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Патент USA US2405106

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July 30, 1946.
J. A. WIDMER ET AL
2,405,106
PHOTOGRAPHIC FILTER AND ANTIHALATION LAYERS
Filed 001;. 27, 1944
FIGJ.
13
BLUE scnsmv: EMULSION
14 '
,FILTER LAYER CONTAINING A PYRROLE
WW4;
‘2
mm?
/
DYE AND AN ANIONIC DISPERSING AGENT
GREEN SENSITIVE EMULSION
RED SENSITIVE EMULSION
SUPPORT
I
j/ E MULSION
15-/“////////'//////:<_/~SUPPORT
/
ANTiHALATION LAYER CONTAINING
A PYRROLE DYE AND AN ANIONIC
DISPERSING AGENT
JULES A.WIDMER
BURT
H. CARROLL
INVENTORS
WM
BY @- MJmJa€~
A TTORNE Y
Patented July 30, 1946
2,405,105
.UNITED STATES PATENT OFFICE
2,405,106
PHOTOGRAPHIC FILTER AND AN TIHALA
TION LAYERS
Jules Arthur Widmer, Oak Ridge, Tenn, and Burt
H. Carroll, Rochester, N. Y., assignors to East
man Kodak Company, Rochester, N. Y., a corpo
ration of New Jersey
Application October 27, 1944, Serial No. 560,626
5 Claims.
(Cl. 95-8)
1
This invention relates to photography and par
ticularly to ?lter and antihalation layers for
CH3——h—CH=CH—OH=C———-C-CH3
H
photographic elements.
Dyes which can be used successfully, by direct
dispersion in gelatin, for the preparation of ?lter 5
layers in contact with photographic emulsions are
very rare. Such dyes must have good spectral
CH3—C
C 3X1?/—CHa
CH3
I
Bis-[1,2,11,5-tetra1nethyl pyrrole-(3)]-trimethinoyanine
iodide
/CH3
——C—-CH3
H
‘
C—CH==CH
\Na
/
CZH5
and Sprague U. S. Patents 2,268,798 and 2,298,731 1'5
C-CHs
/N\
CH3
absorption properties and be readily dispersible
in gelatin without crystallization. In addition,
such dyes should bleach readily in photographic 10
processing baths, should not diffuse in multi-layer
coatings, nor either sensitize or desensitize the
emulsion layers with which they are in contact.
It is difficult to ?nd dyes which ful?ll all of
these requirements. The pyrrole dyes of Brooker
\
/
OH:
—N
__
\
CH3
C104
2-p-dimethylamino-styryl-l-ethyLB,3~dimethyl-4,5
benzoindolenium perchlorate
are satisfactory in many respects for use in ?lter
and antlhalation layers but do not ful?ll all of
the necessary requirements.
___(CHs)2
We have found that many of the properties of 20
the pyrrole dyes of the Brooker and Sprague
C
\NfCH— H—
patents may be improved by dispersing the dyes
C 6 H 5 \CIO 4 CH
with an excess of an anionic dispersing agent.
Such dispersing agents include water-soluble
salts of alkyl naphthalene sulfonates, water-sol 25
uble salts of esters of sulfoaliphatic dicarboxylic
acids, and tannic acid.
The accompanying drawing shows sectional
views of photographic ?lm constructed accord
CH 3
|
(311115
[l-n-heptyl-2,5-dimethyl pyrrole- (8)]-[3,3-dimctl1y1~l
phcnylindoleniue- (2)1-dimethincyanine perchlorate
——<oH@>.
30
The pyrrole dyes which We propose to use are
I
ing to our invention.
/\
l I
\N%-CH_OH——C—\N/
I
polymethine dyes having a conjugated methine
chain joining two heterocyclic nuclei, at least one
/ \
C2H5
of which nuclei is a pyrrole nucleus. In addition
to the dyes disclosed in the Brooker and Sprague 35
U. S. Patents 2,268,798 and 2,298,731, the follow
ing are suitable:
I
CH3—G=C—OH3
[l-ethy1-3,3~_dimethyl_
indole-(2)]-[2,3-di1nethyl
pyrrocollne-(l)]-dimeth1ncyan1ne iodide
/
C—CH=CH—~CH=CH—~_
40
\N/
/ \I
OZHB
CH3‘\N/~CH3
I
(Oetyl-l-octadecyl)
GzHs
Cl
[3-ethyl—2-benzoxazole]-[2,5-dimethyl-l-heptyl
pyrrole(3)1-dimethincynanine chloride 1
45
[3-cthyl-2<benzoxaz0le}-[l-eety1+octadecyl(mixture)-2,5-dimethyl
pyrrole (3)1-tetramethincyanine io dide‘
The anionic dispersing agents which may be
used with the pyrrole dyes include water-soluble
salts of alkyl naphthalene sulfonates, such as
Alkanol B sold by E. I. du Pont de Nemours 8.:
50 Company, Nekal A sold by General Dyestu? Cor
poration, N ovonacco sold by National Aniline and
Chemical Company, Inc., and Aerosol OS sold by
American Cyanamid and Chemical Corporation.
