CC
I Patented Jan. 29, 1%33
2
sensitive silver halides. Still other objects will be appar
3,075,841
ELEliiENTS CONTAENING SAME
Roland James Lehman, Sayreviile, and Gustave William
ent from the following description of the invention. "
It has been found that a decrease in ‘back transfer
of dye mordant in dye transfer processes results when a
‘It/EGRDANT TREATING X’RQCESS AND
Moessen, New Brunswick, NJ, assignors toE. I. du
Pont de Nemours and Company, Wilmington, Dei., a
corporation of Delaware
polymeric acid dye mordant is used in the image receiv
ing ?lm element in the dye transfer printing operation,
which mordant has been treated by admixing the mordant
"
No Drawing. Filed June 19‘, 1956, Ser. No. 592,245
6 Claims. (Cl. 96-77)
in solution with polyvalent metal ions each having a
10
This invention relates to photography and more par
,ticularly to a process for improving photographic poly
meric acid dye mordants useful in dye imbibition or dye
transfer printing elements. Still more particularly, it
valence of two or more. The undesired characteristics of
'back transfer are further markedly decreased if the treated
mordant is given an aging treatment as described below
prior to inclusion of the mordant in the water-permeable
colloid, e.g., gelatin, hinder, the coated layer of which is
‘
relates to film elements containing improved polymeric 15 to ultmiately receive the transfer dye.
The ‘invention in its broadest aspects comprises a proc
acid dye mordants. More speci?cally, this invention
ess for reducing the diffusing or back transfer tendencies
relates to photographic silver halide emulsions containing
of a polymeric acid dye mordant of the type having
polymeric acid dye mordants which have been admixed
recurring extralinear‘amino groups by admixing the mor
in solution with polyvalent metal ions. The invention
further relates to a process for reducing the back transfer 20 dant, prior to inclusion in the image receiving element,
in solution with polyvalent positive metal ions each hav
properties of metal ion-mordant solutions by aging and
to water~permeable colloid emulsions and ?lm elements
containing the resultant solutions.
It is well known that the dye mordant used in mor
danted ?lms in dye imbibition or dye transfer printing
operations tends to diffuse out‘ of the mordanted image
receiving element and into the image bearing gelatin
ing a valence of two or more, said metal ions being present
in an amount of at least 0.006 mol per 100 grams of
mordant present. The metal ions may conveniently be
introduced by adding a corresponding metal salt to ‘a
solution already containing the mordant, or by adding
the mordant to a solution of the metal salt, or by ad
mixing two separate solutions, one of which contains the
mordant and the other of which contains the metal ions
called “back transfer” and is highly objectionable in
dye imbibition or dye transfer printing. Specially, upon 30 which may have been introduced as a metal salt. ' After
mixing, the mordant-metal ion solution can then be added
‘repeated transfer of successive dye applications from
to a water-permeable colloid binder for making a ?lm
the same matrix in routine printing operations, the matrix
matrix. This migrating or diffusion of the mordant is
‘becomes infused with dye mordant, accumulated from the
premordanted image receiving element with each suc
cessive printing, and the efficiency and usefulness of the
matrix is thus impaired. In addition, the dye mordant
element.
'
‘
'
'
'
’
In a more speci?c aspect, the invention comprises va
process for reducing the diffusing or back transfer ten
dencies of a polymeric mordant for acid dyestuffs, said
may typically spread into the areas of the matrix which
mordant being of the type having recurring extralinear
should not contain the transfer dye and thus ultimately
cause lack of sharpness and objectionable dye density
dant, prior to inclusion in the image receiving element,
in highlight areas of the ?nal print.
‘
amino groups, which process comprises mixing the mor
40 in solution with polyvalent positive metal ions each hav
ing a valence of 2 or more, said metal ions being present
An object of this invention is to provide a process,
for improving the back transfer properties of a photo-‘ " in an amount of at least 0.006 mol per 100 grams of
graphic acid dye mordant. A further object is to provide
a process for treating acid dye mordants which results
in reduction in the amount of back transfer of the mordant
‘during dye imbibition or dye transfer printing. A still
further object is to provide such a process for treating a
polymeric mordant for inclusion in a dye print receiving
?lm element, and particularly in a light-sensitive silver
halide photographic emulsion without causing any delete
rious effect to either the emulsion or the polymeric
‘mordant. Another object is to provide such a process for
obtaining improved dye mordants which exhibit reduced
back transfer and do not harmfully a?ect the photographic
mordant present, followed by an aging step. The'aging
step comprises subjecting the solution to certain condi
tions of time and temperature which can be varied over
45 wide limits to suit the particular conditions.
it has been
found that suitable aging with its subsequent reduction
in back transfer can even be carried out at refrigeration
temperatures of about 45 ° F. if the aging period is allowed
to take place for a sufficiently long time. Temperatures
as low as 32° F. and as high as 212° F. are considered
satisfactory. Further, there is no required minimum or
maximum period of time necessary for aging of the
mordant-metal ion solution; the longer the aging period,
the greater the reduction of back transfer. For example,
fog and fog stability.
