Note: Descriptions are shown in the official language in which they were submitted.
525
630~
--1--
This invention relates to photography, and, more
particularly, to magenta dyes for use in providing
diffusion transfer color images, and to photographic
products and processes employing such magenta image dyes.
Multicolor images formed in accordance with the
principles of subtractive color photography employ yellow,
magenta and cyan image dyes. The yellow dye ideally
transmits only green and red light and absorbs only blue
light, and thus is sometimes referred to as "minus blue".
10 In like manner, the magenta ("minus green") dye ideally
absorbs only green light and transmits only blue and red
light, and the cyan ("minus red") dye ideally absorbs
only red light and transmits only blue and green light.
Unfortunately, the dyes available for use in subtractive
15 color photography are not "ideal" dyes, but tend to absorb
some of the light that they ideally should transmit.
This extra absorption results in less effective reproduc-
tion by the final image of one or more colors present in
the original subject.
This problem may be illustrated by considering
the reproduction of blue light: A multicolor photosensi-
tive elemen-t, comprising a blue-sensitive silver halide
layer, a green-sensitive silver halide layer and a red-
- sensitive silver halide layer, said silver halide layers
25 having associated therewith, respectively, a yellow
image dye-providing material, a magenta image dye-provid-
ing material, and a cyan image dye-providing material, is
'~
5,45
exposed to blue light in an amount effective to fully expose the
blue-sensitive layer. Only the blue-sensitive silver halide layer
is exposed; the green-sensitive and red-sensitive silver halide
emulsion layers remain unexposed. If such an exposed photosensi-
tive element were processed by diffusion transfer techniques, the
yellow image dye-providing material would remain in the developed
photosensitive element (negative component) but magenta and cyan
image dyes would be transferred to the image-receiving layer
(positive component). Since the magenta and cyan image dyes are
"minus green" and "minus red" respectively, the combination of
magenta and cyan dyes appear blue, i.e., they transmit blue light
to the viewer and absorb green and red, thus reproducing the blue
record of the original subject.
From this illustration it will be readily apparent that
if either the magenta or cyan image dyes also absorb blue light,
the purity and quality of the "blue image" will be impaired. In
the world of practical color photography, such unwanted absorption,
sometimes referred to as "tail" absoption, is the rule rather than
the exception. Magenta image dyes typically exhibit significant
absorption in the blue region.
The present invention is concerned with providing
magenta image dyes exhibiting reduced blue absorption, i.e., in-
creased blue transmission.
This invention is concerned with providing magenta image
dye-providing materials which yield diffusion transfer color
images exhibiting more desirable color characteristics; and which
preferably transmit a high proportion of blue light,
The magenta image dye-providing materials of this
- 2
525
invention are useful in dye release diffusion transfer processes,
e.g., of the redox dye release or the silver-catalyzed dye release
types, to provide magenta image dyes exhibiting high blue trans-
mission.
Additionally, this invention is concerned with providing
magenta image dye-providing materials which exhibit good absorpt-
ion of green light while transmitting a high proportion of blue
light,
For a fuller understanding of the nature and objects of
the invention, reference should be had to the following detailed
description.
This invention is particularly directed to photographic
processes wherein the desired image is obtained by processing an
exposed photosensitive silver halide material, with a processing
composition distributed between two sheet-like elements, one of
said elements including said photosensitive material. The process-
ing composition is so applied and confined within and between the
two sheet-like elements as not to contact or wet outer surfaces
of the superposed elements, thus providing a film unit or film
packet whose external surfaces are dry. The processing composi-
tion may be viscous or non-viscous, and preferably is distributed
from a single-use rupturable container; such pressure rupturable
processing containPrs are frequently referred to as "pods". The
final image may be monochrome or multicolor, and is formed in an
image-receiving layer included in one of said sheet-like elements.
In a first embodiment the invention provides a diffusion
transfer color process wherein a photosensitive element containing
a silver halide emulsion and an image dye-providing material is
ZS
exposed and developed with an aqueous alkaline processing composi-
tion, and an imagewise distribution of a diffusible image dye is
formed from said image dye-providing material as a function of said
development, and at least a portion of said imagewise distribution
of diffusible image dye is transferred to an image-receiving layer
in superposed relationship with said silver halide emulsion to
provide a diffusion transfer dye image, and wherein said image dye
is a magenta dye containing the chromophoric system represented
by the formula:
R R
N ~ N
~ SO3-
wherein each R is the same or different and is an alkyl group, and
each X is the same or different and is hydrogen or an alkyl group.
In a second embodiment the invention provides a photo-
sensitive element comprising a support, a silver halide emulsion
in a layer carried by said support, and an image dye-providing
material in a layer carried by said support on the same side there-
of as said silver halide emulsion, said image dye-providing
material containing at least one diffusion control moiety and
providing a magenta image dye containing the chromophoric system
represented by the formula:
- 3a -
ZS25
R R
N ~ X
~ S03-
wherein each R is the same or different and is an alkyl group,
and each X is the same or different and is hydrogen or an alkyl
group.
In a third embodiment the invention provides a photo-
graphic image containinga magenta image dye, wherein said magenta
image dye is a magenta dye containing the chromophoric system
represented by the formula:
R X
N ~ N
~ S03-
wherein each R is the same or different and is an alkyl group, and
each X is the same or different and is hydrogen or an alkyl group.
In a fourth embodiment the invention provides a
compound of the formula:
- 3b -
C'
Z5
R
~$ ~,r
so3-
~.X
Yn
wherein each R is the same or different and is an alkyl group, each
Y is a diffusion control substituent containing a diffusion control
moiety D, each X' is the same or different and is hydrogen, alkyl
or -(CH2-X2-D)n wherein x2 is a divalent linking group, and n is O
or 1, provided that at least one n is 1.
As is well known in diffusion transfer photography,
image dye-providing materials which may be employed in such pro-
cesses generally may be characterized as either (1) initially
soluble or diffusible in the processing composition but which are
selectively rendered no~-diffusible imagewise as a function of
development; or (2) initially insoluble or non-diffusible in the
processing composition but which selectively provide a diffusible
product imagewise as a function of development.
.
~,i
- 3c -
5~5
--4--
These image dye-providing materials may be complete dyes
or dye intermediates, e.g., color couplers. The requisite
differential in mobility or solubility may, for example, be
obtained by a chemical action such as a redox reaction, a
5 coupling reaction, or a cleavage reaction.
In accordance with this invention, it has been
found that magenta image ~yes containin-j the chromophoric
system represented by
X
~ N ~ N ~3
~ SO3-
Formula A
wherein each R is an alkyl group and each X is either
hydrogen or an alkyl group (including substituted alkyl),
exhibit highly desirable spectral properties, including
high blue transmission. Each R and each X may be the
15 same or different. In the preferred embodiments, each R
is an alkyl group of 1 to 4 carbons, and preferably each
R is a methyl group. In particularly useful and preferred
embodiments, each R and each X is an alkyl group, with at
least one said X being a substituted al~yl, such as an
2~ aralkyl.
Image dye-providing materials capable of
providing image dyes containing the chromophoric system
of Formula A may be provided by including a diffusion
control substituent Y which substituent includes a
25 diffusion control moiety D. One such group of image
525
dye-providing materials may be represellt~ by Formllla R:
X X
n ~
~-' ~SO
Yn
Formula B
wherein each Y is a substituent containing a diffusion
5 control moiety D, X' is hydrogen, alkyl (including
- substituted alkyl) or -(CH2-X2-D)n wherein x2 is a
divalent linking group (preferably an alkylene group of
1-4 carbons), and each n is 0 or 1, provided that at
least one n is 1. Image dye-providing materials within
10 Formula B, as a function of the particular diffusion
control moiety D, are suitable for use in diffusion
transfer processes employing either initially diffusible
or initially nondiffusible image dye-providing materials.