These compounds are generally sold as the so
CGHE
[3,3-dimethyl-l-phenyl-indolenino (2)]-[2,5-dimethyl-l
phenyl pyrrole (3)1-dimethincyanine perchlorate
55 dium salts, for example, Aerosol OS is isopropyl
naphthalene sodium sulfonate. Other Water
soluble salts may, however, be used.
2,405,106
4
a
0
Another class of anionic dispersing agents
which We may employ is that of the water-soluble
the Aerosol OT and diffusion was found to be
prevented.
salts of esters of sulfo aliphatic dicarboxylic acids,
Example 5
A coating was made as in Example 1 but using
such as Aerosol AY and Aerosol OT sold by Amer
Corporation.
as the dye [1-n-heptyl-2,5-dimethylpyrrole (3) l
Aerosol AY is the diamyl ester of sodium sulfo~
succinic acid and Aerosol CT is the dioctyl ester
of sodium sulfosuccinic acid. .water-soluble salts
other than the sodium salts may be used.
. [3,3-dimethyl-l-phenylindolenine (2) l-dimethin
ican
Cyanamid
and‘ Chemical
cyanine perchlorate. The coating was found to be
free from diffusion.
Example 6
A third type of dispersing agent which we may 10
use for the pyrrole dyes is tannic acid or tannin.
The pyrrole dye and the anionic dispersing
agent used according to our invention should be
chosen so that in equivalent quantities they form
a dii?cultly soluble precipitate which is colloidally
dispersed by an excess of the anionic material.
This procedure has several advantages which per
mit the use of pyrrole dyes not otherwise appli»
cable to ?lter layers for multi-layer photographic
elements. The true solubility of the pyrrole dye 20
in water can be reduced to an extremely low
value, thus preventing diffusion while retaining
good dispersability in colloidal form. In addition,
many dyes which in a puri?ed state crystallize
readily from gelatin layers so that their disper~
sion in sufficient tinctorial strength is poor, can
be incorporated in gelatin with greatly reduced
tendencies to crystallize. Further advantages are
improved spectral absorption and increased fast
ness to heat and moisture. Fading is usually re
A coating was made as in Example 1 but using
as the dye [l-ethyl-3,3-dimethyl-indole (2) l
l2,3-dimethyl-pyrrccoline (1) l-dimethincyanine
iodide. Diffusion of the dye was found to be con
siderably reduced over a similar coating not con
taining the dispersing agent.
Example 7
Dyed gelatin for a coating was made as in EX
ample 1 but omitting the dispersing agent and
using as the dye [3-ethyl-2-benzoxazolel-[1
cetyl+octadecyl (mixture) -2,5-dimethyl pyrrole
(3)l-tetramethincyanine iodide. Considerable
fading of the dye resulted upon holding ‘this gel
at 40° C. for four hours. Similar gels made with
the addition of 0.1 to 0.2 gram of Aerosol OT,
Alkanol B or Nekal A before the dye was added
showed no fading of the dye in four hours at
40° C.
It will be evident from a consideration of the
tarded by the anionic material which presumably
pyrr01e dyes described above that the dyes which
combines with the pyrrole dyes to give an in
we use may have either a pyrrole nucleus or an
indole nucleus, substituted or unsubstituted, at
soluble and more stable salt.
the end of a polymethine chain and that the
Our invention will be further illustrated by ref 35 opposite end of the polymethine chain may be
erence to the following examples:
attached either to a similar or dissimilar pyrrole
Example 1
or indole nucleus or to an aromatic nucleus.
Where we refer to “pyrrole nucleus” it is to be
To 25 cc. of a 10% gelatin solution at pH 6.3
understood that we intend to include both pyrrole
diluted with 20 cc. of water, there were added 50 4-0 and indole nuclei, the indole nucleus being con
milligrams of [3-ethyl-2-benzoxazole]-[2,5-di
methyl - 1 - heptylpyrrole
(3) l-dimethincyanine
chloride dissolved in 3 to 5 cc. of methyl alcohol.
To this was added 4 cc. of 5% solution of Aerosol
OT in a solution containing 50% methyl alcohol
sidered a substituted pyrrole and the term, pyrrole
nucleus, being generic to both pyrrole and indole
nuclei.
The amount of pyrrole dye used in ?lter and
antihalation layers according to our invention
will generally vary from about 50 milligrams to
which when coated on a glass or ?lm support
about 150 milligrams of dye in 25 cc. of 10%
dried to give a clear yellow coating. The dye in
gelatin solution. The dispersing agent is used in
this coating did not diffuse when immersed in
of the equivalent amount of the dye so
tap water, whereas the dye-forming coating made 50 excess
that an excess of the dispersing agent is present
up in a similar manner by omitting the Aerosol
in the dispersion.
