach-Fixing Solution:
Iron sodium ethylenediamine-tetra
acetate 180 g :~;
Ammonium thiocyanate 200 g
Water balance
. .. _
Total 1 liter
-120-
~53~5~3
The pH of the liquid was adjusted to 500 by addition
of aqueous ammonia.
Composition o Stabilizing Liquid:
Formalin (37% aqueous solution) 105 ml
Konidax (product of Konishiroku
Photo Industry Co., Ltdo) . 7.5 ml
Water balance
.
Total 1 liter
The density of each of dye images formed on the samples
was measured in the same manner as in Example 1 except that the
the density was determined as the transmission density, to
. examine formation of color turbidity in each photosensitive
emulsion layer caused by the influence of the adjacent photo-
sensitive emulsion l~yer or layers. Results are shown in Table
~; ,
.:
.
; "'
~71
' ' '
- ;
~53~58
_ ~ . .... .
D
C~ ~ ~ C~l ~ C~l ~ ~ C~l C~ ~ ~ ~ ~ ~ ~ C~l C~ C~
. ~ ~ a ............... ,.... ,
oooooOooooooooo 000
~ ~)
.. I . . ~_
.
~d o~ ~ o ~ ~ ~ ~
~ ps o o o o o o o _ ~1 _ ~ ~ _ _ _ o o o
H ~1 O O O O O O O O O O O O O O O O O O
U~ 1~ . _.
. J a~ ~ ~ o o c~l ~ ~ _ o _ ~'O`~
Z; ~: ~ c~ ~I ~ ~ ~) ~ ~ ~ u~ ~1 ~ ~1 ~ ~ In C~l 1~ C~t
a) 1::~ ~ ........ ~ ~ .. ~ ... ~ . I I ~ . I I ~ .
I:lO OOOOOOOOOOOOOOO OO O
.~ . . ___ .. _
~ ~ '
~ O ~ ~ O ~ ~ 0'~ ~ o o ~`C~
3 0 C~) ~ ,1 ~ ~1 _ ~ _ _ ~1 _ ~1 _ _ ~1 0 0
0 ~1 C~ ................. l l l I .
~: 00000000000000000 0 .,
~ :,,
_ . . ~
U~ ~_
~ u~ ~ ~ : :
E~ u~ o o c~l o o c~ o o C~l O O C~l O o C~l , O ,,:
a~ , ...................... i i, I I I
Q o ~ ~ ~ ~ o ~ ~ c~ ~ ~ o ~ ~ o ~ ~ o ~
,~, ~ :. .
. ._ . - , . _ :~ .
,~ ~ _ ~ .~
~ ~ , .. C, . _ ~ _
,~ ~
. ~ _ ~ _ ~:
~ ~ ~ . _
o .. _ .__ _ _
. ,~
ta , " , - ~ - - , ", , , , ,
.. . ........... _ _
~ . , .
o ~ c~ O ~ ~ ~ ~ L~l ~ I~ 00 a~ o _ c~J
. _. ~ ~ 1
~ ,
-122-
.
.. ; : ; . . . :
1~53(~5~
With respect to samples 52 and 72, the dye image
stability was tested as mentioned in Example l except that the
transmission density was measured in place of the reflection
density. The results are shown in Table 6.
T~BLE 6-
. . .
. ¦ DYE IMAGE STABILITY
. ,
. ....................... Density after the
. treatment at the
SA~LE COMPOUND area of density l.O Density of
NO. ! USED before the treatment unexposed area
. . ¦ Yellow ¦Magenta ~ Cyan Before the¦After the
. .~. . . ~ dye area dye arealdye area~treatment ltreatment
Cpd.(N-5~ 1 .
52 0.93 0.95 0.94 0.02 0.05
. .Cpd~(V-2)
72 I Cpd. C1 0.79 0 80 O 49 0.~2 0.16
,~ -
.
.