55 an approximately equal reduction in back transfer occurs
by carrying out the aging 'proces for 264 hours at 45° R,
An additionalobject of-this invention is to provide im
48 hours at 95 ‘’ F.‘fo_r 21/2 hours at 140° F. More or, less
proved ?lm elements,'including gelatin blanks, light-sensi
aging treatment at any given temperature results respec~
tive silver'halide emulsions andgphotographic ?lmshaving
tively in a higher or lower degree of ‘improvement in back
light-sensitive layers, which elements contain polymeric
'
acid dye mordants which exhibit negligible back transfer 60 transfer reduction.
properties of the emulsion, such as sensitometric gamma,
when used in dye imbibition or dye transfer processes.
The invention also comprises the ,Water permeable
colloid emulsions and photographic emulsions contain
Yet another object is to provide suchmordanted elements
in which mordanted acid dy-e images of good resolution
ing the mordant whichlhas been improved as described
colloid layers and have'no deleterious action on‘light
Vm‘ay be used as the image receptive element in adye
above, and film elements made from such emulsions.
may be formed. A further and more speci?c object of
the invention is to provide photographic silver halide 65 The emulsions are madeby simply mixing the polymers
treated according to the process .of this invention with‘a
emulsions which contain non-fogging polymericacid dye
dispersion of a colloid, e.g., gelatin, which acts as ,a
mordants which have been admixed in aqueous solution
binderfor the mordant. Such an emulsion, which may
with polyvalent metal ions. A still further object is to
ormay not be lightsensitive, can be coatedonto a suit
provide such emulsions containing such metal ion-treated
able support or layer to make a ?lm element, which
‘mordants which are non-diffusing in water-permeable
imbibition transfer process.
3,075,841
1;
t2)
In a prefered embodiment of this invention, a photo
graphic emulsion can be made by simply mixing the mor
dant treated according to the above described processes
of this invention with an aqueous dispersion or emulsion
of light-sensitive silver halide in a water-permeable col
loid, which may contain the usual emulsion adjuvants,
e.g., sensitizing dyes, stabilizers, hardeners, anti-foggants,
4
by the amount of brittleness which can be tolerated‘ in
the ?lm product, and brittleness is also affected by other
factors, e.g., emulsion additives and ambient conditions
of temperature and humidity. Metal ions in an amount
as great as 0.085 mol and more per 100 grams of mor
dant are considered satisfactory. The preferred range
of iron concentration is from 0.02 to 0.055 mol per 100
grams of mordant.
Surprisingly, it has been found that it is essential to
etc., prior to coating onto a suitable support or layer to
form a photographic element. in general, the amount
admin the metal ions with the polymeric mordant prior
of mordant used is about 25 to 55 grams per mol of 10 to the inclusion of the mordant in the photographic emul
silver halide. The resulting products have excellent mor
sion or ?lm element. Mere addition of the metal ions to
danting properties with respect to acid dyes, and are
particularly distinguishable by the superior non-diffus
ing properties of the polymeric mordant.
the photographic emulsion, or to the water-permeable
colloid as is done when the ions are used as colloid
hardening agents does not attain the outstanding im
The polymeric mordants within the scope of this inven 15 provement in reduction or" the diffusion tendencies of
tion include polymeric acid dye mordants having recur
dye mordants.
ring extralinear amino groups. By amino groups we
The colloids used as the binders in the emulsions ac;
mean either an amino group itself or an acid salt or
cording to this invention may be of any of the usual
quaternary salt thereof. The polymers may be sub
colloids used by photographic manufacturers. They are
stituted or unsubstituted and may include polymers of 20 generally water-permeable and may be of natural or syn
amines, amine acid salts and quaternary ammonium salts,
thetic composition. Thus, the colloid, which is pref
and copolyrners of two or more said amines, amine acid
erably gelatin, may be agar-agar, albumin, zein, col
salts and quaternary ammonium salts with each other or
with other polymerizable ethylenically unsaturated com
pounds in an amount not exceeding about 50% of the
latter. Preferably, the polymeric mordants of this inven
tion are selected from the group consisting of (a) vinyl
lodion, polyvinyl alcohol, partly hydrolized polymeric
acetals, and hydrophilic copolymers thereof with ethyleni
cally unsaturated monomers such as ethylene, vin‘l chlo
ride, etc; polyvinyl acetals, e.g., the acetals of poly
vinyl alcohols with acetaldehyde or benzaldehyde; or
water soluble or hydrophilic cellulose derivatives. Suit
having tertiary amine salt groups and monoethylenically
able binders or water-permeable colloids of the above
unsaturated compounds having quaternary ammonium 30 types are described in US. Patents Nos. 2,110,491,
copolymers of monoethylenically unsaturated compounds
salt groups, (1;) vinyl copolymers of said unsaturated
compounds with up to 50% by weight of another mono
2,211,323, 2,276,322, 2,276,323, 2,286,215 and 2,397,866.