OT di?used almost completely into tap water in
In the accompanying drawing, We have shown
and 50% water. This yielded a heavy yellow gel
30 minutes.
photographic elements coated according to our
invention. As shown therein, Fig. 1 illustrates
A coating was made in the same manner as 55 a multi-layer photographic element having a
support l0 of cellulose acetate or other suitable
in Example 1 but using as the dye [3,3-dimethyl
material ?ltered with successive layers H, [2
1 - phenylindolenine (2) l-[2,5-dimethyl-1-phen
and I3, sensitive respectively to the red, green
ylpyrrole (3)1-dimethincyanine perchlorate. A
and blue spectral regions. Between layers I2
clear orange coating was obtained which on mi
croscopic examination was found to be free from 60 and I3, there is coated a layer M of gelatin con
taining a pyrrole dye and an anionic dispersing
crystallization. A similar coating Without the
agent for the dye.
Aerosol OT crystallized quite badly.
Example 2
Example 3
Fig, 2 illustrates a photographic element com
prising a support l5 of cellulose acetate or other
A coating was made as in Example 1 but using 65 suitable material having on one side thereof a
sensitive emulsion layer 16 and on the other side
as the dye bis-[1,2,4,5-tetramethylpyrrole (3)]
trimethincyanine iodide. This coating was found
to be free from diffusion and crystallization of
the dye.
70
Example 4
A coating was made as in Example 1 but using
an antihalation layer ll containing pyrrole dye
and an anionic dispersing agent according to our
invention.
While we have shown the use of our invention
in ?lter and antihalation layers, it is obvious that
the dispersion of dye and dispersing agent may
be applied in other positions in the photographic
element. For example, the dispersions may be
dispersion of the dye was greatly improved by 75 used in overcoating layers or in ?lter layers be
as the dye 2-p-dimethylamino-styryl-1-ethyl-3,3
dimethyl-‘lj-benzoindolenium perchlorate. The
2,405,106
tween any two of the emulsion layers of a multi
layer element or between the emulsion layer and
the support. Supports of glass, cellulose ester,
synthetic resin, paper, metal, or other suitable
material may be used.
The examples and modi?cations included here
in are to be considered as illustrative only and
our invention is to be limited only by the scope
of the appended claims.
We claim:
1. A photographic element comprising a sup
port having thereon a light-sensitive layer and a
layer containing a colloidal dispersion of (l) a
class consisting of water-soluble salts of alkyl
naphthalene sulfonates, water-soluble salts of
esters of sulfo aliphatic dicarlooxylic acids, and
tannic acid.
3. A photographic element comprising a sup
port having thereon a light-sensitive layer and a
layer containing a colloidal dispersion of a poly
methine dye having a conjugated methine chain
joining two heterocyolic nuclei, at least one of
which nuclei is a pyrrole nucleus, and an amount
in excess of the equivalent amount of said dye of
a water-soluble salt of an alkyl naphthalene sul
fonate.
'
polymethine dye having a conjugated methine
4. A photographic element comprising a sup~
chain joining two heterocyclic nuclei, at least 15 port having thereon a light-sensitive layer and a
one of which nuclei is a pyrrole nucleus, and
(2) an amount in excess of the equivalent amount
of said dye of an anionic dispersing agent selected
from the class consisting of water-solublasalts
of alkyl naphthalene sulfonates, water-soluble
salts of esters of sulfo aliphatic dicarboxylic acids,
and tannic acid.
2. A photographic element comprising a sup
port having thereon a plurality of layers sensi
tive to different regions of the visible spectrum
and between two of said layers a layer contain
ing a colloidal dispersion of (1) a polymethine
dye having a conjugated methine chain joining
two heterocyclic nuclei, at least one of which
layer containing a colloidal dispersion of a poly
methine dye having a conjugated methine chain
joining two heterocyclic nuclei, at least one of
which nuclei is a pyrrole nuclus, and an amount
in excess of the equivalent amount of said dye of
a water-soluble salt of an ester of a sulfo ali
phatic dicarboxylic acid.
5. A photographic element comprising a sup
port having thereon a light-sensitive layer and
a layer containing a colloidal dispersion of a
polymethine dye having a conjugated methine
chain joining two heterocyclic nuclei, at least one
of which nuclei is a pyrrole nucleus, and an
amount in excess of the equivalent amount of
nuclei is a pyrrole nucleus, and (2) an amount in 30 said dye of tannic acid.
excess of the equivalent amount of said dye of
J ULES ARTHUR WIDMER.
an anionic dispersing agent selected from the
BURT H. CARROLL.
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