1~
~i _
.. .... ~,r~
' 1 , :
lQS3~5~
As is apparent from the results shown in Table 5, in
samples 51 to 53 of this invention, as seen in Examples 1,
and 2, formation of color turbidity was hardly observed in
dye images formed in respective photosensitive emulsion
layers and clear color images were obtained even if the
thickness of the intermediate layer was extremely reduced.
In addition, as is apparent from Table 6, the sample containing
the com~ ation of compounds IV-5 and V-2 of this invention
hardly changed or faded incolor when compared with the ~'
sample not containing the compounds and had excellent dye
image stability.
~7-
. . - . . . ~
- . . .. . . .
~: . ..
. .. ~ ... .
. . . . . . . . . ..
.: , : , . .
3~ 5
Example 4
A comparative photographio material 73 was prepared in a same
manner as sample 27 of Example 1 except including Yellow
coupler Y-49 instead o~ Y-34~
A test sample 74 was made in a same manner as comparative
~ample 73 except including VI-l instead of comparative
compound A ( di-ethyl hexyl sodium sulfo succinate ~
Another test sample 75 was made in a same manner as compara-
tive sample 27 except including VI-l instead of comparative
compound A,
With respect to samples 74 and 75 together with compara-
tive samples 73 and 27 the quality of color changing and or
fading ( dye image stability ) was tested according to the
following method after the samples were exposed to light and
then processed as mentioned before. The samples were stored
for two weeks at 65C and 70 % Relative Humidity ( R~H. ) in
a ~onstant temperature-humidity chamber. Then, densities of
parts of the samples were measured to see the degree of color
fading, the densities of which parts had been 1.0 before the
above treatmentO Densities of unexposed areas of the samples
( in which areas no dyes were expected ) were also measured
and compared with densities of the areas before the above
treatment in order to detenmine the degree of color changing.
The densities of each o the dye images were measured through
. ,
f~ltersO A blue filter was used for measuring the yellow dye
area, a green filter for the magenta dye are, and a red-filter
or a cyan dye area. The unexposed area was measured through
a biue filter.
The results are shown in Table 7.
~h '
' '' .
~C)5~S~ ~
I I I ~~ la 1, 1~
1.1 ~ O O O r .
(d ¢)-1 .
~U ~1 '
o~a ~ ~ o o o
~ .r~ Q~-I.IU . .
E~ ~ X ~ ~ O O . O O
~ a) ~a~ ~
~ ~ ~q~ . ~ ' .
IE-~ ~
~ ~ 1 ~_1 ~ '~D ~D ot~ '
~ o ~a) o~ ' o' o o
. .
a~ ~ ~ ...... _
C~ ~ ~ 0
J~ ,~ ~1~ S-l O~ cr~ O I~
~ ~ ~ ~ ~ I~ . O~ ~0 ~
a~ J-b~ a~ o o o o
I~ ~U ~ ' ~ ~ .
l ~ -
. ~ 3 ~ ~ u~ ~ ~o .
E~ ~ v.,~ ~ o ta ~ c~ ~ a~ .
U~ ~ . .
. ~ ~ ., ~ :~ . o o o o
_ ~V~ ~ . _ ._~
". a . . ~ .
~ ~ ~ ~ ~1
o ~ o ~ o. o ~ Qa
~ :a . ~7 v ~ c~ ~ ~
.. - . -c~l
1~ . C~ ~ ~ ~ ~7 1 a ci~
~ , ~;t t.7 ~ t~ ~t ~ ) ~ C.)
o~ a~ ~ :~, ~ . - ,.
. . _ __ ' ..
' ~.. 1 _~, . , S~ .
', _ U~Z _ , r~ ~ ~0~ ~ U~ . ,
,. `,___ . ,~ .
l,.k . ' '
~ ~ I~Lt B
D .~ . .
. .
. ' ', ,
. .
', . . .
: ~S30
As is apparent from Table 7, the samples containing the
compound Vl-I of this invention hardly changed or faded in
color when compared with the samples containing comparative
ccmpound A and had exellent dye image stability,
.
'
.
:
C
, - . ...
,
.
