ilat-‘iterated July 22, 1947
2,424,256
UNITED STATES PATENT" OFFICE
COLOR DEVELQPEBS COMPRISING‘ ARYL
SULFONHYDRAZIDES
METHODS OF
DEVELOPING
SAME
Willy A. Schmidt‘ a'ii'd" Joseph A, Sprungl Eastqn,
Pa., assignors to Generalv Aniline‘ &_Film ‘Cor
porati'on, New York, N. Y-., a corporation or
Delaware
No Drawing, Application January 23, 1945,
Serial N0. 574,810‘
1
21 Claims‘; (CI. 954-88‘)
2
The present invention relates to color ph‘ol'
not produced from the iii-aromatic sulfonhy
tography and particularly to the product-ion'of
azo dyestu? images by the utilization of color de'#
drazide during the development with an azo dye
stu? coupling component. It appears that the”
velopers which during development are condi
oxidation‘ conditions which prevail ‘during such
tioned for reaction with an aim dyestuff coupling‘ 3 development convert said “(i-aromatic sulfonhy
component to produce an azo dyestu?.
drazide to ‘an aromatic'diaz'o sul'fone; The latter
Considerable attention has been given by‘ the‘
compound is capable ofr'eactihg with a coupling
component the same as any true diazoniiim salt.
inpther words; during the reduction of‘ the sn'ver
art to the employment of azo 'dye‘st‘u?s for the
formation of color images in color photography.
It is known that the azo dyestuffs are more stable
than the azo methine and quinon'eimine ‘dyes
salt‘, the" Biarolnatic suirsnhyurazide is condi
tioned for‘ reaction with the az‘o coupling com
ponent; as a consequence of which an aZo' d'y'e
which constitute the dyestu? images produced
in color ?lm by the color forming development
method devised by Fischer and described‘ in"
U. S. P. 1,102,028. Furthermore, the'azodvyeistu?‘s“
give brilliant images and because of the great‘
number of components which may be reacted to
produce such dyes, they provide a greater 'n'unr
ber of alternates for forming the dyest'uff images.
Many methods have been proposed by which 20
azo dyestu? images'are formed'in color ?lm. ‘One
method, known as the silver d'ye‘ bleaching’
images" are to be understood as those obtained
method, involves the pre~dy6ing of a silver halide
by rebonvers'ibnof a} negative or positive silver
emulsion, the exposure and development of the
stuff image is formed in situ with the silver
image-
.
.
w.
,
..
It is to be pointed out that by “prints’f‘we mean
latent images which have been obtainedby ex
posing a sensitive photographic emulsion of
higher contrast than is ordinarily used for nega
tl‘irv'e', material, fora longer period‘ of time than is
customarily used for negative eiiposu'r'e‘ in a
camera; On the‘ other hand; “bleached silver
image into a silver salt image after treatment
same and a bleaching of the dyestu? at the places
with an: oxidizing agent in the presence oi‘ an
of the silver image.
anion capable of forming a'nins'olub'le silver salt.
nate‘ an imageresintm'gnan-the development
an originallatent image to a silver image and
consists’of the silver halide un'a?écte‘d'b'y origi
Thi’s'method is disadvan
The ?eriii- “residual silver saltiimagéfismtodesig}
tageous for the reason that the colored emulsions
act as ?lters requiring long exposures to give bal
anced images in the various emulsion layers.
Another method takes advantage of the fact
that diazonium compounds are capable of form
ing silver antidiazotates. According to this pro
sarexpashre
It is-a'ccordiii‘gly
and‘ ?rst
an-o'bjectiof
development.
the present 'invenf
_
cedure a silver image is bleached and treated with
an alkali antidiazotate to convert the bleached
non-memorials
by the utilizationlasl
azo'dyes'tu?
a developing
imagesagent
‘in color
of a [3'
silver image lntc a silver antidiazotate. The
treated emulsion is then subjected to the action
a'romatic sulfonhydr‘azide.”
of a coupling compound in the presence of an
acid medium to produce the dyestuff image.
Still another method proposes to'incorporate
in an emulsion a coupling component, to expose,
develop and fix the emulsion and to couple the
coupling component with a diazonium compound
in the presence of a heavy metal salt. Through
the agency of such salt, the dyestuff is formed
in the areas free from metallic silver.
