Note : Les descriptions sont présentées dans la langue officielle dans laquelle elles ont été soumises.
~~S894~.
Th:i~; inven-tion relates to color photography. More
specifically, the present inventiorl is directed to color photo-
graph]c elements ~ ich are internal:Ly color-corrected by the
incorporation thereinto of a colored coupler having the capability ,~
of correcting the unwanted green and blue absorption of certain
cyan color-forming couplers to a surprising extent.
Background of the Invention
Color-fornling coupler compounds which react during
photographic development with the development product of
10 aromatic amino developing agents to form color images are well j -~
known. Generally, these color-forming compounds are colorless
or substantially colorless. This lack of color is usually
desirable ~en the coupler is to be incorporated in the emulsion
.
layer and the unused coupler remains after formation of the
colored image. `~
; ; Unfortunately, the absorption spectra of conventional
dyes formed from color-forming coupler ma-terials are never 1
"clean". Thus, invariably, cyan dyes exhibit various degrees of
unwanted absorption in the green and blue regions of the spectrum,
20 while magenta dyes exhibit unwanted absorption in the blue region ~ ;
and to some degree also in the red region of the spectrum. The term ~
, ~ .
"unwanted absorption" is intended herein to mean, with respect
to a cyan dye, measurable absorption in the green and blue regions
'~ ~
-2- -
, ~ .
1 ~ -
_, .... .. . . ... ...... .. ... . .
~L~S~ 4~
,~ -
of tile v:isible Spet`'i,~'UIn. Ul-lWan'ted abSOr'}.)'t:iOrl i'; illustrzlted inFigllre 1~ as -that por-tion of the curve above the base line at
wavelengths lo~ler th~r.Lrl about 600 microns.
l~hereas the human eye and brain have the capability
of automati.cally compensating f`or a certain amount of such
un-~anted absorption in positive color photographs and trans~
parencies ~hich contain such conventional dyes, machines and
equipment f`or reproducing photographs and transparencies do not :
have such compensating capability. ~Ience, photographic materials
which must be mechanically reproduced, for example, from color
negatives or positive transparencies, must be color-corrected
so as -to largely overcome the effects of unwanted absorption.
Color correction becomes increasingly necessary when it lS ` ~,.'~'~ ' ,.'
desired to reproduce the color element by means of a series
of negative-positive-negative-positlve steps such as those ~
usually used in the preparation of (from valuable "master" '~;
films) motion picture films for release.
One very useful method of compensating for the unwanted
bsorption caused by a dye deri.ved from a given dye-formlng coupler
20~ involves the inclusion of a special colored coupler into the photo- .
graphlc element (in addltion to the image-forming coupler that is ;~
to be "color-corrected"). The colored coupler absorbs both
green Ind blue light, in the case of correcting for unwanted
absorption in a~cyan~dye. This colored coupler theoretically
lS capable of reacting with oxidized color developer (durlng the
color development processing step) to yield the usable cyan image - ~
dye ~rhlle simultaneously losing its ability, in propo~rtion to ~-
development, to absorb in the green and blue regions of the
spectrum, thereby "correcting" f`or the unwanted green and blue
absorption of the dye derived from the major cyan dye-forming
-3-
... _,... _ ___ . . .. , . -
.. . . . ... ... . ..
394~ ~
coupler :in the phot;ographic element. (See Chapter 13, "Masking
and ~oloured Couplers" of R.r~ G ~-lunt's book, The Reproduction
of Colour, ~ages 233, 263, published by John T~liley ~ Sons, 1967).
Couplers which are in themselves more or less strongly
colored by virtue of containing a chromophore group which is
split off or destroyed during and by means of the coupling reaction
with the resul-t that the original color of the coupler is destroyed
and a new dye is formed upon coupling are disclosed in U.S.
Patents 2,l~53,661, November 9, 1948; 2~455~16g~ November 30, 1948;
o 2,455,170, November 30, 1948; 2,521,908, September 12, 1950; and
2,706,684, April 19, 1955.
