Note: Descriptions are shown in the official language in which they were submitted.
` ` 1041~6
This il~vention rclates to diffusible yello~Y-dye-
I forming coupler compounds ~xhibiting good solubility properties,
unusually high color-forming efficiency and, in the dye form,
unusually ~ood aging and absorption characteristics. Also, the
present inve~tion relates to de~eloper compositions containing
- such valuable ~iffusible yellow-dye-forming coupler materials.
i The coupler compounds of this invention are halo-
; anilidophenoxycarboxy compounds having the structure I:
1 0 o ~i
, R-C-C-C-NH- ~ X
~ X
- B
! : :
wherein R is a branched alkyl group containing 3 to 6 carbon
atoms; X is Cl or Br; Y is X, hydrogen or alkyl (1 to 8 carbon
atoms); and A and B differ and are either H or -COO~I, wherein M
is a photographically inactive cation, a methyl group or an
ethyl group. This invention also includes developer compositions
containing one or more of the compounds of the structure I and
one or more organic aromatic amino developing agents, which
developer compositions are used in the form of aqueous solutions
.;i ~ , . .
comprising water and having a pll of at least about 10.
The formation of colored photographic images in silver
halide emulsion layers by coupling the oxidation products of
aromatic amino developing agents with color-forming coupler com-
; pounds is well known. Color-forming coupler compounds have been
. ~ . .
~; classified as "incorporated" and '!diffusible", based upon
~, the way sucl- compounds are ordinarily used. For example,
"incorporate~" couplers have fairly large molecules ln order
~, to~prevent the diffusion or substantial movement of such couplers
within the particular hydrophilic colloid layer into which
they were incorporated during the manufacture of the photographic
` ~041~
lement. ~y comparision, "~iffusible" cou~lers are soluble in
. alkaline solutions hhich a~so usually contain one or more organic
. aromatic amino developing agents. Thus, when diffusible couplers
are used, their capability of diffusing into (and through) the
emulsion layers of the photographic element being treated makes it . ~ -
possible for them to react (couple) with oxidized aromatic amino
color developer(s) and thereby become effectively bound into the
emulsion layer. In this situation, unreacted diffusi.ble coupler
can be readily removed from the photographic element via simply
washing the element with water. .
Although many very useful diffusible couplers have been .
manufactured and used commercially heretofore, manufacturers of `- ::
developer compositions are continually striving to discover
' . couplers having outstanding solubility, coupling efficiency and '
hydrolytic stability in developer compositions and excellent aging .'
.
' characteristics after they have been converted into the correspond-
' ing dyes during the color developing process. . .... "'
Diffus1b1e couplers that form yellow'dyes have, to date,
exhib1ted more of a need in this respect than have other types : '' ... '
~-~ 20~; of.color-forming couplers. ' ' ~' '' "'
~` ' '' Deiscription o the Invention :
It has now been discovered that a small group or class
'o~ pivalyl a-aryloxy anilide, yelIow-dye-forming coupler compounds
. ;displays the valuable characteristics set out above.
The valuable properties of the couplers (and composi~
`tion9 containing them) of the present invention apparently result ' 'i
from the~'unique combination of substituents on the basic keto-`~ .'.
methylene backbone structure of the coupler compounds encompassed
by~F:o~mula I above,.' Thus, i~t was known heretofore,.as disclosed ~
O~:~`in~U~.~S~ Patent~s~3,265,506~now~Reissue No. 27,S48) and 3,408, 194,
'that v~r:`y ~ood~yellow dye`'stability and anti-stain properties
-: result:when;coup'lers having ` :~::~ :.: '.
~ .
loqi~
(a) an aryloxy "couplin~ oLf" group attached through
the ether linXa~e directly to the active carbon atom
of the coupler and
. . (b) a branched alkyl group (such as "R" in structure
I above) attached to one of the activating carbonyl
groups in an acetanilide_coupler.