H
i
H
_
'
It is" ailirtlierfrobjectiof thisinve'ntioni t'o'_'proé
duce and dressing images in color‘?l’m by the'utri
liza?on as a- developing agent: of a p-aromatic
sul'fyoiihydrajzide in'wjhich‘t-he sulfur atom is subj
stituted' by hydroxyl true corresponding alkali
pi‘smiiipmum salts,v or by an alkyl or an
aromatic
45:
radical.
v
V
‘
a
V
_
I
>
It is'a further‘object'lof this invention to pro
duce az'o'v dyést‘u’ff images‘ by reacting a'couplin'g
component with’ the‘ product resulting rrqmjt-he
_
.
.
.
.
These latter methods, a study'reveals, have
oxidation of an aforesaid ?-aromat'ic sulfonhyi
many shortcomings ‘which have militated against
drazi'de‘ ‘during the'development of a‘ print; ‘a
their general adoption for practical purposes and
bleached1 silver image or a‘ residual silver salt
have been applied only to a limited extent.
We have now discovered’ that azo dyestuif 50: It is‘ajfurth'er obl'e'ctof this invention to ping;
images can be prepared by the simple method of
imfelgé.
developing latent silver halide images, particu- '
larly prints, bleached silver images and residual
1,,
..
.
a
H
_
‘containing
esssilve‘r halide‘
azo‘ ‘dyestuff
emulsions‘
images
leading
by developing’
to vcolor a‘
‘print; a'b'leachecl silver image or a residual silver
salt-image with an aforesaid p-aromatidsulfom
drazide and the subsequent coupling of the prod- 6B: hydrazide" andreacting the oxidation product of
silver salt images with a ,s-aromatic sulfonhy
2,424,256
3
4.
therefore be more speci?cally de?ned by the fol
lowing formula:
said c-aromatic sulfonhydrazide with an azodye
stuif coupling component.
It is a further object of this invention to pro
vide a color developer comprising an aforesaid
c-aromatic sulfonhydrazide and an azo dyestuff 5 wherein X1 is an aromatic hydrocarbon such as
phenyl, naphthyl, diphenyl and the like, and such
coupling component,
radicals substituted by a neutral or electroposi
tive radical such as alkoxy i. e. methoxy, ethoxy,
It is a further object of this invention to de
velop a silver halide emulsion containing an azo
propoxy and the like, aryloxy i. e. phenoxy and
means of an aforesaid ?-aromatic sulfonhydra 10 the like, primary amino, substituted amino such
as alkylamino i. e. methylamino, dimethylamino,
zide by which an azo dyestuff is produced in situ
ethylamino, diethylamino, propylamino, butyl
with the silver image.
amino and the like, arylamino such as phenyl
It is a further object of this invention to facili
amino and the like, acylamido such as alkyl car
tate the aforesaid coupling reaction by the utili
15 bonamido i, e. acetamido, propionamido, butyr
zation of a nitrogenous base.
amido and the like, arylcarbonamido such as
Other and further important objects of the in
benzamido and the like, sulfonamido such as
vention will be apparent as the description pro.
alkyl sulfonamido i. e. methylsulfonamido, ethyl
ceeds.
sulfonamido and the like, and arylsulfonamido
The p-aromatic sulfonhydrazides which we
employ according to the present invention are 20 such as phenylsulfonamido and the like, R is
OH or the corresponding alkali metal and am
embraced by the following general formula:
monium salt groups, alkyl such as ethyl, methyl,
dyestu? coupling component fast to diffusion by
propyl, butyl, hexyl, decyl, dodecyl, stearyl and
the like, or such radicals containing a water
in which X is an aromatic radical such as phenyl,
solubilizing
group such as sulfo, carboxy, hy
naphthyl and the like, R is hydroxy or the cor 25
droxy ethenoxy and the like, or an aromatic
responding alkali metal or ammonium salt radi
radical such as phenyl, naphthyl, diphenyl, chlor
cal, alkyl or an aromatic radical. While the
phenyl,
nitrophenyl, chlornaphthyl, hydroxy
invention can be effected with compounds of this
phenyl,
hydroxy
naphthyl, alkylphenyl, alkoxy
formula, it has been ascertained that certain
properties of the aromatic sulfonhydrazides must 30 phenyl, hydroxy diphenyl, aminophenyl, alkyl
aminophenyl, arylaminophenyl and amidophenyl,
be taken into consideration in selecting those
the
alkoxy, amino, alkylamino, arylamino, amido
which will give the best results. Among these
and alkyl groups having the values stated pre
factors are
viously, and n being 1 or 2.