Upon development of an emulsion layer conta~ning one ~ -
of these colored couplers, the original color of the colored
coupler is destroyed and a new color is formed by the coupling ~ ~
reaction at those points where development occurs. There is ~ ;
formed in this wa~ a composite dye image consisting of the new ~ ; -
dye and the residual colored coupler. The theory of color correc- ~ :
tion requires that the sum Or the absorption of the residual -
; ~ colored coupler and the undesired absorption of the image dye
2~ shou]d be as constant as possible. Conventional color correctlon
to date has re~sulted either in non-ideal (non-uniform) correction,
or~unlform correction wlth somewhat higher Dmin than is desirable.
(The higher Dmi.n apparently results from the necessity to use
relatively large amounts of certain color-correcting couplers
which have relatively low activity.) Another shortcoming that !'~ ~'
exists with respect to certain of the conventional color~
correcting couplers that otherwise exhibit good correction -
relates to their color prior to their reaction with oxidized .
color developer. The peak absorption of such colored couplers
3 ~as often too hypsochromic, by several wavelengths, and thus
~ielded corrections which were somewhat less than desirable.
1~ ` ~:
1~5~941
`. ~
rrhe ~Ise oL` certain prior art color-correcting couplers,
such as those descr:ibed in the ~xamples~ below, yield excellent ~
dyes, but are not capable of yielding "ideal". or 'luniform" color~
correction. This fact is illustrated by ~igures 3 and 4. Note `~
that substantially uniform absorption in the green and blue regions `
(particularly in the green) is not achieved by the materials used i~
in the preparation of Figures 3 and 4. Ideal color correction
should result in perfectly level "G'l and l'B" curves in the Figures, ^ .-
such as those marked "ideall' in Figures 3 and 4
., :
~:
:~ : ` ~:
~ :
- 4a - ~: ~
. ,.. ..... . . .... .. _ . ... _ . ...... ---
.... ..... , .. ,,,.. ., . j, .... , . .. , .. ~ . ~ - . , ".. ;. , .~ .. .. --
f~
,~5~9~
UniforM color-c~rre~ction throl1ghou-t the development
of' tl-le color emuls:ion has been extremely dif'f`lcult -to achieve
because of the apparen-t re(lulrement of uniformity or similarity
in each of the rnany different chemical and physical parameters
involved in the color-correcting process. For example, the
reaction rates and relative reactivities of each of the couplers '
in any "color correction" combination must be matched at every
stage of -the development step, even though the concentration
of developer, pl-l, concentration of reaction by-products and
many other aspects of the chemical color development process ''
not only differ widely from one photo-finisher to another, but ' ~ '
also differ widely during any single color development operation.
; Brlef Description of the Invention
It has now been discovered that certain combinations '
of (a) colorless naphtholic cyan-producing color couplers with '~
(b) certain naphthylazophenoxy phenolic couplers have the '~
surprising capabilLty, when they are uniformly distributed through ~ '
at least one e1nulsion layer of' a photographic emulsion, of
color-correcting almost perf'ectly during the entire color
development operation
The napllthylazopheno~y phenolic color couplers to which ` ~
this invention relates have struc-tures like that of formula "I" '1~ 1
-~ - NIIC-C-0- ~ R3
Cll R
0
B
-5- - ` ' ~'
:
._ ..
: , . - . ., ,, . . ,, ., - .,.
'' 1~5~g4~ . -
-herein R is an alkyl group containing 1 to 6 carbon
'~toms, R~ and R4 are independently selected and are
alkyl groups con-talning 2 -to 6 car~on atoms, B is a hydrogen , ~ ;
atom or a COGR group wherein R6 is an alkyl group '
containing 1 to 8 carbon atoms~ X is ha]o~en such as, for
example~ chlorine, bromine or f'luorine and A is a sulfonated
napllthylazo group selected from those having the structure: ,
OH NHCoR5
(I) ~N= ~
~\ . '~
M03S S03M ~ ;;
or ' ~ ~'
OH NHCoR5
(II) -N=N ~ ¦
H03_ \0 H Ml
:: ~
wherein R is an alkyl group containing l to 4 carbon atoms,
M and Ml are photographically lnactive, M is a monovalent
~ cation, and Ml is a tertiary amine.
~ ~ The naphtholic cyan dye-producing color couplers which
~;function~so ~ell in color-corrected~combination With the
compounds of formula I, above, in photographic color f'ilm '~ -;
e~lements~have structures~like that Or formula "II"~
~, ~ j
wherein R and R are independently selected and are alkyl groups ~' -
con~aining 1 to 8 car~on atoms and n is an integer from 1 to 6.