It has now been discovered that a still better coupler can
result when
~c) there are two halogen substituents on the aromatic
ring of the anilide portion of structure I, provided
that one of the halogens is attached at the "2" position
on the aromatic ring and that the halogens are
identical; and
td) there is a carboxyl substituent (either a carboxylic
` ~cid or a photographically ina~tive salt or lower alkyl
ester thereof) attached at either the "3" or "4" ;~
position on the aromatic ring of the "aryloxy" coupling-
^ ~ff groupL
Preferred halogens, as in part "(c)" of the above dis-
i ~r
closure, are Ci and Br Of these, Cl is still further
preferred. Similarly, it is preferred that a halogen be at
both the "2" and "4" position on the aromatic ring o the
~acetanilide portion of structure I, Regarding the photo-
;1 graphically inactive cation designated "M" in structure I, above,
it is preferred that M be selected from the group consisting of
~1, alkali metal and ammonium cations and tertiary amines. Of
those couplers having the structure I, partlcularly preferred
in th~ practice of the present invention is alpha-pivalyl-alpha-
~-carboxyphenoxy)-2,~-dichloroacetanilide.
Hydrolytic Stability Test
30 ~ As it was stated above, one of the valuable properties
of the materials of the present invention relates to ~heir
su~rprlsingly hl~h resistance to hydrolysis under condltions
, ~ : - -
r ~, ~- , -
- 1041~16 -
which simulate cnd-usc con~itions; namely, in aqueous solution
- at a buffered p~l of 1~.06 and at a temperature of 23.9 C. Under
such conditions, with the coupler being dissolved in the aqueous
buffered solution at a concentration of coupler about 6.6 x 10-5
molar, many couplers have been found to degrade ~hydrolyze) at
varying rates of hydrolysis. The rates of hydrolysis are apparently
unaffected b~ the presence or absence of color developing agent
in the solution. By monitoring the rate of disappearance of the
coupler from the buffered solution (by measuring the solution
absorption at the optimum wavelength at ~hich the particular
coupler anion absorbs), it was found that, generally, hydrolysis
proceeded in a linear fashion, when the log of the absorption ,
was plotted vs. time. As a result, relative rates of hydrolysis t
of couplers can be set out in terms of their respective "half- ,
lives" in this standard test. In terms of hours, practical
acceptability for very high quality diffusible couplers is believed
to require half-lines of at least about 1000 hours. The half-
; lives of all of the coupler materials of the present invention
are believed to substantially greater than 1000 hours in this
test. tThis has been confirmed by tests on some of the coupler
compounds oE structure I above.)
In order to demonstrate the excellent hydrolytic
stability that can result from coupler compounds having the
structure I, a number of coupler materials were submitted to the
. . . :,,
"hydrolytic stability" test described above. Results from that
test are set out in Table I.
.i, - 5 ' ~'
:~ :`. . : ~:
' ' . .,
:~ : :
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,,
.,~ .
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104~16
T~ble I ~ :
. ' HYDROLYTIC STABILITY D~TA ~ -
.(Test at p~l = 12 and at T = 23.9C.)
" , " ~ B5 ..
: . Structure II (C~13)3CC-C-C-N~ O ~ B3
~ 4 :
,. - , B 2 : .
Coupler No. Z B2 B3 B4 B5 Half-life ~hrs.
.. 1 Cl -OCH3 H H H 0.026 .
:~ . , : . .
2 o ~ NO2 -OCH3 H H H 233
i . .
~ 3 O- ~ COOH -OCH3 H ~ H H 1132
~" ~ ~ .
4 O - ~ :OCH3 H H H 1430
. ; COOH . .
`10 ~~ 5 ~Cl ~H -OCH3 H H 0.012
6 O- ~ NO2 : : H -OCH3 H H 8
7 ~ ~ Cl Cl H H H 0.082
8:: O~- ~ - COOII C1 H H H 2180
;: :. 9 O - ~ -COOH Cl C1 H H ~2500
l0 ~acetoxy H H H H o.oi
;It is expected that the presence of another substituent (such ` :.
as~alkoxy, halogen or alkyl) on~the::.aromatic ring of the acet~
;`.anilld~e~portlon of the~couplers.~of~:this invention would not have ;~
..~ i.al-:appreclable;~ è~trimental~effect ùpon the hydrolytic stability
..... ~ 20 :~of the~resulting couplers;as compared to that of the couplers
whlch~were~ lnvol~red in~.th~ls~test.~
~041:116
It is also note~ortlly that the coupler compounds
of the present inve~tion ekhibit a very high degree of color-
forming efficiency. In vie-i thereof, they can be used at
some~hat lo-~er concentrations in photograpllic processes if
desired, in ordcr to obtain yellol~ dye levels comparable to
those presently obtainable by conventional methods using present
commercial processes and coupler/color developer compositions
Alternatively, colored photographic materials having greater
yello~ dye density may be obtained via the practice of this
. .
invention, particularly ~hen the invention is practiced commer-
ciallyJusing aqueous solutions of coupler, color developer
and alkaline materials in the usual manipulative manner.