As examples of diffusion control moieties D, mention may
15 be made of hydroquinonyl groups, color coupling groups,
sulfonamido phenol groups which cleave or ring close
following oxidation to release a diffusible dye or dye
intermediate, and of thiazolidine groups whose cleavage
is silver catalyzed. The diffusion control moiety D may
20 be attached to a covalent bond or a divalent linking group,
e.g., an alkylene radical of 1 to 4 carbons to complete
the substituent Y. Dyes wherein X' is not hydrogen are
preferred, and have been found to exhibit a shift in
absorption maximum towards middle green and a narrowed
25 absorption band width, as compared with dyes where X' is
hydrogen. Further, dyes wherein X' is not hydrogen show
less color shift in alkali. In contrast to dyes where
Z5Z5
--6--
the -SO3 is replaced by a -COO group, the dyes of this
invention resist ring closure and resultant decolorization
in acidic environments. Where the image dye-providing
material is initially diffusible, a suitable ballast group,
5 e.g., a long chain alkyl group, may be attached to the
diffusion control group.
One resonance form of the chromophoric system
represented by Formula A also may be represented as
follows:
~_X X _~
so3
Formula C
In the preferred embodiment of this invention,
the diffusion control group is a hydroquinonyl moiety,
and the resultinq dye developers are initially diffusible
15 image dye-providing materials. As described in U. S.
Patent No. 2,983,606 issued May 9, 1961 to Howard G.
Rogers, a photosensitive element containing a dye
developer and a silver halide emulsion is photoexposed
and a processing composition applied thereo, for example,
20 by immersion, coating, spraying, flowing, etc., in the
dark. The exposed photosensitive element superposed prior
to, during, or after the processing composition is applied,
on a sheet-like support element which may be utilized as
an image-receiving element. In a p~eferred embodiment,
25 the processing composition is applied to the exposed
photosensitive element in a substantially uniform layer as
the photosensitive element is brought into superposed
relationship with the image-receiving layer. The
processing composition, positioned intermediate the
photosensitive element and the image-receiving layer,
permeates the emulsion to initiate development of the
5 latent image contained therein. The dye developer is
immobilized or precipitated in exposed areas as a
consequence of the development of the latent image. This
immobilization is apparently, at least in part, due to a
change in the solubility characteristics of the dye
10 developer upon oxidation and especially as regards its
solubility in alkaline solutions. It may also be due in
part to a tanning effect on the emulsion by oxidized
developing agent, and in part to a localized exhaustion of
alkali as a result of development. In unexposed and
15 partially exposed areas of the emulsion, the dye developer
is unreacted and diffusible and thus provides an imagewise
distribution of unoxidized dye developer, diffusible in the
processing composition, as a function of the point-to-point
degree to exposure of the silver halide emulsion. At least
20 part of this imagewise distribution of unoxidized dye
developer is transferred, by imbibition, to a superposed
image-receiving layer or element, said transfer substan-
tially excluding oxidized dye developer. The image-
receiving layer receives a depthwise diffusion, from the
25 developed emulsion, of unoxidized dye developer without
appreciably disturbing the imagewise distribution thereof
to provide a reversed or positive color image of the
developed image. The image-receiving element may contain
agents adapted to mordant or otherwise fix the diffused,
30 unoxidized dye developer. In a preferred embodiment of
said U. S. Patent No. 2,983,606 and in certain commercial
applications thereof, the desired positive image is
revealed by separating the image-receiving layer from the
photosensitive element at the end of a suitable imbibition
35 period. Alternatively, as also disclosed in said U. S.
Patent No. 2,983,606, the image-receiving layer need not
be separated from its superposed contact with the
photosensitive element, subsequent to transfer image
SZ5
--8--
formation, if the support for the image-receiving layer,
as well as any other layers intermediate said support and
image-receiving layer, is transparent and a processing
composition containing a substance, e.g., a white pigment,
5 effective to mask the developed silver halide emulsion or
emulsions is applied between the image-receiving layer and
said silver halide emulsion or emulsions.
Dye developers, as noted in said U. S. Patent
No. 2,983,606, are compounds which contain, in the same
10 molecule, both the chromophoric system of a dye and also
- a silver halide developing function. By "a silver halide
developing function" is meant a grouping adapted to develop
exposed silver halide. A preferred silver halide develop-
ment function is a hydroquinonyl group. In general, the
15 development function includes a benzenoid developing
function, that is, an aromatic developing group which
forms quinonoid or quinone substances when oxidized.
Multicolor images may be obtained using dye
developers in diffusion transfer processes by several
20 techniques. One such technique contemplates obtaining
multicolor transfer images utilizing dye developers by
employment of an integral multilayer photosensitive
element, such as is disclosed in the aforementioned U. S.
Patent No. 2,983,606 and in U. S. Patent No. 3,345,163
25 issued October 3, 1967 to Edwin H. Land and Howard G.
Rogers, wherein at least two selectively sensitized
photosensitive strata, superposed on a single support, are
processed, simultaneously and without separation, with a
single common image-receiving layer. A suitable arrange-
30 ment of this type comprises a support carrying a red-
sensitive silver halide emulsion stratum, a green-
sensitive silver halide emulsion stratum and a ~lue-
sensitive silver halide emulsion stratum, said emulsions
having associated therewith, respectively, for example, a
35 cyan dye developer, a magenta dye developer and a yellow
dye developer. The dye developer may be utilized in the
silver halide emulsion stratum, for example in the form
of particles, or it may be disposed in a stratum behind
5~5
_9_
the appropriate silver halide emulsion strata. Each set
of silver halide emulsion and associated dye developer
strata may be separated from other sets by suitable
interlayers, for example, by a layer or stratum of
5 gelatin or polyvinyl alcohol. In certain instances, it
may be desirable to incorporate a yellow filter in front
of the green-sensitive emulsion and such yellow filter may
be incorporated in an interlayer. However, where
desirable, a yellow dye developer of the appropriate
10 spectral characteristics and present in a state capable of
functioning as a yellow filter may be so employed and a
separate yellow filter omitted.
Particularly useful products for obtaining
multicolor dye developer images are disclosed in U. S.
15 Patent No. 3,415,644 issued December 10, 1968 to Edwin H.
Land. This patent discloses photographic products and
processes wherein a photosensitive element and an image-
receiving element are maintained in fixed relationship
prior to exposure, and this relationship is maintained as
20 a laminate after processing and image formation. In
these products, the final image is viewed through a
transparent (support) element against a light-reflecting,
i.e., white background. Photoexposure is made through
said transparent element and application of the process-
25 ing composition provides a layer of light-reflecting
material to provide a white background. The light-
reflecting material (referred to in said patent as an
"opacifying agent") is preferably titanium dioxide, and
it also performs an opacifying function, i.e., it is
30 effective to mask the developed silver halide emulsions
so that the transfer image may be viewed without
interference therefrom, and it also acts to protect the
photosensitive silver halide emulsions from post-exposure
fogging by light passing through said transparent layer if
35 the photoexposed film unit is removed from the camera
before image-formation is completed.
U. S. Patent No. 3,647,437, issued March 7, 1972
to Edwin H. Land, is concerned with improvements in
2S
- 1 o -
products and processes disclosed in said U. S. Patent No.
3,415,644, and discloses the provision of light-absorbing
materials to permit such processes to be performed,
outside of the camera in which photoexposure is effected,
5 under much more intense ambient light conditions. A
light-absorbing material or reagen-t, preferably a pH-
sensitive phthalein dye, is provided so positioned and~or
constituted as not to interfere with photoexposure but so
positioned between the photoexposed silver halide emulsions
10 and the transparent support during processing after photo-
exposure as to absorb light which otherwise might fog the
photoexposed emulsions. Furthermore, the light-absorbing
material is so positioned and/or constituted after
processing as not to interfere with viewing the desired
15 image shortly after said image has been formed. In the
preferred embodiments, the light-absorbing material,
also sometimes referred to as an optical filter agent,
is initially contained in the processing composition
together with a light-reflecting material, e.g.,
20 titanium dioxide. The concentration of the light-
absorbing dye is selected to provide the light trans-
mission opacity required to perform the particular
process under the selected light conditions.
In a particularly useful embodiment, the
25 light-absorbing dye is highly colored at the pH of the
processing composition, e.g., 13-14, but is substantially
non-absorbing of visible light at a lower pH, e.g., less
than 10-12. This pH reduction may be effected by an
acid-reacting reagent appropriately positioned in the
30 film unit, e.g., in a layer between the transparent
support and the image-receiving layer.