In Figure 5, the surprlsing~uniformity in cyan color~
correction that can result from practicing the present invention
.~.
is illustrated. ~xperimental details relating to 'the acquisition
;
; 6- ~
"' , '
. . .
5~3~4'~ ` ~
of the data depicted in the Figures 2 through 5 are set out in
the Examples hereinbelow.
Detailed Descri~tion of the Invention
Each photographic element of this inven-tion comprises
a photographic support upon which has been coated at least one
photographic emulsion layer containing, uniformly dispersed
therein, photosensitive silver halide and a combination of (a) a
naphtholic color coupler compound which, upon reaction with
oxidized amino color developer,forms a first cyan dye, plus (b)
a naphthylazophenoxy phenolic color-correcting coupler compound
which, upon reaction with oxidized amino color developer, splits
out the naphthylazophenoxy group and forms a second cyan dye,
thereby uniformaly correcting for the unwanted absorption
characteristics of said first cyan dye. The colored compound
derlved from the naphthylazophenoxy group is subsequently
washed out of the film element.
The types of coupler materials to which the presellt
invention is directed are set out in formulae I and II, above.
In these formulae, R and Rl are preferably the same and contain
4 to 6 carbon atoms. It is also preferred that R3 and R4 be ;~
the same and contain 4 to 6 carbon atoms. It is still fur-ther
preferred that R, R1, R3, R4 are tertiary alkyl groups. R2
and R5 preferably contain l to 3 carbon atoms and n is pre~
férably 2 to 4. Preferred alkyl groups for R include ethyl,
. propyl and~butyl. It is preferred that X is Cl. In the
practice of this invention, the naphthylazophenoxy coupler '~
compounds of formula I can con-tain any monovalent cation (M ;~
, . . -
in group A), the presence of which does not excessively fog
or other deteriora-te its desired photographic properties. :
', ''"',' ~.
--7-- ~
. : . . ~, . ''' ' :, .
,. . , ~ . .
~C~58~4~ ~
~ .
Such ca-tions include ca-tions of alkali metal such as sodium ,~;
and potassium~ and ni~rogen-containing cations sueh as, for
example, ammonium, me-thylammonium, e-thylammonium, diethylammonium,
-triethylammonium, ethanolammonium, diethanolammonium as well
as cyclic ammonium cations such as pyridinium, piperidinium,
anilinium, -toluidinium, p nitroanilinium, anisidinium, and
the like. Of -these, because of their solubility properties
in the sulfona-ted phenylazo salt form of the colored coupler,
it is preferred that M be tertiary amino, and still further
preferred to be cyclic, such as for example, that derived from ,
pyridine. ~
Preferred colored naphthylazophenoxy phenolic couplers '
of the present invention include the following~
a. 2-Chloro-6~ -(2,4-di--t-pentylphenoxy)butyramido7-
4-~ -(8-acetamido-3,6-disulfo-1-hydroxy-2-naphthyl- ~ -
azo)-4-(n-carbobutoxy)phenox~7-3-methylphPnol
dipyridine salt
b. 2-Chloro-6- ~ -(2,4-di-t-pen~y~phenoxy)butyramido7-4- '~
r -(8-acetamido-3,6-disul:~o--1-hydroxy-2-naphthlazo)
phenoxy7-3-methylphenol dipyridine salt ~ ;~
c. 2-Chloro~6-rC-(2,4-di-t-pen-tylphenoxy)butyramido7 "
-4-~ -(8-acetamido-3,6-disulfo 1-hydroxy-2- -
naphthylazo)phenox~7-3-methylphenol dipyridine salt
d. 2-Chloro-6-r~ -(2,4-di-t-pentylphenoxy)butyramido7
-4-/~-(8-acetamido-3 6-disulfo-1-hydroxy-2-naphthyl-
azo~-4-(carbomethoxy3phenox~7-2-methylphenol
dipyridine salt
and also include other tertiary amine salts. `
Preferred naphtholic colorless eoupler materials of '
~ this invention (whieh form cyan dye upon reaetion with oxidized
eolor developer) include the following~
a. l-Hydroxy-2- ~ (2,4-di-t-pentylphenoxy)-
ethyl7naphthamide,
b. I-Hydroxy-2 r~ -(2,4-di-t-pentylphenoxy~-n-butyl7-
naphthamide.