The compositions of the present invention comprise
one or more p-phenylenediamine type color developing agents.
Such agents are well known and need not be described in detail
herein, since any phenylenediamine color developing agent can be
. .
used. A preferred p-phenylenediamine-type color developing agent
. .
` is 4-amino-N-ethyl-N-(2-methoxye~hyl)-m-toluidine, di-p-toluene-
sulfonate salt. The coupler compounds of structure I can be
; 20 used successfully in combination with such color developing
agents. The ratio of color developing agent to coupler in the
compositions of this invention can vary widely, but will generally
` ~e within the (molar) range of from about 0.~ to 1 to about 10
to 1, respectively, and preferably within the (molar basis) range
.,j .
j of from about 0.5 to 1 to about 3 to 1. The coupler/color
developer compositions of this invention are preferably blends
~;~ of solid crystalline or powdered materials which blends can
rea~ily be ~issol~ved in aqueous compositions in the preparation
. ,~,.................................................................. : .
of color dfeveloper baths. Such baths, which contain yellow
30 ~ dye-orming coupler dissolved therein, can then be used in the
conventional manner during the "yellow developer" step in a -~
multi-step process for manufacturing colored photographic articles.
7 - -
:~, ,. , : .
1041116
Use o~ the coupler compositions of this invention is demonstrated
beloi. in the ~xample.
The couplers of this inve~tion can readily be manu-
factured via ~.ell known techniques, as set out in U.S. 3,408,19~,
for example, by simply using the appropriate raw materials.
In the following Example, all parts are by weight
unless otherwise specified.
EXA~IPLE
A conventional photographic element comprising a
transparent poly(ethyleneterephthalate) support coated with a
gelatin/Lippman emulsion (coating 910 mg silver/m2) ~.as exposed
conventionally to a step scale of increasingly intense light.
The exposed element was then subjected to the following
developing procedure: (23.8C)
Step ~ Time Accomplished
1 5 minutes Color Develop(l)
.
- 2 S minutes Wash
.i~ .
'~ 3 S minutes Fix(2)
- 4~ 5 minutes l~ash
~; 20 5 5 minutes Bleach(3)
6 5 minutes Wash
7 5 minutes Fix(2)
"~ , . . .
~; 810 minutes Wash
~ (i) Color Developer
;~ soluble coupler (5 x 10-3 moles)
3 N,N-dietl-yl-p-phenylenediamine HCl 3 0 g/l.
~; potasslum bromlde ~ 1.0 g/l.
sodium sulfite s 0.65 g/l.
~ potassium~triphosphate ~ 15.0 g/l.
pH adjusted to 12.0 at 23.8C.
.. . . .
~04~1~6
(2) Liquid li~ t
.,
sodium thiosulfate 220 g/l,
, sodium sulfite 10.0 g/l.
sodium hydroxide 0.15 g/l.
(3) Bleach
- sodium bromide 35,0 g/l.
- potasslum ferricyanide-10 H2O 200 g/l.
sodium hydroxide 0.1 g/l.
sodium tetraborate-5 H2O 1.0 g/l.
, Data resulting from subjecting the processed film
strips to spectrophotometric absorption tests were recorded. In
the following Tables II and III, "Dmax" values for several
diffusable yellow-dye-forming couplers resulting from this type
of test are shown. Couplers providing data for, Table II were
so-called "four-equivalent" couplers, while those providing data ,
. for Table III wer,e "two-equivalent" couplers. Substituent groups
appearing at the column headings in these Tables refer to the
`, structural formula at the beginning of each table, ~ ,
.,. . ~.- ~: .