11~.'~5~5
The dye developers are preferably selected for their
ability to provide colors that are useful in carrying out sub-
tractive color photography, that is, the previously mentioned cyan,
magenta and yellow. The dye developers employed may be incorporat-
ed in the respective silver halide emulsion or, in the preferred
embodiment, in a separate layer behind the respective silver
halide emulsion, and such a layer of dye developer may be applied
by use of a coating solution containing the respective dye develop-
er distributed, in a concentration calculated to give the desired
coverage of dye developer per unit area, in a film-forming natural,
or synthetic, polymer, for example, gelatin, polyvinyl alcohol,
and the like adapted to be permeated by the processing composition.
In accordance with the present invention magenta dye
developers containing the chromophoric system of Formula A may be
provided by dye developers as defined in Formula B wherein the
diffusion control moiety D is a silver halide developing moiety,
e.g., a hydroquinonyl group. In such image dye-providing materials
the diffusion control substituent Y may be represented by
-A-D
wherein D is a hydroquinonyl group and A is a covalent bond or a
divalent linking group, e.g., alkylene.
Examples of such dye developers include:
X - 11 -
~l~Z52S
--12--
CH CH 3
CH~ +
~ S03 CH2--CH2 CH2
. bH
Dye 1
CH CH
CH~
6C3 ~,503 C3 6
Dye _?_
il~2525
--13--
3 CH3
C2H5~ 1C2 C 3 OH
6C3 ~503 3 6
OH H
Dye_3
[~ Cl H 3~ CEI ~ ~
SO3 _3
Dye 4
ZS
CH3 CH3
H H OH
~:[ CH~ 1~502-NH-CH-CH
03 CH3 OH
Dye 5
C~ ~ ~C~ ~ CH
503 502-NH-CH-CH
OH
Dye 6
j~ - 14 -
ll'~Z5~S
--15--
CH CH
~ ~i~3 ~ li ~, ~
~3--so3-
SO2
-C132-C~32
~i
Dye 7 OH
Dye 8
ZS25
CH3 CH3
I H H
N ~ ~ -502-NH-CH-C
SO3
OH
Dye 9
CH CH3
CS~ ~3
SO3 CH -CH -CH
OH
Dye 10
- 16 -
,
--1 7--
CH ~'H
`H~3-CHI~ OH
[~-.503 CH2 CH2--C11
OH
Dye 1 1
CHCH
~ N ~ ICHi~ OH
[~H6C3 ~ 503 C3H
Dye 1 2
~l'l.'ZS;~S
--18--
3 ~1 H CH 3
01 ~ '3H6
OH
Dye 1 3
3 H C ~ 3
OH ~H3G~H3~ OH
(~H6C3 ~-- S03 C3 6
OH
OH
Dye 1 4
5f-5
--19--
CH3 CH
2)3 ~ ~ 3
H
Dye 1 5
CH 3 CH
CH~= CH~
3 ~ S03 CH2--CH2 CH
Dye 1 6
i~ S~5
--2Q--
C114N~3 50~ IH2CH3
NO
Dye 1 7
OH
2 2 2
$ CH~_
~6C3 ~SO3- C3i36
H H
Dye 1 8
~1~25Z5
OH OH
CH2--CH2 CH2 fH2--CH3 CH
H C ~ '1$ OH
¢~ 6 3 [~ 53-C3~6
OH
Dye 1 9
3 1 3 CH3
N ~ N ~lb
(CH )
1~j3 ~ 3_S03- 'S)3
HO ~OH HO ~ OH
Dye 2 0
-- 2 1 --
il~ 5~5
--22--
CH CH
; r I
OH (3 53 (C 2) 3
OH
Dye 2 1
~N~N~3
12
NH
H 3C-CH -CH 2
Dye 2 2
OH
S~S
--23--
OH OH
[~( CH~3
~(CH2~ 3 ~so3 ( 2) 3
OH
Dye 2 3
CH ~OH HO~CH 3H
[~( 1 2 )~ ICH~
~SO3
Dye 2 4
11'~;~525
HO ~ CH3
2
(CH2)3 ~ (CH2)
OH OH
Dye 25
CH3 CH3
CH ~ ~H ~
(CH2)3 ~ so3 NH SO
H3C-CH-CH
OH
Dye 26 OH
Dyes 18 and 19 are the subject of applications which have
issued as United States Patents 4,264,507 and 4,264,704 respectively.
, - 24 -
-25-
Dye developers of the type described above may
be prepared, for example, by the reaction of dichloro-
sulfone fluorescein
Cl ~ Cl
[~S2
5 with, e.g., a compound of the formula
OR
~R
wherein X, R and Y are as defined above, and each R2 is
the same and is hydrogen or a lower alkyl group. Where
R is alkyl, dealkylation of the resulting product
10 regenerates the hydroquinone moiety. Where it is desired
to have only one hydroquinonyl group in the dye developer,
the dichloro starting material is first reacted to replace
one chloro group with an anilino group, followed by the
above described reaction to introduce the hydroquinonyl-
15 containing anilino group. Alternatively, an aminoalkyl-
hydroquinone may be reacted with a sulfonyl chloride-
substituted anilino-substituted sulfone fluorescein to
obtain dye developers such as Dyes 5 and 6 above.
Compounds within Formula D wherein A is an
20 alkylene group of 1 to 5 carbons are described in U. ~.
Patent No. 3,236,893, issued February 22, 1966 to Blout,
Green, Rogers, Simon and Woodward. Compounds within
Formula D wherein A is a covalent bond are described in
-26-
U. S. Patent No. 3,134,811 issued May 26, 1964 to Simon.
Compounds within Formula C wherein A is -SO2- are
described in U. S. Patent No. 3,218,312 issued November 16,
1965 to Green. Compounds within Formula D wherein A is
5 -S-alkylene ("alkylene" containing 1-5 carbons), e.g.,
OH CH3
2 2 ~ NH2
OH
are described in U. S. Patent No. 3,009,958 issued
November 21, 1961 and U. S. Patent No. 3,081,339 issued
March 12, 1963, both issued to Green and Rogers.
10 Compounds within Formula D wherein A is -S- are described
in U. S. Patent No. 3,009,958 issued November 21, 1961
to Green and Rogers. Compounds within Formula D where
A is -O- are described in U. S. Patent No. 3,061,434
issued October 3, 1961 to Green and Solodar. For
15 convenience, the disclosures of these U. S. patents are
hereby incorporated herein.
Where the anilino group(s) contain an amino or
an aminoalkyl substituent, a hydroquinonyl group may be
introduced by reaction with a carboxylic acid-substituted
20 hydroquinone, e.g., homogentisic acid lactone or
homogentisic acid chloride, following the procedures
described in U. S. Patent No. 3,288,778 issued November
29, 1966 to Blout, Cohen, Green, Rogers, Simon and
Woodward. Alternatively, a compound such as
OH 2
CH2- C -NH ~ CH3
OH
may be rea~ted with one or both chlorines Qf dichloro-
sulfone fluorescein; compounds of this type are described
in U. S. Patent No. 3,214,469 issued October 26, 1965 to
Green and Husek.
The following examples of the preparation of dye
developers in accordance wi~h this invention are given for
purposes of illustration and are not intended to be
limiting.
~xample 1
5.0 g. (0.012 m) of dichlorosulfone fluorescein
and 5.0 g. (0.041 m) of 2,6-dimethylaniline were refluxed
together in 50 ml. of methanol for 0.5 hour. Excess
methanol was stripped off, and the residue was triturated
with diethyl ether until it was solid. The solid was
15 filtered off, washed well with diethyl ether and dried.
Chromatography on florisil (90/10 chloroform/methanol, by
volume, as solvent) gave 3.0 g. (44%) of the monochloro
intermediate
Cl
SO3
20 as an orange powder. 25 ml. of ethylene glycol was
heated in an oil bath set at 130C and nitrogen was
bubbled in, with stirring, for 1 hour. To the hot,
deoxygenated ethylene glycol was added 3.0 g.
(5.2 x 10 ~m) of the above monochloro intermediate and
25 4.0 g. (15.7 x 10 3m) of
OH
~( CH2 ) 3~CCNH3
H
Z5
-28-
This solution was stirred at 130C while nitrogen was
slowly bubbled through. Aliquots were periodically worked
up (TLC in methanol~chloroform, 15/85 parts by volume).