-8-
. _.. ...
:3LC3 S~4~
The par-ticular levels of usage of -the color-correction
co~lpler combination of the presen-t invention will vary
subs-tantially, depending upon ~the par-ticular density of cyan
color and the par-ticular hue desired in -the developed color
elemen-t. For example, in one pre~erre~ aspec-t of the practice
of -this invention, the ratio of colorless cyan-producing ,~
naphtholic coupler to colored naphthylazophenoxy phenolic
coupler (Formula I material) in the photographic elements of
the inven-tion should be from about 2.5 to 1 -to about 3.5 to 1,
and ideally about 3 to 1, respec-tively. Preferred usage also
~` includes using colorless cyan-producing naphtholic coupler at a
level of from abou-t 175 to about 810 mg per square meter of
coated photographic element, although more or less than this
.
-' amount can of-ten be used satisfactorily.
In addition, although any particular procedure can be used
. j .
for incorporating the respective coupler materials described into ;~
a photographic silver halide emulsion layer, generally, it is
preferred that such coupler materials be used in association wi-th
(preferably dissolved in) one or more high boiling coupler sol- ;
vents. In a fur-ther preferred embodiment, each coupler (of the
color-correction coupler combination) should preferably be
separately dissolved into a coupler solvent and then each
": . ~ . .
solution should preferably be introduced into a fluid photo-
graphic emulsion. Techniques for preparing photographic silver
halide emulsions containing couplers and high boiling coupler
solvents are well known in the art and need not be detailed herein. '~
See, for example, Product Licensing Index, December,1971, page 110.
If desired, other coupler materials such as, for example, the
,, ,~,
development inhibitor releasing couplers described in U.S.
30 3,227,554, in addi-tion to the color-correction coupler
combinations discussed herein, can also be present in the cyan-
forrning emulsion layer(s) of the present emulsions. For multi- ~ ~
_g_ ~,
.: ,~ , . . .
58~
: .
c:olor photogxa~)h:ic e:lements, of course~other couplers will be
present in o-ther emulsion layers in our elements It has been
observed tilat m~nufacturing procedures and chemical development
methods affect the degree of color-correction effectiveness of
the photograpllic elements of this invention to some extent; how-
ever, excellent color correction can be obtained in the generic
prac-tice of this invention by simp]y following the details and
teachings set out above in combination with known prior art
manufacturing methods. Much has been published concerning ~ -
... ..
the manufac-ture of "color" photographic elements, including
multi-layer elements. See, for example, the several pro- ;
¦ cedures referred to in Section XVIII on page 109 of Product
Licensing Index, December, 1971. The successful practice ;~
~'~ of this invention does not depend upon any particular mani
pulative procedure being used in the manufacture of the
photographic elements described above; nor in the use of any
particular type of manufacturing equipment, so long as the
essentlal features regarding the constitution of the color- -
correction coupler combination in the silver halide layer(s)
of the present photographic elements, as set out herein-
before, are observed.
, :
The photographic elements of the present invention
can also contain any desired emulsion addenda that do not
. ~ , :. .
``~ interfere excessively wLth the desired photographic and
; color-correcting properties of such elements. Examples
of such addenda and methods for their use are set out
at pages 107 through 110 of Product Licensing Index,
December, 1971. Similarly, chemical processing of
~, -
photographic elernents is described in Section XXIII, page
110 of Product Licensing Index, December 1971. Chemical
"processing" which involves the reaction of oxidized
~ .
' --1 0--
:,, .
. .
organic amino color developer materials with color coupler mater-
ials~ as described in said Section XXIII, can be used in the
practice of this invention, although the use of p-phenylenediamino
materials such as N,N-diethylamino-p-phenylamine, 4-amino-3-methyl- ~ '
N-ethyl-N-~-(methanesulfonamido)ethylaniline and the like is
preferred.
Methods are known for manufacturing the coupler mater-
ials used in the color-correction coupler combination of the
present invention. For example, the naphthylazo phenolic coupler ';
materials of Formula I, above, can be manufactured by a multi-
` step procedure such as that illustrated below:
Manufacture of Naphthylazo Phe'n'o'lic Coupl'ic Materials
Step 1 --
.