While it is true
35 that the aromatic radical represented by R may
bear negative substituents, it is advisable when
(1) Stability of the compounds,
(2) Speed of development, and
(3) Speed of coupling.
employing such groups to limit the substitution
of the aromatic ring to one such group since
otherwise the stability of the compound may
It has been further ascertained, and this is an
important aspect of the invention, that these
factors are greatly affected by the substituents 40 suffer.
Examples of compounds which fall within this
on the aromatic ring joined to the [fl-nitrogen
general classi?cation are listed below:
atom on the one hand and on the aromatic
radical joined to the sulfur atom on the other
hand. Thus experiments have shown that where
0
0
O
O
0
O
2) CH:
the aromatic ring joined to the nitrogen atom 45
Sodium salt of phenyl hydrazine sulionic acid
on the one hand and the aromatic radical repre
sented by R on the other hand are substituted
by electropositive groups or substituents, the rate
of development is most rapid. The stability of
the compounds is decreased considerably when
the aromatic radical joined to a sulfur atom is
substituted by an electronegative substituent.
The rate of coupling of the diazo sulfones lead
ing to the azo dye is more rapid when the sub
stituent on said aromatic ring joined to a nitro
gen atom is neutral or weakly electropositive. An
electronegative substituent on said aromatic radi
cal represented by R is found in many cases to
increase the speed of coupling. From these ex
periments the conclusions have been reached that
in the preferred compounds the substituents on
the aromatic radical joined to the p-nitr'ogen
atom should be either electropositive or neutral,
whereas the substituents on the aromatic radical
represented by B may be neutral, electropositive
or electronegative.
NH-NHS OYSNHL
Ammonium salt of phenyl hydrazine sulfonic acid
50
?-phenyl-ethanesulfonhydrazide
55
?-phenyl-methanesulionhydrazide
60
?-phenyl-dodecancsulionhydrazide
NH-NHSOiCHa
65
_
B-(3'-methoxy-pbenyl) methanesulfonhydrazide
By electropositive radicals is meant those radi
cals which are electron donating in character,
such as the acylamido and alkoxyl radicals.
Neutral radicals or groups are hydrogen and alkyl 70
groups. The electronegative radicals are those
which possess electron attracting properties, such
as halogen, nitro, sulfo, carboxy and the like.
The ?-aromatic sulfonhydrazides which have
been found most suitable for my purposes may 75
@
B-(p'-octadccyl-phenyl)-methanesulionhydrazidc
0
-
H3701
NH-NHSOzCHs
(C2115) 2N
NH-—-NHS 0202115
?-(4’-diethylamino-phenyl)~etl1anesulfonhydrazide
‘2,424,253
2;?
.
sotic acid, 2-hydroxy-3-naphthoic acid anilide,
acetoacetanilide, I-phenyI-S-pyrazolone and the
ing acetoacetanilide to form the azo dye with
elimination of a sul?nic acid group;
‘
like.
.
.
The process of ‘producing azo dyestuif images
by the utilization of said B-a‘romatic sulfonhy
drazides may be effected in various ways.
For
instance, a ?lm may be exposed and developed in
a black and white developer, ?xed, the image
II Ar——N=NSOzR '+ OHaCOCHzCONHO __->
bleached to a silver salt image and re-developed
O O CH:
+ RSOzH,
ArN=NCH
with said ,B-aromatic sulfonhydrazide in the pres
ence of an azo coupling component.