After 4 hours, the hot reaction mixture was poured into
5 5~ hydrochloric acid. The precipitate was filtered off,
washed with water and dried. A small amount of the
monochloro intermediate was found to be present, and this
was removed by extraction with chloroform in a Soxlet
extractor. 3.0 g. (81~ yield) of the thus purified
10 Dye 1
CH CH
~ CH ~ T ~
~ SO3 CH2--CH2----CH2 ~
H
was obtained, and this product exhibited maximum absorp-
tion in methyl cellosolve*at 534 nanometers, epsilon
64,000. Column chromatography with methanol/tetrahydro-
15 furan, (15/85 parts by volume) gave a more pure sampleof Dye 1 exhibiting an epsilon of 79,000 at 534 nanometers
in methyl cellosolve.
Example 2
In a 250 ml. flask were placed 30 ml. of
20 dimethyl sulfoxide, 6.0 g. (0.0148 m) of dichlorosulfone
fluorescein, 9.0 g. (0.0300 m) of
OCH~
(CH2)3 ~ C~13 CH3
OCH3
* cellosolve is a trademark; methyl cellosolve is 2-
; methoxythanol.
.: ~
.
Z525
-29-
and 6.0 g. of magnesium oxide. Argon was bubbled through
the stirred mixture for a few minutes, and the flask was
then placed in an oil bath set at 140C. The reaction
was followed by TLC (QSF plates, 10/90 methanol/chloroform,
5 by volume). After 2 1/2 hours the reaction appeared to
be nearly complete. Sodium sulfanilate ~10.0 g.) was
added, and the reaction mixture kep at 140C for an
additional hour. After cooling to 90C, 30 ml. of water
was added, and the mixture was stirred and cooled until
10 the dye mass solidified. The solid was filtered off,
washed well with water, dissolved in chloroform and dried
over calcium sulfate. Evaporation of the chloroform ga~e
15.0 g. of crude dye. The crude dye was redissolved in
chloroform and placed upon a florisil column. The column
15 was eluted with methanol/chloroform (15/85 parts by
volume), and dye being collected as it washed off the
column. Evaporation of the eluent gave 8.0 g. (58%) of
CH CH
N ~ ICH ~ CN3
6C3 ~ ~o3 C3H
CH
3 OCH3
A solution of 8.0 g. (8.6 x 10 3m) of this dye in 500 ml.
20 of chloroform was cooled in a dry ice-acetone bath, and
8.0 ml. (21.1 g., 0.084 m) of boron tribromide dissolved
in 50 ml. of chloroform was 510wly dripped into the
stirred solution. Upon complete addition of the boron
tribromide, the mixture was allowed to come to room
25 temperature and was then stirred overnight. A solution
of 50 ml. of concentrated hydrochloric acid in 450 ml. of
water was cautiously added, and the mixture was stirred
S
-30-
and refluxed for 1 hour. The warm mixture was filtered,
and the solid was washed well with water and dried to
give 6.0 g. (80~) of Dye 2:
CH3 CH
H OH
5 Dye 2 was found to exhibit maximum absorption in methyl
cellosolve at 548 nanometers, epsilon 104,000.
The dimethoxy intermediate
OCH3
(CH2)3 ~ UHI CH3
H3
employed in Example 2 above was prepared as follows:
Example 2-A
600 g. (362 ml.) of concentrated sulfuric acid
and 100 g. (71.5 ml.) of concentrated nitric acid (d. 1.42)
were combined in a 3-liter three neck round bottom flask
and cooled to 0C in an ice-salt bath. To this was added
15 120 g. (1 mole) of tolualdehyde, with stirring and
dropwise at a rate that kept the temperature at about
5C. After addition of the aldehyde, the solution was
stirred at 0C for one hour and then dumped onto ice.
Crude 4-methyl-3-nitrobenzaldehyde precipitated as a
20 pale yellow solid which was filtered off, washed with
water and dried (m.p. 41-43C). 18.0 g. (0.1 m) of
Sf~5
2,5-dimethoxyacetophenone and 16.5 g. (0.1 m) of 4-methyl-
3-nitrobenzaldehyde were dissolved in 75 ml. of absolute
ethanol by gentle heating on a steam bath. Gaseous
hydrogen chloride was bubbled in with stirring for a few
5 minutes. The now hot, green solution was stoppered and
left at room temperature overnight. Crystalline 3-nitro-
4-methyl-2',5'-dimethoxy chalcone
[~ C--CH=CH~CH 3
NO
OCH3 2
was filtered off and washed well with cold alcohol;
10 yield 28 g. (86%). Material recrystallized from toluene
melted at 146-147C. 30 g. (0.046 m) of this chalcone
was hydrogenated on a Parr apparatus in ethanol at
40 lbs./in.2 pressure using 10% palladium-on-charcoal
catalyst. After hydrogen uptake ceased, the bottle was
lS removed and the precipitate dissolved by heating. The
catalyst was filtered from the hot solution. Upon
cooling of the filtrate
~C--CH2--CH2~CH3
H3 NH2
crystallized out as white crystals. 5.8 g. (0.019 m) of
20 this ketone was refluxed in 25 ml. of absolute ethanol
with 2.5 g. (0.05 m) of hydrazine hydrate for 1 hour.
The ethanol was stripped off, an~ 4.0 g. (0.071 m) of
powdered KOH was added. This mixture was stirred and
heated under nitrogen at 235 (oil ~ath temperature) for
25 45 minutes. After cooling, the residue was stirred in
water to dissolve crystallized KOH, and the oily material
11f~2525
-32-
was taken up in diethyl ether. After washing with water,
the ether solution was dried over drierite. Evaporation
of the diethyl ether gave an oil which solidified upon
standing. This solid was dissolved in 5 ml. of hot
5 toluene and 15 ml. of boiling petroleum ether was added.
On cooling the amine
(C~2~3 ~ CH3
OCH3
crystallized out as a white powder (3.1 g., 57% yield;
m.p. 65-66C). 10.0 g. (0.035 m) of this amine was
10 refluxed in 150 ml. of toluene containing 6 g. of 88%
formic acid. Water was removed by a Dean-Stark trap;
when no more water came over (about 2 hours), the solution
was cooled slightly and another 6 g. of formic acid was
added. The solution was again refluxed until water did
15 not come over. TLC (50/50, by volume, diethyl ether/-
petroleum ether) showed all startinq material was gone and
that a second compound had been formed. The solvent was
evaporated under vacuum and the residual oil was dissolved
in boiling ether. Upon cooling, the formamide
OCH
(C~2)3 ~ CH3
NH-CH
~CH3 o
precipitated as a white powder (m.p. 107-108C; 95% yield).
4.5 g. (0.0144 m) of the formamide was dissolved in 50 ml.
of tetrahydrofuran and treated with 6.6 g. (0.087 m) of
~S~5
BH3 DMS (boron-dimethyl sulfide). The solution was stirred
over a weekend at room temperature, during which time a
gelatinous precipitate formed. The reaction mixture was
poured, with stirring, into 150 ml. water containing 10 ml.
5 of concentrated hydrochloric acid. After cooling, the
mixture was made strongly basic by the addition of solid
sodium carbonate. The organic layer was taken up in
diethyl ether and dried over drierite. Evaporation of the
solvent gave an oil which crystallized on cooling. The
10 solid was triturated in petroleum ether and filtered to
give 4.0 g. (93% yield) of
OCH3
(CH2)3 ~ C 3
H-CH3
OCH3
as a pure white powder, m.p. 39-40C.
The following example illustrates the prepara-
15 tion of a sulfonyl chloride-substituted intermediate
which may be employed to prepare a variety of dye
developers within the scope of this invention.
Example 3
6.0 g. (0.012 m) of the monochloro intermediate
CH3
Cl
~ SO3-
and 8.0 g. (0.036 m) of
525
-34-
S03Na
HC 1
3 ~1 1
~ CH3
NH2
were heated in ethylene glycol overnight. The hot purple
solution was poured into aqueous HCl, and the solid
filtered off. The solid was slurried in water and solid
5 potassium carbonate was added until a solution resulted.
The solution was extracted twice with chloroform, and
the aqueous layer was isolated and acidified to about
pH 1 with concentrated hydrochloric acid. After heating
to 90C, salt was slowly added with stirring until solid
10 dye began to precipitate. Stirring was continued until
the temperature fell to 45-50~C, and the dye was filtered.