4-chloro-3-nitro-n-butylbenzoate
N 2 50Cl2 n-C4~9H
COOH OOC H ' '
Procedure ~ '
s -~:
A 3 liter, 3-necked flask was charged with 600 g (2.9~
' moles) of 4-chloro-3-nitrobenzoic acid, 840 ml of thionyl chloride
f and 12 ml of dimethylformamide. The flask was equipped with a
stirrer and a condenser with a drying tube, and the mixture was '~
refluxed on a steambath overnight.
The thionyl chloride was removed under reduced pressure,
leaving a yellow crystalline solid. One liter of n-butanol was '-'
added slowly with stirring, keeping the temperature at 25C with '
an ice bath. The mixture was stirred overnight at room tempera-
ture. ~'
''
--1 1--
:,
,, .. . . ,.. .. - .. . . . . . .
The crystalline solid was removed by filtration, air
dried, and recrystallized from 2500 ml of methanol. All crops
were combined to yield 314 g (24.5%) of white crystalline solid,
having a thin layer chromatogram of one spot on silica (benzene).
Step 2
.. : .
~-~ 4-Fluoro-3-nitro-n-butylbenzoate
- Cl FNO
C
COOC4H9 n OC4Hg n
; Pro edure
7 A 5 liter, 3-necked flask was charged with 314 g (1.22 ' ~ ;
mole) of 4-chloro-3-nitro-n-butylbenzoate, 2400 ml of dimethyl-
formamide and 168 g of anhydrous potassium fluoride.
.
~;' The mixture was refluxed for 4 hours on a heating mantle ~ -
and concentrated to a volume of 500 ml under reduced pressure.
Upon addition of 1500 ml of benzene, a white solid appeared and
was removed by filtration. The filter cake was washed with ben- -~
. ! . ,~ . .
zene and the filtrate was concentrated to an oil under reduced
pressure. The oil was distilled for purification and the purity
established by thin layer chromatography, yielding 202 g (68.7%)
of yellow liquid. .! ."
- Step 3 `~
2- ~-(2,4-di-t-pentylphenoxy)butyramido~-6-chloro-5-methyl
benzoquinone
~,. ..
-OH Ç2H5 ~=\ . . HOAC
Cl~NHCOCH-O~ 5Hll NaNO2
3 ~ C H ~tJ ~-
:., 1 .
~ 30 Cl ~ NHCO~H-O ~ C ~l (t)
: !
~ -12-
., , ~'
.
" , ~ , ,
1~51~3~4~ilL
Procedure
A solution of 704 g (1.42 moles) of 2-la-2,4-di-
t-pentylphenoxy)butyrarnido]-4,6-dichloro-5-methylphenol in 6000
ml of acetic acid at 100C in a 12 liter 3-necked flask was pre-
pared by stirring while the flask is held in an electric mantle.
The amber solution was cooled with external water to 15C at
which time 111 g (1.61 moles) of sodium nitrite dissolved in
600 ml of water was added over a 1/2 hour period keeping the -
temperature less than 15C. Solution occurred near the end of
10 the addition. `~
The reaction was allowed to come to room temperature
over a 2-hour period and then poured out into a large volume of `~
ice-water with good stirring to precipitate the orange/brown
product.
Upon recrystallization from methanol with seeding, a
yellow solid was collected and air dried to yield 398 g (59
with a m.p. of 70 - 72C. Thin layer chromatography on silica ` ;
gel (benzene) gave a single spot.
Step 4 .`
2-C~-(2,4-di~t-pentylphenoxy)butyramido~-6-chloro-5
methyl hydroquinone
o C 2H5 , ~
Cl ~ NHCOlH-O - ~ C5Hll (t)
3 ~ 5Hll T.H.F.
O ',''~
Cl~NHCOCH O -,~CSHll ( ~
i ; `
-13- "~
- ;
~L~S~3~4~
P cedure_
~ solution of 65 g (0.137 mole) of 2-C~-(2,4-di--t-
pentylphenoxy)b~ltyramido]-6-chloro-5-methylbenzoquinone dissolved
in 250 ml of tetrahydrofuran was reduced using palladium on
charcoal catalyst in a shaker under 40 P.S.I. of hydrogen. The
reduction was complete after absorbing the theoretical (0.137 mole)
amount of hydrogen at room temperature. The product was removed
from the catalyst by filtration and was used in its tetrahydro-
furan liquors in the blocking reaction with d-bromotoluene.