\CONHO
Or a silver
halide emulsion‘may be exposed, developed in a
black and white developer, re-exposed and devel
oped with the p-aromatic sulfonhydrazide in the
presence of the coupling component. Again, a
Similar reactions takeplace when the coupler is a
phenol or the like. -
silver halide emulsion containing a coupling com
I1; has been stated above that‘the sulfonhy
ponent fast to diffusion may be processed as above.
drazides may contain an electronegative group in
The color developing solutions are generally
the aromatic radical represented by R. It is pre
alkaline
in nature and the alkalinity may be sup
ferred, however, that such radical either be un
substituted or be substituted by a-neutral group -. 20 plied by means of an alkali metal carbonate such
as sodium carbonate, potassium carbonate and
such as alkyl or by an electropositive group such
the like, or an alkali metal hydroxide such as
as an alkoxy, amino, acylamido or the like group,
sodium hydroxide, potassium hydroxide, etc. The
since it has been found that any sacri?ce in cou
said ,B-aromatic' sulfonhydrazide is ‘dissolved or
pling speed due to the presence‘ of such a group
is more than compensated for byv an increase in v25 dispersed in the alkaline solution. Generally the
--NHSO2R group ofthe hydrazide is sufficiently
the stability of the compounds.v Should it tran
acidic to make the compound soluble in the alka
spire that the compounds selected have a low
line solution. ‘ In the event, however, that such
rate of coupling, coupling may be facilitated by
grouping does not ‘render the compound sul?
the utilization of small quantities of a ni
trogenous base incapable of coupling with‘ a di 3.0 cientiy soluble, a water-solubilizing group such as
a sulfonic acid or carboxylic acid group should
azonium compound to form an azo dye such as
be incorporated into the alkyl or aryl radical
ammonium hydroxide, an aliphatic amine, i. e.,
linked to the sulfur atom. It is of course evident
meth'ylamine, dimethylamine, ethylamine, di
that where R in the above formula stands for OH
ethylamine, trimethylamine, ethanolamine, di
ethanolamine, triethanolamine, propanolamine,
or the corresponding alkali metal or ammonium
salt group, ‘the compound will be soluble in an
butylamine and the like or heterocyclic ni
alkaline solution.‘
trogenous base such as pyridine, quinoline and
As is evident, the gradation of the dyestuif
the like. The aromatic amines are of course ca
images .will vary with the particular p-aromatic
pable of coupling and consequently are-excluded.
sulfonhydrazide selected. Should a sulfonhydra
Best results are secured while employing the 40 zldebe employed which gives poor gradation, the
heterocyclic nitrogenous bases and the's'e'are ac
selection however being dictated because of ad
cordingly recommended for use.
vantages resulting from stability of the developer,
The p-aromatic sulfonhydrazides are best
speed of development, speed of coupling or the
suited for reducing an undeveloped print, a
production of a particular dyestuff shade, the
bleached silver image or a residual silver salt im-e.
gradation may be improved by the utilization of
age to give, with coupling ‘components, azo dye
small amounts of an aliphatic aldehyde such as
images of excellent density and gradation, It.
‘formaldehyde or acetaldehyde which may be
may be noted however, that theymay also be
incorporated'inthe developing bath. Good re
used to reduce normal latent'negative images
sults have been obtained when utilizing amounts
particularly when the emulsion is one of extreme "50 of the aldehyde ranging from 1 to 5 parts for each
contrast which has been given ‘sufficient ex
liter of developer.
posure in the camera. , Where R in the above for
mula is 01-1 or a corresponding alkali. metal or
>
As previouslyv indicated, the process may be
effected while utilizing the coupling components
ammonium salt group the coupling reaction oc
curs satisfactorily only in the presence of ultra- ‘
in the silver halide emulsion provided that the
coupling components are rendered fast to diffu
sion. This result may be accomplished by includ
ing in the molecule of the coupling component a
violet radiation.
Any coupling component utilizedin the azo
dyestuff art may be employed for reaction with
substantive group such as benzidine, stilbene or
a like radical, or by the introduction of a'molec
the diazosulfone compounds. These components,
as is known, are aromatic compounds which con 60 ular enlarging group such as a natural resin, a
tain a phenolic hydroxyl group, an amino group,
synthetic resin, a sterol, a carbohydrate, a terpene,
an alkylamino group such‘ as, methylamino,
or a long fatty chain. The means by which fast
ethylamino and the like, an arylamino group
ness to diffusion may be effected are described
such as phenylamino and the like, said com
pounds having replaceable hydrogen atoms or
groups in the 0-. or p-positions thereto. They
may also be compounds which contain a reactive
methylene group such as acetoacetic acid deriva
tives, pyrazolones, and- the like. ;
‘
.
.
f
Examplesof such compounds are .—naphtho1,
N- (p-naph‘thyl), -3,-hydr_oXy-2 - naphthamide, .-N
(o-tolyl) -3-hydroxy-2- —. ,anthramide, ,N ‘- ,(1'-.an.