Purification gave 4.0 g. of
CH3 I H CH3
N ~ ~ SO3Na
~ SO3-
4.0 g. (6 x 10 3m) of this dye was slurried in S0 g. of
15 thionyl chloride. 2 0 ml. of dimethyl formamide was added,
and the solution was stirred at room temperature for 1
hour. After pouring onto ice, with stirring, the
sulfonyl chloride was filtered off and washed well with
water. After sucking under a rubber dam, the damp
20 material was dissolved in tetrahydrofuran, dried over
drierite and evaporated to give
'Z525
-35-
CH CH
N ~ ~ 502-Cl
~ S03-
The sulfonyl chloride prepared in Example 3 may
be reacted with a wide variety of amino-substituted
hydroquinones to provide dye developers within the scope
S of this invention. Thus, for example, Dye 5 above may be
prepared by reacting this sulfonyl chloride with
H3 C 3
CH2- CH -NH2
OCH3
followed by demethylation. It will be readily recognized
that a dye developer containing two such sulfonamido-
10 linked hydroquinonyl groups may be obtained by replacingboth chlorines of dichlorosulfone fluorescein with, e.g.,
CH3
- NH
~S02Cl
CH3
and reacting the resulting bis-sulfonylchloride with two
equivalents of the desired amino-substituted hydroquinone.
-36-
The following example is given to illustrate the
use of a dye developer of this invention in a diffusion
transfer process.
Example 4
A photosensitive element was prepared by coating
a subcoated transparent 4 mil polyethylene terephthalate
film base with a solution of Dye 2 and cellulose acetate
hydrogen phthalate dissolved in a 50:50 mixture, by volume,
of acetone and methyl cellosolve to provide a layer
10 containing approximately 24 mg./ft.2 of Dye 2 and
approximately 24 mg.~ft.2 of cellulose acetate hydrogen
phthalate. Over this dye layer was coated a green-sensi-
tive silver iodobromide emulsion at a coverage of about
44 mg./ft.2 of silver and 88 mg./ft.2 of gelatin. Over
15 the silver halide emulsion layer there was coated a gelatin
layer containing about 30 mg./ft.2 of gelatin and 7.5
mg./ft.2 of 4'-methylphenylhydroquinone. The resulting
photosensitive element then was exposed (2 meter-candle-
seconds) on a sensitometer to a test exposure scale or
20 step-wedge. In the dark, a layer approximately 0.0020
inch of a processing composition containing (approximate
concentrations):
Potassium hydroxide (45% solution) 380 g.
Carboxymethyl hydroxyethyl
cellulose 52 g.
Titanium dioxide 2028 g.
6-methyl uracil 14.2 g.
bis-(~-aminoethyl)-sulfide 1 g.
5-bromo-6-methyl-4-azabenzimidazole1.5 g.
Benzotriazole 27 g.
Lithium nitrate 0.1 g.
Colloidal silica (30% aqueous solution) 88 g.
N-2-hydroxyethyl-N,N',N'-tris-
carboxymethyl-ethylene diamine40 g.
Lithium hydroxide 5 g.
Polyethylene glycol
(molecular weight 6,000) 26 g-
11'~;~,5~5
-37-
N-phenethyl-~-picolinium bromide
(50% aqueous solution) 70 g.
N-benzyl-~-picolinium bromide
(50% aqueous solution) 121 g.
6-benzylamino-purine 19 g.
Water 1757 g.
between the exposed photosensitive element and a trans-
parent image-receiving element as said elements were
brought into superposed relationship. The resulting
10 laminate was kept in the dark for 10 minutes (to avoid
fogging the developed silver halide emulsion by light
passing through the transparent film base). When brought
into the light, a well defined positive magenta dye image
(reflection density DmaX 1.70, Dmin
15 through the transparent base of the image-receiving
element against the white layer of titanium dioxide
provided by the processing composition, without separating
the superposed elements. Inspection of the developed
photosensitive element through the transparent film base
20 of the photosensitive element showed a well defined
negative silver image in the developed silver halide
emulsion layer, and very little magenta dye developer
left in undeveloped areas, indicating an efficient use of
the coated dye developer.
The image-receiving element used in Example 4
comprised a 4 mil transparent polyethylene terephthalate
carrying, in order:
1. a mixture of about 8 paxts, by weight, of a
partial butyl ester of polyethylene/maleic anhydride and
30 about 1 part, by weight, of polyvinyl butyral to provide a
polymeric acid layer having a coverage of about 2500
mg./ft.2;
2. a mixture of about 7 parts, by weight, of
hydroxypropyl cellulose (Klucel J12HB, Hercules, Inc.,
35 Nilmington, Delaware), and about 4 parts, by weight, of
polyvinyl alcohol; to form a spacer layer having a
coverage of about 500 mg./ft. ; and
525
-38-
3. a mixture of about 3 parts of (a) a mixture
of about 2 parts of polyvinyl alcohol and 1 part of poly-
4-vinylpyridine and 1 part of a graft copolymer of 4-
vinylpyridine and vinyl benzyl trimethyl ammonium chloride
5 on hydroxyethyl cellulose (mole ratio 1:0.5:1) to form an
image-receiving layer having a coverage of about 300
mg-/ft.
The FIGURE is a graph of the percent reflectance
of visible light against wavelength in nanometers of a
10 magenta monochrome reflection print prepared in substan-
tially the same manner as in the above example, made three
days after processing and using magnesium carbonate as the
reference material.
As noted above, magenta image dye-providing
15 materials containing the chromophoric system:
~ SO3-
in accordance with this invention are not restricted to
dye developers, but include many other types of initially
diffusible and initially non-diffusible image dye-provid-
20 ing materials.
Thus, for example, an initially diffusiblecoupling dye useful in the diffusion transfer process
described in U. S. Patent No. 3,087,817 issued April 30,
1963 to Howard G. Rogers may be prepared by substituting
25 one or both of the anilino groups with a color coupling
moiety, such as a phenol or naphthol having a free
position para to the hydroxyl group. As an example of
such a coupling dye, mention may be made of:
ll~Z525
- 39 -
CH3 CH3
~H~O~ ~ qH
2 - NH -
~ SO3-
This dye is initially diffusible, but is rendered non-
diffusible by coupling with the oxidation product of a
color developer, e.g., a p-phenylene diamine or a
5 p-aminophenol, to form a less diffusible product. If the
coupling position is substituted by a substituent which
renders the dye initially nondiffusible by virtue of a
ballast group and which substituent is displaceable upon
coupling, such a dye may be employed to provide a
10 diffusible dye where coupling occurs, employing the
principles described, e.g., in U. S. Patent No. 3,227,550
issued on January 6, 1966.
As an example of an initially non-diffusible
"redox dye releaser" dye useful in the diffusion transfer
15 process described in V. S. Patent No. 4,076,529 issued
February 28, 1978 to Fleckenstein and Figueras, mention
may be made of
CH3 CH3
~S2 - NH
o3 ~C15H3
-40-
Other sulfonamido phenol or naphthol groups known in the
art, e.g., in U. S. Patent No. 4,053,312 issued October 11,
1977 to Fleckenstein and in U. S. Patent No. 4,055,428
issued October 25, 1977 to Koyama et al, to cleave, in
5 alkaline solution, at the sulfonamido group following
oxidation may be used in place of the p-sulfonamido-
naphthol group illustrated above.