Step 5
3-~ -(2,4-di-t-pentylphenoxy)-butyramido~-5-chloro-6
methyl-4-benzyloxyphenol
H C~ 2H5 ~ CH Br
Cl~NHCOCH-O~ 5Hll 2
~ Acetone
3 ~ H C5 ll 2 3
OCH2 ~ C H (t)
CE ~ HCOICH-O ~ 5 11
3 OH
20 Procedure ;-
Two of the 65 g reduction tetrahydrofuran filtrates ~
prepared by the procedure described in Step 4 were combined ~ ;
(0.274 moles) and added to 3500 ml of sieve dried acetone con-
taining 90 g of potassium carbonate in a 5 liter flask equipped ~ -
with a stirrer, condenser and nitrogen bleedline.
47 g (0.272 mole) of ~-bromotoluene was added and the
reaction refluxed for 24 hours on a steam pot and under a nitrogen
blanket.
The reactant was poured out into 10 liters of cold
water containing 50 ml of concentrated hydrochloric acid.
.
-14- ~
, . ...................................... . :
.. , : : : . . ., : . . :
~ o~ a~
The tan gum quickly solidified and was slurried in hot hexane.
There were obtained 130 g (83~ yield) of a light tan
solid, m.p. of 183 - 187C and having a single spot on thin
layer chromatography using a silica gel slide and eluting with
benzene containing 5 volume percent of ethyl acetate.
Step 6
5-benzoyloxy 2-(4-carbobutoxy-2-nitrophenoxy)-6-chloro-4-
~-(2,4-di-t-pentylphenoxy)butyramido~-toluene
OCH- ~ 5 11 F
Cn ~ HC08H-O _ ~ C5Hll ~ N 2 + NaOH
OH CO2C~Hg
OCH2 ~ C H -t
Cl ~ NHCOCH-O ~ C5Hll
C02C4Hg
' ~
Procedure
A 12 liter, 3-necked flask was charged with 384 g
(0.678 mole) of 3-L~-(2,4-di-t-pentylphenoxy)butyramido~-5-chloro-
6-methyl-4-benzyloxyphenol, prepared by the procedure of step 5,
3.5 liters of DMF, and 164 g (0.678 mole) of 4~fluoro-3-nitro- ;
n-butylbenzoate prepared by the procedure described in Step 2. - ~
Under a blanket of nitrogen the mixture was stirred -~ ;
and cooled to 10C. A solution of 29.8 g of sodium hydroxide ;
(.746 mole) in about 150 ml of water was added dropwise, keeping ;~
the mixture cold. When addition was complete, the mixture was
stirred at room temperature for 30 min.
-15-
:,
.... . .. .
~` iLQ15894~L
The mixture was poured into 25 liters of ice-water
to which 350 ml of hydrochloric acid had been added. The solid
was removed by filtration, washed well with cold water, and air
dried yielding 533 g (99.8~) of yellow solid having a thin layer
chromatograph of one spot.
Step 7
4-(2-Amino-4-carbobutoxyphenoxy)-6-chloro-2-~(2,4-di-t-
pentylphenoxy)butyramido~-5-methylphenol t '
OH C5Hll ;
OCH2 ~ ~ Cl ~ NHCOCH-O- ~ C5Hll
CH ~ NHCOCH-O ~ C5~11-t 3 ~ 2 5
2 TÉIF C02C4EIg n
C2C4H9 n
Procedure
A 1500 ml stainless steel pressure bottle was charged
with 533 g (0.678 mole) of 5-benzoyloxy-2-(4-carbobutoxy-2-
nitrophenoxy)-6-chloro-4-[~-(Z,4-di-t-pentylphenoxy)butyramido~
toluene, prepared by the procedure described in Step 6 and enough
tetrahydrofuran to fill the container. Under a blanket of
nitrogen 2 spoonfuls of 10% palladium on charcoal catalyst were
added. The mixture was placed on the Parr apparatus under 40 psi
of hydrogen pressure.
When the reduction was completed, the catalyst was
removed by filtration and the solution was concentrated to an oil ;
under reduced pressure and used directly in the next step. -
.,' ~,
;
-16-
;"~'
.
:. .~, i . " :,. . . . . . .. .