.1 65
in United States Patents 2,178,612, 2,179,228,
2,179,238, 2,179,239, 2,179,244, 2,186,685, 2,186,719,
2,186,732, 2,186,733, 2,186,734, 2,186,849, 2,186,851,
2,186,852, 2,280,722, etc. Thepreferred method
for rendering the vcoupling components fast to .
diffusion is by the introduction of a long fatty
chain and good results have been securediwhen
using as such chain a decyl, dodecyl, stearyl and
similar radicals. The coupling components may
be
located inemulsion layers of a three-layer ?lm,
_acid,.J_.acid, chromotropic acid-R salt, resorcinol,
diacetoaceticeo-tolidide,: .salicyclic ; acid, _ o-cre :75 a bi-pack or the like, or in a gelatin layer super
thryl) glycine,- G salt, _H_ acid, K acid, gamma
2,424,256
9
imposed on the emulsion layer.
10
The coupling.
components are selected so that. subtractively
colored dyestu?‘ images are obtained in- each of
the layers.
Said ?-aromatic sulfonhydrazides may be pro
duced by methods already described in the liter
After. development, the ?lm is then bleached I
withableaching solution of the following com
Position:
Parts
Water ______________________________ __ 1000
ature. Such methods involve condensation of an
Potassium ferricyanide ________________ __
Disodium phosphate __________________ __
arylhydrazine with a sulionyl chloride, reduction
Monopotassium phosphate ____________ __
100
4.3.
5.8
of a diazo sulfone with zinc dust or sulfur‘dioxide,
condensation of an arylhydrazine with a sul?nic 10 The ?lm isthen thoroughly washed andl?xed in
anaacid hardening hypo bath. After removal of
acid, and reduction of a diazonium salt with sulfur
the hypo by washing, and drying of the ?lm,
dioxide or sodium hydrosul?te.
there remainsablue azo dye image having the
The following examples are illustrative of the
following constitution:
invention but it is to be understood that the inven
O C2135
tion is not restricted thereto. The parts are by 15'
Weight unless otherwise stated.
Example 1
A solution of 2,5-diethoxy-4-benzamido-ben
zene-diazonium chloride prepared from 30 parts 20
of 2,5-diethoxy-4-benzamidoaniline in_500 parts
W
of water is added to a cold solution ofv 22 parts of
p-acetamidobenzene'sul?nic'acid and 13.8 parts
Example 2
of potassium carbonate in 500 parts of water. The
An exposed strip ?lm bearing a silver bromide
combined solution is slowly acidi?ed with. cold
4-N-hydrochloric acid to a pH of- 2. After the 25" emulsion is processed as in Example 1 through
the second exposure and is then developed in a
mixture has remained at room temperature for
one-half hour, the orange-colored diazo sulfone
is removed by ?ltration- and washed Well withv
water.
The material after drying in a’ vacuum 30
desiccator over phosphoruspentoxide amounted
to 33 parts, representing a yield of 65 per cent.
It melted at 110° C. with decomposition. The
product is 2,5-diethoxy-4-benzamidobenzenedi
azo- (p-acetamidophenyl) ~sulfone,
35
A solution of 25.5 parts of the above diazo
color developer having the following composition:
0.2 part of p43’-(p-di-acetamidobenzenesulfon
yl(-3.3’-dimethyl-4.4’-dihydrazinobiphenyl
dis
solved in
Parts
Ethanol ____
___
10
N -(o-tolyl) -3-hydroxy-2-anthramide ____ __ 0.2
Aqueous potassium hydroxide ___________ __ l0
Pyridine
__
5.0
37% aqueous formaldehyde solution ______ __ 0.2
sulfone in a mixture of 500 cc. of acetone, 7.5
Water
____ __
____
_
85
parts of glacial acetic acid and 10 parts of H20
is slowly treated at room temperature under vigor
The emulsion is bleached and ?xed, yielding. a
ous stirring with zinc dust until the solution 40 ?lm strip containing a green azo dyestu? image
turns from a deep orange to a faint yellow color.
having the following constitution:
CH3
CH3
HO
CH:
The zinc compounds are removed by ?ltration,
and the cooled ?ltrate is diluted with 250 parts of
water. The sulfonhydrazide, which separates, is
The pp’-(p-di-acetamidobenzenesulfonyl)-3.3'
removed by ?ltration and dried in a’ vacuum‘
sulfonhydrazide of Example 1.