. , . . ,. ' :
:.,
~!
.~,1 , .
;,. - . ' ~ ' ~.
:, , .
,,',~ , ' ,', ~ ."
,s,
-: -:
~ 9 ~, ,
. .~ ,
~0413 1~
- Ta~lc II
o o l6 S
- " " H ~
tC~l3)3c-c-cH2-c-N~ 4
: . 2 3
Coupler No. 2 3 4 5 6 Dmax
- 11 F H F H H 1.93
12 Cl C1 H H H 2,42
- 13 C1 H Cl }I H 2.63
14 Cl H H Cl . H 2.73
lS H Cl Cl H H 2.02
16 C1 H H H Cl 0.32
17 ~ Cl ~,' Cl-~iOz H 1.98 :
18 Cl H Cl -NH2 H 1.80
19 . Cl H C1-NHSO2CH3 H 1.03
-: ~ 20 ~ Cl H Cl . H 2,15
: -Nllso2-~-cH3
21 Cl - H -NO2 C1 H 2.10 ~ :
;22 ~ C1 H H -NHSO2CH3 H 0.40
23 Cl H. H -CP3 H 2.60
' ` ' ' ~' . , `
,
. .
., . . ~ . . .
. .
.
109~116 - ~ -
Y ~ U7 00 0 ~ ~ ''' '' ~'
.. . - . ~
P. T c ~ 5 :
', ~ ,~ o o o
O ~J ~ 2: o o o
~o ~ I ~ o ~ ~ b ,~
lo,o ~ o,
o o o o , .
o
~: U7 _1
X ~ ~ X
-1 ~ ~
o ~ zl ~ u u ~ u . `. .
~ U ~ X
. ,, .... o U , . . .. . ..
. . . ~ , i .
U
.. . . , ~ ... ... ..
. .. , . ~ o
.. ~ U ~ ~ U ~ ~ ~ ~ ~- C~ .
.
~ ; . ~ .. ~ , . . . . ..... .
1041116
Illustr~ti~c ~lanuf~cture of Coupler ~lateri~l
St~p 1
.
- . o ~, o R~ -
(C ~l3 ) 3C - C - C C - N~l ~}C 1 + (~1 ~ t 3N
Cl C02CH2C6H5
- ~I) (II) :
,
O ~1 0
" ~ "
(CH3) 3C-C -C -C -NHJ~ O ~Cl ` :
O ~ : ,.': '
/~ Cl
,
co 2 C~1 2C 6H 5
~ I I I )
- ~
- A solution of 76.9 g of the amide (I) and phenol (II) , ,
in 400,ml,of acetonitrile containing 30.1 g. triethylamine was ,,
- heated at reflux for 2-1/2 hours. The solution was then evapora- ' ,
10' ted in vacuum. The resulting solid material was dissolved in
500 ml chloroform, extracted 3 times with 100 ml water and then
dried ovcr ~gSO4, filtered, and concentrated in vacuum. The
resulting yellow syrup was dissolved in 200 ml methanbl and ,
crystallized at room temperature, The dried crystalline product
had a melting point of 92-95C.
' Step'2
.
O ~1 0 -'
Product from Step 1) H2lPd>C " ' " ~ Cl
EtOAc ~ 3 3
III)
~ Cl
I O I
(IV)
' ' COzH
,
,,. . ~ . .
2 -
.
~ : , , : : -
104111~i
~ solution of ~1.4 g of the product from Step l,
above, in 300 ml ethyl acetate and 2.0 g of 10% palladium on
carbon was shaken under 40 psi of hydrogen until hydrogen uptake
ceased. Then the solution was warmed to completely dissolve the
product. The resulting suspension was filtered to remove
catalyst, and the filtrate was dried. The pale, pink solid
material was recrystallized twice lth methanol containing
charcoal (for color improvement) to yield a product (Compound
IV) having a melting point of 185-187.5C.
The invention has been described in detail with
: ... . .
particular reference to preferred embodiments thereof, but, it
will be understood that variations and modificatîons can be
: . .
effected within the spirit and scope of the invention.
.
.
: ' , ' ' ' :
; ~
.
" ; ' ' .
, : ~
..
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~ .
. . .
:..
~ 3