.. . . . . .
Step 8
2-Chloro-6 [~-(2,4-di-t-pentylphenoxy)butyramido~-4-~2-(S-
acetamido-3,6-disulfo-1-hydroxy-2-naphthylazo)-4-(n-carbobutoxy)
phenoxy~-3-methylphenol dipyridine salt
C H -t ~ ~
OH C2H5 \5 11 ~-
~ NHCOCH-O ~ C5Hll ~ ~
p HCl OH NHCOCH
NH~ ~ NaNO2 ~ ~ SO Na
2 4 9 3
H C2Hs C5Hll
Cl ~ NHCOlH-O ~ H -t
3 OH ~HCOCH3
HO ~ ~ ~SO3H 2
CO2C4H9 n
Procedure
A 5 liter, 3-necked flask was charged with 453 g
(.678 mole) of 4(2-amino-4-carbobutoxyphenoxy)-6-chloro-2-
20 L~- ( 2,4-di-t-pentylphenoxy)butyramido] 5-methyl phenol, prepared
by the procedure described in Step 7 and 2.2 liters of glacial
acetic acid. To this mixture 635 ml of concentrated hydroehloric
acid was added dropwise. The solution was chilled to 10C. A `~
solution of 51.5 g (0.746 mole) of sodium nitrite in 200 ml of
water was added dropwise. - ~ -
The above mixture was poured slowly into a 3-necked, ~-
,
12 liter flask containing a chilled solution of 260 g (0.678 mole) ~ -
of 8-aeetamido-3,6-disulfonaphthol (disodium salt) in 4.2 liter -
of methanol. A solution of 2 liters of pyridine in 2 liters of
methanol was triekled into the eold mixture. When addition was
eompleted, the reaetion mixture was stirred for 30 min. at room
.. . . .
-17-
. -
.: . ":., , , ~ , ~ .. , - ~, .
~si3~4~
temperature and concentrated to a volume of 6 liters under reduced
pressure.
The oily mixture was poured into 30 liters of ice-
water with vigorous stirring. The mixture was allowed to stand
undisturbed for 24 hours and the supernatant fluid decanted off.
The magenta sediment was collected by filtration and dried in a
warm air oven for 2 days.
The resulting 529 g of dark magenta solid was re~
crystallized from 5 liters of dry acetone, yielding 350 g. ' ~
The preferred colored naphthylazo phenolic coupler b. ' -
mentioned on page 5 was synthesized by a similar procedure wherein ~;
5teps 1 and 2 were omitted, and in Step No. 6 the 4-fluoro-3-
nitro-n-butylbenzoate was replaced with l-fluoro-4-nitrobenzene~
N2
Manufacture of Color'l'e's's'Naphtho'l'ic Co'upl'er'Ma'te'ri'al's '
: ~:
The colorless naphtholic coupler materials useful in
the practice of this invention can be manufactured by the general '~
process illustrated in U.S. Patent 3,476,563, by selecting the '~
appropriate raw materials for such process. ''~
Control'Example'No'. l''-'No Co'lor'Correc'tion
Onto one surface of a conventional transparent subbed -
poly(ethylene terephthalate) photographic film support was coated
conventionally (from a 3% gel) a photographic emulsion which, ''~
after drying, yielded a coating containing the following com~
ponents: ~ -
-18- ~
~: :
Silver chlorobromide (as Ag) 972 mg/m2
Gelatin 2376 mg/m2 ~
Coupler (naphtholic)* 551 mg/m2 :.
Coupler solvent** 275 mg/m2
* l-hydroxy-2[~-(2,4-di-t-pentylphenoxy)-n-butyl]-naphthamide
** Tricresyl phosphate - coupler dissolved in coupler
solvent before dispersion into emulsion
The silver halide in the emulsion was spectrally sensitized
conventionally to red light. The resulting film element was ~ ~ :
exposed through a graduated-density test object and then color
processed conventionally in the following sequence: -
1. Color develop*
: 2. Stop ~ ;?
3. Bleach
4. Fix
5. Stabilize
6. Dry ` ~.
* Using as color developing agent 4-amino-3-methyl-N-ethyl-N-
~-(methanesul~onamido)ethylanillne ;
20 A~ter color processing, the characteristic curves for red, green :
and blue light absorption were obtained conventionally, and ,~
are set out herein as Figure 2. Note that the curves labeled `.