Example 3
desiccator over phosphorus pentoxide. The yield 55
is 16 parts or 62%. The material when recrystals
lized from dilute ethanol melted at 166° C. with
dimethyl-4.4'-dihydrazinobipheny1 is obtained by
a method similar to that utilized in preparing the
To a solution of 43 parts of phenylhydrazine
in 180 parts of ether chilled in an ice bath, there
is slowly added with stirring
A photographic ?lm containing a light-sensi
60
tive silver bromide emulsion is exposed and. de
44.3 parts of'3-chlorosulfonyl benzoic acid in 180
veloped in a metol-hydroquinone developer. The
parts of ether.
?lm after. washing is re-exposed to light and:
After the mixture has remained at room tem
processedfor 15 minutesv at 15<to 20° C; in a'colori
perature for one hour, 25000. of a low boiling
developer of- the following composition:
65 petroleum ether is added and the solid material
0.2 part of ,B-(2.5-diethoxy-4-benzamidophen
is removed by ?ltration and washed with petro
yl). -p.-acetamidobenzenesulfonhydrazid'e;dissolved
leum ether. The product is digested with one
in.
liter of dilute hydrochloric acid to remove the
Parts‘
phenylhydrazine hydrochloride and the residue
Ethanol _______________________________ __ 10
is recrystallized from dilute ethanol. 44 parts of
N- (p-naphthyl) -3-hydroxy-2-naphthamide- 0.2
a product are obtained representing a yield of
10% aqueous potassium hydroxidesolution__ 10
75%‘. The product is p-phenyl-B-carboxyben
Pyridine ___________________________ __g____ 1.0_
zenesulfonhydrazide which has a melting point of
decomposition.
37% aqueous formaldehyde _____________ __
Water
02-
____ __ 85
178910: with decomposition.
A photographic ?lm containing a silver halide
2,424,256
11
V
.
,
tion:
in the patent, however, do not contain an alkyl
or aryl sulfonyl group or sulfo salt groups as in
Tithe compounds of our invention. Accordingly,
‘the reaction by which the dyestuffs are formed
is different. In addition, as previously pointed
out, it is possible with our color developers to
vary the properties by suitable selection of the
.substituents on the various aryl groups present
'
0.2 part of ,8-phenyl-3-carboxybenzenesulfon
hydrazide dissolved in
Parts
Ethanol ____
____
p-naphthol _________ _'_ _________________ __
10
0.2
Aqueous potassium carbonate ____________ .._. >10
Pyridine ______________________________ __
1.0
37% aqueous formaldehyde solution ______ __
0.2
Water _____ __
_
10 in the molecule. Inasmuch as said properties
have a direct bearing upon the processing of the
?lm, as previously explained, the processing can
be better regulated when using the sulfonhydra
‘_ ‘zides in lieu of the phenyl hydrazines of the pat
85
After development, the ?lm is washed and
bleached for 5 minutes in a bath as described in
Example 1. The washed ?lm strip is then ?xed
in a bath of 20% aqueous sodium thiosulfate.
The resulting ?lm contains an orange azo dye
image of the following constitution:
12
emulsions. The aromatic hydrazines employed
emulsion is exposed and developed in a metol
hydroquinone developer. The ?lm is washed, re-g
exposed to light and developed for 15 minutes at
15 to 20° C. in a bath of the following composi
15
- ent.
Various modi?cations of our invention will oc
- our to persons skilled in the art and we there
fore do not intend to be limited in the patent
granted except as necessitated by the prior art
20 and the appended claims.
We claim:
1. The process for the production of azo dye
stuff images in an exposed silver halide emul
M3
sion layer which comprises subjecting said emul
25 sion to development with a solution of a B-aro
matic sulfonhydrazide in the presence of an azo
do‘ OH
dye coupling component.
2. The process as de?ned in claim 1 wherein
Example 4
the azo dye coupling component is located in the
A multilayer ?lm sold under the trade name 30 solution of the ,B-aromatic sulfonhydrazide.