U. S. Patent No. 3,719,489 issued March 6, 1973
to Cieciuch, Luhowy, Meneghini and Rogers discloses
10 diffusion transfer processes wherein a diffusible image
dye-providing material is formed by the silver-catalyzed
cleavage of a thiazolidine group of an initially non-
diffusible image dye-providing material. Examples of
image dye-providing materials within the scope of this
15 invention and which may be used in said thiazolidine dye-
release system include:
S02~ 0!1
3 ~ -C18H37
( H3)2
--41--
CH3 CH3
~_ ~C2~_ ~C2
52 [~ ~B2
( H3C ) 2Ts~ ~45~CH 3 ) 2
Ot~ 0~1 I
~37~ C18~37
$ lH ~_ ICH~
Z ~ S03- Z
Z = -C-NH-cH2-cH2-NH-so2~oH
S C1~3~37
(H3C)2
525
-42-
Another class of initially non-diffusible image
dye-providing materials are described in U. S. Patent
3,433,939 issued May 13, 1969 to Bloom and Rogers
release a diffusible dye following oxidation and intra-
5 molecular ring closure. An example of an image dye-
providing material within the scope of this invention
which may be used in the processes of said patent is
CH3 CH3
So2- NH
CH3 NH
3- ~ C15H31
OH
It will be recognized that the above illustra-
10 tive initially non-diffusible image dye-providing
materials may be prepared in a routine manner from, e.g~,
sulfonyl chloride of the chromophore-containing moiety
(e.g., the sulfonyl chloride prepared in Example 3) and
the appropriate amino-substituted diffusion control
lS group, the syntheses of which are described in the noted
patents and to which reference may be made for detailed
descriptions, including photographic utilization.
Other image dye-providing materials which cleave
in alkali following oxidation may be provided by use of a
20 compound within Formula D above wherein A is -O- or -S-
and the hydroquinonyl group contains a ballast group,
e.g.,
CH3 OH
2 ~ ~ ~ C15H31
OH
5Z5
-43-
in accordance with the disclosure of U. S. Patent No.
3,725,062 issued April 3, 1973 to Anderson and Lum.
While the ballast group in the above illustra-
tions has been a long chain alkyl group, it will be
5 understood that other ballast groups shown in the cross-
referenced patents may also be used.
In the use of a non-diffusible image dye-
providing material which releases a diffusible image dye-
providing material following oxidation in an alkaline
10 environment, the requisite oxidation may be effected by
the oxidation product of a mobile developing agent used
to develop the photoexposed silver halide emulsion. A
particularly effective developing agent for this purpose
is l-phenyl-4,4-dimethyl-3-pyrazolidone; other suitable
15 developing agents are described in the cross-referenced
patents.
Example 5
A film unit was prepared as follows: the
negative element was made up of a polyethylene
20 terephthalate photographic film base with the following
layers coated thereon in succession:
1. a magenta dye developer layer at a coverage
of 32 mgs/ft2 (344.4 mgs/m2) of Dye 19 dispersed in
32 mgs/ft2 (344.4 mgs/m2) of cellulose acetate hydrogen
25 phthalate;
2. a green-sensitive gelatino silver iodobromo
emulsion coated at a coverage of 75 mgs/ft2 (807.3 mgs/ft2)
of silver and 88 mgs/ft2 (947.2 mgs/m2) of gelatin;
3. a layer of 30 mgs/ft2 (322.9 mgs/m2) of
30 gelatin.
The image-receiving element comprised a
transparent polyethylene terephthalate photographic film
base with the following layers coated thereon in
succession:
1. as a polymeric acid layer, approximately
9 parts of a half-butyl ester of polyethylene/maleic
anhydride copolymer and 1 part of polyvinyl butyral coated
at a coverage of about 2600 mgs/ft2 (27,986 mgs/m2) and
ll'~;~S25
-44-
including an ultraviolet absorbing material;
2. a timing layer containing about 450 mgs/ft
(4843.8 mgs/m2) of a 60-30-4-6 tetrapolymer of butyl
acrylate, diacetone acrylamide, styrene and methacrylic
5 acid including about 7~-8~ polyvinyl alcohol; and
3. a polymeric image-receiving layer of: (a)
3 parts of a mixture of 2 parts polyvinyl alcohol and 1
part poly-4-vinylpyridine and (b) 1 part of a graft
copolymer comprised of 4-vinylpyridine (4VP) and vinyl-
10 benzyl trimethyl ammonium chloride (TMQ) grafted ontohydroyethyl cellulose (HEC) at a ratio of HEC/4VP/TMQ of
2.2/2.2/1 coated at a coverage of about 300 mgs/ft
(3229.2 mgs/m ).
The film unit was processed with a processing
15 composition comprised of:
Water 1757 gms
Bis-(~-aminoethyl)-sulfide 1.04 cc
Titanium dioxide 2028 gms
Potassium hydroxide (50% solution) 380.3 gms
Carboxymethyl hydroxyethyl cellulose 51.8 gms
Benzotriazole 26.9 gms
6-methyluracil 14.2 gms
N-Hydroxyethyl-N,N',N'-tris-
carboxymethyl ethylene diamine40.2 gms
6-methyl-5-bromo-4-azabenzimidazole1.34 gms
6-benzylaminopurine 19.0 gms
Lithium nitrate 4.72 gms
Polyethylene glycol (MW 6000)26.1 gms
Colloidal silica
(50~ aqueous dispersion) 88.5 gms
N-benzyl-~-picolinium bromide
(50~ solution) 121.3 gms
N-phenethyl-~-picolinium bromide
(50% solution) 70.0 gms
The film unit was exposed (2 meter-candle-
seconds) on a sensitometer to a test exposure scale with
green and blue light and then passed through a pair of
rollers at a gap spacing of about 0.0020 inches. The
unit was allowed to remain in the dark for about 10
525
-45-
minutes. The film unit was kept intact and maximum and
minimum reflection densities were measured.
Example 6
The procedure of Example 5 was repeated with
5 the exception that the dye developer layer of the negative
element was made up of 28.0 mgs/ft2 (301.4 mgs/m2) of
Dye 18 and 28.0 mgs/ft (301.4 mgs/m ) of cellulose
acetate hydrogen phthalate.
Example 7
The procedure of Example 6 was repeated with
the exception that the gelatin layer of the negative
element also included 7.5 mgs/ft2 (80.7 mgs/m of 4'-
methylphenyl hydroquinone.
Example 8
The procedure of Example 7 was repeated with
the exception that the gelatin layer of the negative
element also included 7.5 mgs/ft2 (80.7 mgs/m2 of 4'-
methylphenyl hydroquinone.
Example 9
The procedure of Example 5 was repeated with
the exception that the dye developer layer of the negative
element was made up of 24.6 mgs/ft2 of Dye 2 and 24.6
mgs/ft2 of cellulose acetate hydrogen phthalate.
Example 10
The procedure of Example 9 was repeated except
that the gelatin layer of the negative element also
included 7.5 mgs/ft2 (80.7 mgs/m2) of 4'-methylphenyl
hydroquinone.
The monochrome, magenta transfer images
30 obtained in Examples 5-10 exhibited the following
reflection densities to green light:
S~5
-46-
max min
Example 5 2.09 0.69
Example 6 2.03 0.64
Example 7 2.20 0.25
Example 8 2.00 0.22
Example 9 2.22 0.57
Example 102.33 0.30
Example 11
A multicolor photosensitive element using, as
10 the cyan and yellow dye developers
CH
HC--NH--02S ~
cyan: 2 ~ Cl H 3
~ H ~ ~N~ H S2 - NH - CH
CH3 ~ ~ C/ ~ C ~ ~ OH
Hl--NH--O2S N C~ ;~C -- N HO
2 ~=< fH3
~OH ~S2--NH--CH
HO
~/ ~OH
H~J
-47-
/ ~ 7 NO2
~ /0~
yellow:\ Cr / H2O
O o OH
~C--C~ CH2~
OH
and Dye 18 as the magenta dye developer, by coating a
gelatin-subcoated 4 mil opaque polyethylene terephthalate
film base with the following layers:
1. a layer of cyan dye developer dispersed in
gelatin and coated at a coverage of about 630 mg/m of
dye, about 391 mg/m2 of gelatin, about 280 mg/m2 of
N-n-dodecylaminopurine, and about 88 mg/m2 of 4'-methyl-
phenyl hydroquinone;
2. a red-sensitive gelatino silver iodobromide
emulsion coated at a coverage of about 1054 mg/m2 of
silver and about 6324 mg/m of gelatin;
3. a layer of a 95:5 mixture cf a 60-30-4-6
copolymer of butylacrylate, diacetone acrylamide, styrene
15 and methacrylic acid and polyacrylamide coated at a
coverage of about 1076 mg/m2;
4. a layer of magenta dye developer dispered
in gelatin and coated at a coverage of about 648 mg/m2 of
dye and about 324 mg/m2 of gelatin;
5. a green-sensitive gelatino silver iodobromide
emulsion coated at a coverage of about 749 mg/m2 of silver
and about 330 mg/m of gelatin;
6~ a layer containing the copolymer referred to
above in layer 3 and polyacrylamide in a 91:9 ratio coated
25 at a coverage of about 1816 mg/m ;
-48-
7. a layer of yellow dye developer dispersed in
gelatin and coated at a co~erage of about 659 mg/m of dye,
about 318 mg/m2 of gelatin, and about 108 mg/m2 of N-n-
dodecylamino-purine;
8. a blue-sensitive gelatino silver iodobromide
emulsion layer coated at a coverage of about 990 mg/m2 of
silver, about 495 mg/m2 of gelatin; and
9. a layer of gelatin coated at a coverage of
about 320 mg/m of gelatin.