G and B in Figure 2 represent unwanted absorption, as herein- .:~
above described. ; .::
,, ~... .
,~:
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. ,,~ ~ .
-19- `~' ' ` ~ '
j~71,' .'~ .` " i
~5~
Control Example No. 2 - Colo:r Correction by
Prior Art Coupler
A photographic film element was prepared like that of
Control No. 1, above, with the exception that 2268 mg gelatin/m2
was used and there was added 216 mg/m2 of a conventional color-
correcting coupler having the structure:
OH
C5Hll t
COCH3
3_U ~ ~2
C=O N
O .
C H -n ::
4 9 :~
,,,; . ~
: ~;
`.`'`:~: ;- ' '
-20- ~ ~
' . ~' ..;
' ~: ' . : .' ~.
i, . . . . .
~58~
Also, the coupler solven-t was dibu-tyl phthala-te for Control
No. 2. (See U~S. 3,476,563). Color processing and trea-tment
otherwise of -this element was the same as for Control No. 1, -
above. The resul-ting characteris-tic curves for red, green and
blue light absorption by the processed element are illustrated ~-~
in Figure 3. ^
Con-trol Example No. 3 - Color Correction b~ a
Second Prior~Art~ Coupler
Similar results (see Figure 4) were obtained when
-the colored coupler of Con-trol Exarnple No. 2 was replaced by
97 mg/m2 of the conventional colored coupler 1-hydroxy-4- ~ -
/b (8 acetamido-3,6-disulfo-1-hydroxy-2-naph-thylazo)phenoxy 7
-2-/L~ -(2,4-di--t-pen-tylphenoxy)-n-bu-ty_7naphthamide dipyridine 5
salt. ~`
Example - Color Correction br a Coupler Combination
of This Invention
A pho-tographic film element was prepared like that
of Control No. 1, above, with the exceptions (1) that 367 mg/m2 ~
of tricresyl phospha-te was used as coupler solvent, (2) that the ~ `;
dispersion of the coupler solvent was aided by use of a small ~;;
amount of an auxiliary solvent composed of 2 parts by weight ~ ~ ;
propyl ace-tate and 1 part methyl alcohol, and (3) -that there "
was added 178 mg/m2 of the colored coupler: ;
OH " ,2 5 ~`
Cl I IIH - C - C - O (~} C5Hll ~~ D
CH3~ I C5Hll --t
O ;
OH NHCOCH
COOC4H9 -n S03H S03H
--21--
,,, , .. .. .. _ . ~ ~-- .
lOSB99Ll
Color processlrlg ancl treatmerlt otilerwlse of -this e:Lement
~ ,
W,lS ti~e same as f'or Con-tro], No, 1, above. The resulting ,;
characteristics curves for recl, green ancl blue light
absorption by the processed element are illustrated in
Figure 5, The surprisingly close approach to ideal color
correction which is possible in the practice of this
invention can immediately be appreciated by comparing
Figure5 with Figures 3 and 4. r
Results like those of Eigure 5 were obtained when ;~
10 187 mg/m2 of the colored coupler:
~ Cl ~l C,zl~s ,~
¦ ~ J ~ C-C-0-~ c~ r CSHlL t
O - ,
"~
0~ Nll(.OCII ~\J
~as used in place of the colored naphthylazo phenolic
coupler material of the first example.
. ~ 20 When fil.m materials such as those described in ~' ~
. thls Example were used as color intermediate fllm for '~.
I - producing motion pictures for distribution from a valuable :,
: color original via the usual procedure involving the use of
. films containing color-correcting coupler during at leas-t
two intermediate steps in the copying procedure, films
color-corrected according to the present invention yielded
,
-22~
,
:
. ,,
~: ,, .
:
1~5~3~314~
, . L
excellent coples without the necessity for extensive equip~
ment adjustment at each step, etc., that :is ordi.narily
needed when conventi.onal color-correcting couplers are
use~. Also, film ma-terials of' this invention make
possible product film copies having surprisingly low
Dm.i.n values. ~ ::
The invention has been described in detail with :~
particular reference to preferred embodiments thereof, . ~:
..
but it will be understood that variations and modifications
lO can be effected within the spirit and scope of the invention, . ~ :
,~
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