3. The process as de?ned in claim 1 wherein
the solution of the ,B-aromatic sulfonhydrazide
and white as in Example 1 and after re-expo
is an aqueous alkaline solution.
sure is color developed for 20 minutes in a bath
4. The process of producing an azo dyestuff
of the following composition: ,
0.2 part of ,8-phenyl-3-carboxybenzenesul 35 image in a photographic element bearing a sil
ver halide emulsion containing an exposed sil
fonhydrazide dissolved in
ver halide image which comprises subjecting said
Parts
emulsion to development with a B-aromatic sul
Ethanol _______________________________ __ 10
“Ansco Color” is exposed, developed to black
Potassium carbonate solution ___________ __ 10
Pyridine _______________________________ __
2.0
37% aqueous formaldehyde solution _____ __
0.2
Water _________________________________ __ 85
The ?lm is then bleached and ?xed as in Example
1, thereby yielding a yellow-green azo dye image
in the ?rst layer, a yellow azo dye image in the
second layer, and a red azo dye image in the third
fonhydrazide whereby said image is converted
40 into a silver image and said sulfonhydrazide is
simultaneously converted into a diazosulfone,
and coupling said diazosulfone with an azo dye
coupling component, in the presence of a nitrog
enous base incapable of coupling to form an
45 azo dye, to facilitate the coupling reaction.
5. The process as de?ned in claim 1 wherein
the solution of the B-aromatic sulfonhydrazide
layer.
contains a small quantity of an aliphatic alde
Example 5
hyde for the purpose of improving the gradation
4 parts of N-(3-octadecamidobenzyl) H-acid 60 of the azo dyestu? image.
6. The process as de?ned in claim 1 wherein
are dissolved in 5 cc. of sodium carbonate of 20%
the coupling takes place in the presence of a
strength and 50 parts of water. The resulting
small quantity of an aliphatic aldehyde to im
solution is added to 1000 parts of a photographic
prove
the gradation of the azo dyestu? image.
silver bromide emulsion. The emulsion is coat 55
7. The process of producing an azo dyestu?f
ed, exposed, developed in a black and white de
image in a photographic element bearing a silver
veloper as in Example 1 and then developed with
halide emulsion, said element containing an azo
the sulfonhydrazide developer described in Ex
dyestuif coupling component fast to di?usion and
ample 3. After further processing the ?lm as
in said emulsion an exposed silver halide image
in Example 1, there is obtained a magenta dye
60 vwhich comprises subjecting said element to the
stu? image of the following constitution:
action of a solution of a p-aromatic sulfonhy
drazide whereby said image is developed to a
silver image, and an azo dyestu? is formed in
situ with the silver image by coupling of the
65 coupling component with the oxidation product
of said hydrazide.
.
‘8. The process as de?ned in claim 1 where
said p-aromatic sulfonhydrazide has the follow- .
'ing formula:
‘ N803S
some
I am aware of the existence of U. S. P. 2,339,213,
70
X being an aromatic radical, R being a member
of the class consisting of OH, O-alkali metal,
which discloses the employment of aromatic hy
O-N'H4, alkyl and an aromatic radical.
drazines with suitable coupling agents for the
production of azo dyestu? images in silver halide 75. 9. The process as de?ned in claim 4. wherein.
2,424,256
13
14
said ,B-aromatic sulfonhydrazide has the follow
ing formula:
of OH, O-alkali metal, O—NH4, alkyl and an
aromatic radical and X1 is a member of the class
consisting
of
aryl,
alkoxyaryl,
aryloxyaryl,
aminoaryl and acylaminoaryl radicals, an azo
wherein R is a member of the class consisting of
CI dye coupling component, and a small amount of
OH, O-alkali metal, O—NH4, alkyl and an arc
a nitrogenous base incapable of coupling to form
matic radical and X1 is a member of the class
an azo dye and serving to facilitate the coupling
consisting
of
aryl,
alkoxyaryl,
aryloxyaryl,
aminoaryl and acylaminoaryl radicals.
of the azo dye coupling component with the
oxidation products of the p-aromatic sulfonhy
10. The process as de?ned in claim 7 wherein 10 drazide.
18. The composition as de?ned in claim 14 in
which there is present a small amount of an ali
said Iii-aromatic sulfonhydrazide has the follow—
ing formula:
phatic aldehyde to improve the gradation of the
B. being a member of the class consisting of OH,
O-alkali metal, O—NI-I4|, alkyl and an aromatic
radical and X1 being a member of the class con
sisting of aryl, alkoxyaryl, aryloxyaryl, amino
aryl and acylaminoaryl radicals.