A transparent 4 mil polyethylene terephthalate
film base was coated, in succession, with the following
layers to form an image-receiving component:
1. as a polymeric acid layer, a mixture of a
partial butyl ester of polyethylene/maleic anhydride
15 copolymer and polyvinyl butyral at a ratio of about 9:1
at a coverage of about 2,500 mg/ft2;
2. a timing layer containing about a 45:0.7
ratio of a 60-30-4-6 copolymer of butylacrylate, diacetone
acrylamide, stryene and methacrylic acid and polyvinyl
20 alcohol at a coverage of about 450 mg/ft2; and
3. an image-receiving layer containing a 2:1:1
mixture of polyvinyl alcohol, poly-4-vinyl pyridine and a
graft copolymer of 4'-vinyl pyridine and vinylbenzyl
trimethyl ammonium chloride on hydroxyethyl cellulose
25 (2.2:1:2.2 ratio) at a coverage of about 300 mg/ft2.
Over the image-receiving layer there was coated about
100 mg/ft of a 70:30 mixture of Pluronic F-127
polyoxyethylene polyoxypropylene block copolymer and
polyvinyl alcohol as a decolorizing layer. (Such
30 "decolorizing" layers are the subject of the copending
application of Edwin H. Land, Leon D. Cerankowski and
Neil Mattuci, Serial No. 33,001, filed April 24, 1979.)
The photosensitive component was photoexposed and then
taped to one end of the image-receiving component with a
35 rupturable container retaining an aqueous alkaline
processing solution fixedly mounted on the leading edge
of each of the components, by pressure-sensitive tapes
to make a film unit, so that, upon application of
5~S
-49-
compressive pressure to the container to rupture the
container's marginal seal, its contents would be
distributed between the decolorizing layer and the
gelatin overcoat layer of the photosensitive component
The aqueous alkaline processing composition comprised:
Water 100 g.
Potassium hydroxide (85~) 10.1 g.
N-phenethyl-~-picolinium bromide2.6 g.
Titanium dioxide 77.1 g.
6-methyl uracil 0.6 g.
bis-(~-aminoethyl)-sulfide 0.04 g.
Benzotriazole 1.1 g.
Colloidal silica (solids based
on 30% SiO2 dispersion) 0.56 g.
N-2-hydroxyethyl-N,N',N'-tris-
carboxymethyl-ethylene diamine1.52 g.
4-aminopyrazolo ( 3, 4d)pyrimidine 0.51 g .
polyethylene glycol (molecular
weight about 4000) 0.91 g.
poly-diacetone acrylamide oxime1.6 g.
OH OH 2,74 g.
C 1 8 H 3 7 ~:`OOH HOOC~
5ZS
-50-
HOOC H }l ~HS2C16~33 n 0 6 g
~``0
A layer approximately 0.0030" thick of the processing
composition was distributed by passing the film unit
between a pair of pressure-applying rolls and into a
5 lighted area. The resulting laminate was maintained
intact to provide a multicolor integral negative-positive
reflection print which exhibited good color quality and
separation.
Example 12
Dye 18 was prepared as follows:
10 g of a xanthene dye represented by the
formula
c~3 CIH3
OCH3 ~ ~ ~ OCH3
--(C112)3 @J--so~3 (CH2)3 ~
OCH3 3
was suspended in 75 ml of dimethyl sulfoxide at room
15 temperature under nitrogen gas. To this suspension there
was added 1.8 g of a 50~ sodium hydride dispersion in oil
and the mixture stirred for 30 minutes at room temperature.
A blue solution developed. To the solution there was
5~,5
-51-
added 10 g of a tosylate compound represented by the
structural formula
OCH ~
(CH2)3-3s ~ CH3
OCH~ ~
and the solution stirred for 3 hours at room temperature.
5 TLC on silica gel with 5/95 methanol/methylene chloride,
by volume, showed that none of the dye intermediate
remained. Methyl iodide (2 ml) was added and the mixture
was stirred for one hour. TLC showed that the reaction
was complete. The reaction mixture was poured into 1 liter
10 of water containing 1 ml of conc. HCl and the precipitate
was filtered off. The precipitate was placed back into
water, stirred well, collected by filtration and vacuum
dried to give 14.0 g. The product was dissolved in 400 ml
of methylene chloride and 125 g of silica gel added to the
15 solution. The stirred mixture was placed in a sintered
glass funnel and filtered while washing with methylene
chloride. The dye was then extracted with 5/95 methanol/
methylene chloride, by volume, and evaporated to dryness.
The dye is represented by the structural formula
5~5
-52-
3 CH OCH
~ Cll2 3 1 ~ CH3
H3CO OCH3
(CH2)3 ~
OCH3
A solution of 5.0 g of the thus-prepared dye in
100 ml of methylene chloride was added to a stirred
solution of 15 ml of boron tribromide ln 500 ml of
5 methylene chloride, under nitrogen and cooled to 5C.
The magenta solution was allowed to warm to room tempera-
ture. TLC on silica gel showed two spots. A sample of
the solution was heated to reflux with no apparent change
in the TLC results. Water was added dropwise to the
10 solution and a magenta precipitate formed. The precipitate
was collected by filtration, washed well with methylene
chloride and vacuum dried at 80C to give 9.0 g of solid.
The solid was dissolved in methanol containing several
drops of conc. HCl, refluxed, and poured into 1000 ml of
15 ether. The precipitate was collected by filtration and
dried to give 3.8 g of product.
The 3.8 g sample was placed on 60 g of sea sand
with methanol. The mixture was placed in a steel column
and an additional 250 g of sea sand were added. The column
20 was placed on line on a high pressure chromatography unit
and washed with a succession of solvents as follows (parts
are by volume):
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1 liter methylene chloride
2 liters 1/99 methanol/methylene chloride
4 liters 2/98 methanol/methylene chloride
4 liters 3/97 methanol/methylene chloride
12 liters 5/95 methanol/methylene chloride
3 liters 6/94 methanol/methylene chloride
The appropriate solvent fractions as determined
by thin layer chromatography were collected and evaporated
to give 1.8 g of the dye developer.
TLC of the material showed traces of impurities.
The sample was again placed on 60 g of sea sand and placed
back in the steel column (which was first washed with 9/91
methanol/methylene chloride, by volume, and then with
methylene chloride). The column was washed with a
15 succession of solvents as follows ~parts are by volume):
1 liter methylene chloride
3 liters 2/98 methanol/methylene chloride
3 liters 3/97 methanol/methylene chloride
1 liter 4/96 methanol/methylene chloride
10 liters 4/96 methanol/methylene chloride
3 liters 6/94 methanol/methylene chloride
The appropriate solvent fractions as determined by thin
layer chromatography were collected and evaporated to
give 1.7 g of Dye 18 which was shown to be pure by TLC.
25 The product exhibited maximum absorption in methyl
cellosolve at 553 nm, ~ = 117,500. An NMR spectrum of
the product confirmed the structure.