11. A color developer comprising a solution of a
B-aromatic sulfonhydrazide and an azo dyestuff
coupling component.
12. A color developer comprising a solution of
a ?-aromatic sulfonhydrazide, an azo dye cou
pling component and a small amount of a nitrog
enous base incapable of coupling to produce an
azo dye and operating to facilitate coupling of
the azo dye coupling component with the oxida
tion products of the ?-aromatic sulfonhydrazide.
azo dye formed by the color developer.
19. The process of producing a reversed azo
dyestu? image in a photographic silver halide
emulsion which comprises exposing a silver halide
emulsion, developing the same in a black and
white developer, re-exposing the emulsion, and
developing the same in an aqueous alkaline solu
tion of ?-phenyl-3-carboxybenzene sulphonhy
drazide and p-naphthol.
20. The process of producing an azo dyestuif
image in a photographic silver halide emulsion
which comprises exposing the emulsion, develop
ing the same in a black and white developer, re
exposing the emulsion, and developing the same
in an aqueous alkaline solution of ?-(2.5-di
ethoxy - 4 - benzamidophenyl) -p-acetamido-ben
13. The composition as de?ned in claim 11
zenesulfonhydrazide and N-(?-naphthyl) -3-hy
wherein the solution is an aqueous alkaline solu 30 droxy-2-naphthamide.
tion.
21. The process of producing an azo dyestu?
image in a photographic silver halide emulsion
14. A color developer comprising a solution of
a ,B-aromatic sulfonhydrazide having the follow
ing constitution:
which comprises exposing the emulsion, develop
in which R is a member of the class consisting
in an aqueous alkaline solution of ,6.,6'-(p-di
of OH, O-alkali metal, O—-NH4, alkyl and an
dihydrazinobiphenyl and N(o-tolyl)-3-hydroxy
2-anthramide.
ing the same in a black and white developer, re
expcsing the emulsion and developing the same
aromatic radical, and X is an aromatic radical
and an azo dye coupling component.
15. The composition as de?ned in claim 14
wherein the solution is an aqueous alkaline solu
tion.
16. A color developer comprising a solution of
a B-aromatic sulfonhydrazide having the follow
ing constitution:
acetamidobenzenesulfonyl) - 3.3’ - dimethyl-4.4’
WILLY A. SCHMIDT.
JOSEPH A. SPRUNG.
REFERENCES CITED
The following references are of record in the
?le of this patent:
UNITED STATES PATENTS
in which R is a member of the class consisting
of OH, O-alkali metal, O——NI-I4, alkyl and an
aromatic radical, and X1 is a member of the class
Number
Name
Date
aryloxyaryl,
1,934,011
2,191,037
2,304,025
Schmidt et a1. ____ __ Nov. 7, 1933
Mannes et al. ____ __ Feb. 20, 1940
Schneider et al _____ __ Dec. 1, 1942
aminoaryl and acylaminoaryl radicals and an
2,339,213
Woodward et al. ___ Jan. 11, 1944
azo dye coupling component.
2,196,734
Marriage ________ __ Apr. 9, 1940
17. A color developer comprising a solution of 55
a p-aromatic sulfonhydrazide having the follow
ing constitution:
2,266,442
Schinzel _________ __ Dec. 16, 1941
consisting
of
aryl,
alkoxyaryl,
‘ 2,276,254
X1—NH--NHSO2R
Number
in which R is a member of the class consisting 60
462,140
Schinzel _________ __ Mar. 10, 1942
FOREIGN PATENTS
Country
1
Date
Great Britain ______ __ Mar. 3, 1937
' Certi?cate of Correction
Patent No. 2,424,256.
July 22, 1947.
WILLY A. SCHMIDT ET AL.
It is hereby certi?ed that error appears in the printed speci?cation of the above
numbered patent requiring correction as follows: Column 5, next to the last formula,
for that portion reading
CH
I
(IJHI
MG
MG
and that the said Letters Patent should be read with this correction therein that the " '
same may conform to the record of the case in the Patent Of?ce.
Signed and sealed this 14th day of October, A. D. 1947,
[am]
THOMAS F. MURPHY,
Assistant Gammz'ssz'oner of Patents.