Example 13
A film unit was prepared as follows:
The photosensitive element comprised an opaque
subcoated polyethylene terephthalate film base on which
the following layers were coated in succession:
(1) a layer of sodium cellulose sulfate coated
at a coverage of about 21 mgs/m2;
~2) a cyan dye developer layer comprising
about 635 mgs/m2 of the cyan dye developer used in
Example 11, about 429 mgs/m2 of gelatin, about 238 mgs/m
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of dodecylaminopurine and about 128 mgs~m2 of 4'-methyl-
phenyl hydroquinone;
(3) a red-sensitive gelatino silver iodobromide
(1.8 microns) emulsion layer coated at a coverage of about
5 1900 mgs/m2 of silver and about 1140 mgs/m2 of gelatin;
(4) an interlayer comprising about 2000 mgs/m2
of a 60-30-4-6 tetrapolymer of butylacrylate, diacetone
acrylamide, styrene and methacrylic acid and about
30 mgs/m2 of polyacrylamide;
(5) a magenta dye developer layer comprising
about 666 mgs/m of Dye 18, about 323 mgs/m2 of gelatin
and about 150 mgs/m2 of dodecylaminopurine;
(6) a green-sensitive silver iodobromide (1.11
microns) emulsion layer coated at a coverage of about
15 700 mgs/m2 of silver and about 308 mgs/m2 of gelatini
(7) a green-sensitive silver iodobromide (1.8
micrans) emulsion layer coated at a coverage of about
600 mgs/m2 of silver and about 288 mgs/m of gelatin;
(8) an interlayer comprising about 1380 mgs/m
20 of a 60-30-4-6 tetrapolymer of butylacrylate, diacetone
acrylamide, styrene and methacrylic acid and about
30 mgs/m2 of polyacrylamide;
(9) a spacer layer comprising about 285 mgs/m2
of 2-phenylbenzimidazole and about 142.5 mgs/m of
25 gelatin;
(10) a yellow dye developer layer comprising
about 820 mgs/m of the yellow dye developer used in
Example 11 and about 328 mgs/m2 of gelatin;
(11) a blue-sensitive silver iodobromide (1.5
30 microns) layer coated at a coverage of about 1050 mgs/m2
of silver, 660 mgs/m2 of gelatin and about 306 mgs/m2 of
4'-methylphenyl hydro~uinone; and
(12) an overcoat layer of about 484 mgs/m2 of
gelatin.
The image-receiving element comprised a
transparent subcoated polyethylene terephthalate film
base on which the following layers were coated in
succession:
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(1) as a polymeric acid layer approximately 9
parts of a 1/2 butyl ester of polyethylene/maleic
anhydride copolymer and 1 part of polyvinyl butyral
coated at a coverage of about 2450 mgs/ft2 (26,372 mgs/m2);
S (2) a timing layer coated at a coverage of
about 270 mgs/ft2 (2906 mgs/m2 of a 60-30-4-6 tetrapolymer
of butylacrylate, diacetone acrylamide, styrene and
methacrylic acid and about 30 mgs/ft2 (323 mgs/m2 of
polyvinyl alcohol;
(3) a polymeric image-receiving layer coated at
a coverage of about 10 mgs/ft2 (108 mgs/m2 of 1,4-
butanediol diglycidyl ether and about 300 mgs/ft2
(3229 mgs/m2 of: (a) 3 parts of a mixture of 2 parts
polyvinyl alcohol and 1 part poly-4-vinyl pyridine and
15 (b) 1 part of a graft copolymer comprised of 4-vinyl
pyridine (4VP) and vinyl benzyl trimethyl ammonium
chloride (TMQ) grafted onto hydroxyethyl cellulose (HEC)
at a ratio HEC/4VP/TMQ of 2.2/2.2/1; and
(4) a topcoat layer of polyvinyl alcohol coated
20 at a coverage of about 40 mgs./ft2 (430 mgs/m2).
A second film unit was prepared which was
identical with the exception that the magenta dye
developer layer included about 540 mgs/m2 of Dye 2 instead
of Dye 18.
The amounts of Dyes 2 and 18 used in the above
film units were chosen so as to provide substantially
equivalent molar amounts of the dye developers. Thus
617 x 10 mole of Dye 18 (MW 1011) and 617 x 10 5 mole
of Dye 2 (MW 875) were present in the respective film
30 units.
The film units were exposed on a sensitometer
to a test exposure scale with white light and then
processed by passing them through a pair of rollers so
as to distribute a layer of the following processing
35 composition approximately 0.0030 inch thick between the
superposed photosensitive and image-receiving elements:
S;~5
Water 1622 ml
TiO2 2312.0 gms
Oximated polydiacetone acrylamide 32.0 gms
Potassium hydroxide (45~ solution) 486.6 gms
Benzotriazole 22.0 gms
4-Aminopyrazolo-(3,4d) pyrimidine10.0 gms
6-Methyl uracil 12.0 gms
N-hydroxyethyl-N,N',N'-tris-
carboxymethyl ethylene diamine30.0 gms
Polyethylene glycol (M.W. 4000)18.0 gms
Bis(2-aminoethyl)sulfide 0.8 gms
Colloidal silica (30~ solids)37.0 gms
N-phenethyl-~-picolinium bromide
(50~ solids) 102.0 gms
15 Since the processing composition did not contain opacifying
dyes the film units were kept in the dark for a period of
about five minutes after the processing composition was
applied. The reflection densities of the neutral area of
the images were:
Red Green Blue
Dye 18: D 1.87 2.36 2.18
max
Dmin 0.12 0.16 0.24
Dye 2: D 1.82 1.88 2.12
Dmin 0.12 0.15 0.26
25 It will be noted that Dye 18 gave a much higher transfer
density than Dye 2. It has been determined that Dye 2
transfers at a much slower rate than Dye 18. Since the
dyes are insolubilized by the pH reduction effected after
a predetermined time by the polymeric acid neutralizing
30 layer, it will be apparent that the difference in the
magenta transfer density is due to the combination of the
difference in transfer rates and the p~ reduction. Other
experiments have shown that if the pH is not reduced,
i.e,, the neutralizing layer is omitted, substantially
35 similar transfer densities may be obtained even though the
rate of density build-up is slower. Similar
experiments have also shown that the transfer rate of
~Z5Z5
-57-
Dye 2 also is reduced by the presence in the processing
composition of opacifying dyes such as used in Example 5.
The magenta image dyes provided by this
invention have been found to provide very desirable
5 spectral properties, particularly high green absorption
and high blue transmission, together with high extinction
coefficients, thereby providing multicolor images exhibit-
ing improved reproduction of blues, greens and pastel
colors. The preferred magenta dyes of this invention
10 exhibit maximum absorption at about 540 to 555 nanometers
(dissolved in methyl cellosolve) and have a narrow band
width. The dye developers of this invention have been
found to give very good transfer control, with very good
deltas between maximum and minimum densities. While it
15 is general practice in dye developer transfer processes
to have an auxiliary developing agent, e.g., 4'-methyl-
phenyl hydroquinone present, it has been found that the
dye developers of this invention exhibit very good silver
halide developing action without such auxiliary developing
20 agents, and that the total amount of auxiliary developing
agent in a given system therefore may be reduced. In
turn, this reduces the potential for stain in highlight
regions of the transfer image due to oxidized auxiliary
developing agent. It has also been observed that the
25 oxidized form of these dye developers, illustrated for
example by Dyes 2 and 18, exhibits a large difference in
alkali solubility compared with the unoxidized form. The
dye developers of this invention also exhibit a strong
resistance to post-processing transfer, e.g., solubiliza-
30 tion and transfer after pH-reduction to impart a stain or
"pinking" to highlight areas. While the reasons for
these desirable properties are not well understood, it is
believed that the presence of the positive charge
associated with the nucleus is a significant factor.
Dyes of similar chromophoric systems, commonly
referred to as rhodamine or xanthene dyes, tend to
exhibit fluorescence, an undesirable property. N-alkyla-
tion has tended to increase fluorescence. The presence
ZS
-58-
of a phenolic group, particularly a hydroquinonyl group,
unexpectedly has been found to reduce fluorescence,
particularly where X' is not hydrogen.
In the above examples the neutralizing and
5 timing layers were positioned between the image-receiving
layer and its transparent support. In certain embodiments
it is advantageous to position the neutralizing and timing
layers in the photosensitive element, i.e., between the
cyan dye developer layer and the opaque support, in the
10 manner described in U. S. Patent No. 3,573,043 issued
March 30, 1971 to Edwin H. Land.
It will also be understood that the image dye-
providing materials of this invention may be used in
film structures of the type described in U. S. Patent No.
15 3,594,165 issued July 20, 1971 to Howard G. Rogers.
Since certain changes may be made in the above
product and process without departing from the scope of
the invention herein involved, it is intended that all
matter contained in the above description shall be
20 interpreted as illustrative and not in a limiting sense.