To form a ?lm element, which may be done according
to well known means, the emulsion containing the metal
ion-mordant solution according to this invention is
for the processes and products of this invention include 35 coated on a suitable support. Such supports include
the polymeric polyamine mordants disclosed in Gray
paper, which may be baryta coated, cardboard, or water‘
U.S. application Serial No. 379,467, ?led September 10,
proofed or transparentized paper or other ?lm. The
1953, now US. Patent 2,753,263, issued Euly 3, 1956,
support may be composed of any suitable hydrophilic
the quaternary salt products of polyvinylpyridine dis
sheet or pellicle, e.g., cellulose derivatives such as cellu
40
closed in Minsk et al. US. Patent No. 2,484,420, and the
lose nitrate, cellulose triacetate, cellulose proprionate,
alkyl amine polymers disclosed in Carroll et al. US.
cellulose acetate butyrate; polyvinyl chloride, polyvinyl
ethylenically unsaturated compound, and (c) quaternary
salts of polyvinylyridine. Suitable polymeric mordants
Patent No. 2,675,316. The especially preferred mordants
chloride/ acetate; hydrophilic acetals, e.g., from formalde
are the copolymeric alpha-alkacrylic acid esters of amino
hyde and acetaldehydes, superpolymers, e.g., polyamides,
alcohols having tertiary and quaternary salt groups in
polyesters such as polyethylene terephthalate, poly
the proportion of 35 to 75 mol percent of the former to 45 styrene, etc. The ?lm supports may be clear or may
65 to 25 mol percent of the latter, which are disclosed in
contain dyes or pigments. The coated polyester ?lm
Gray and Webers U.S. application Serial No. 478,544,
base described in Alles and Saner US. Patent No. 2,627,
?led December 29, 1954-, now U.S. Patent 2,839,401,
088 is especially useful as a support material.
issued June 17, 1958. l’olymeric moi-dents having
In admixing the polymeric mordant with the metal ions
50
molecular weights above 10,000 are preferred.
in a solution, the solvent must be a common solvent for
The metal ions useful in this invention include those
both the mordant and the metallic salt. Pmticularly when
which are well known in the photographic art as gelatin
the usual water-permeable colloids listed above are used as
hardening agents. Such hardening or cross-linking of
a binding material, the solvent is typically and preferably
gelatin or other proteinaceous material is well known.
55
water.
Suitable metal ions which may be introduced, as stated
The processes and products of this invention will be
above, in the form of an appropriate ionizable salt in
further described but are not intended to be limited by
clude chromic, cupric, aluminum and ferric ions. Suit~
the following examples.
able salts containing suitable metal ions include chromic
EXAMPLE I
bromide, chromic sulfate, aluminum chloride, potas
sium aluminum sulfate, ferric chloride, ferric sulfate, 60
A washed positive-type light-sensitive lode-bromide
ferric ammonium sulfate, cupric chloride, cupric sulfate,
gelatin photographic emulsion was given a customary sec
etc. Of the useful salts, those which contain ionizable
ond digestion treatment and divided into four equal parts.
trivalent metal ions are preferred, and, in particular, the
To the ?rst part was added a 5% aqueous solution of di~
preferred metal salt is chrome alum.
ethylaminoethylmethacrylate tertiary salt-diethylaminoeth
65
It has been found that the range of concentration
ylmethacrylate quaternary salt copolymer having a mol
of metal ions, when used in the processes and products
ratio of 60% tertiary salt to 40% quaternary salt copoly
of this invention, is limited to a minimum amount of at
mer made according to the procedures described in Gray
least about 0.006 mol per 100 grams of mordant present.
et al. application Serial No. 574,593, ?led March 29, 1956,
‘It has been found that below the stated range the amount
in the amount of 22.0 grams of copolymer per 100 grams
of metal ion added is insufficient to eii’ect any signi?cant 70 of emulsion gelatin. To the second part of the emulsion
improvement in the back transfer properties of the mor
there was added an equal amount of copolymer mordant
dant. The upper limit is not as critical but it has been
solution which had been aged at 140° F. for 21 hours. To
found that larger amounts of metal ions cause brittle
third part of the emulsion there was added an equal
ness of the water-permeable colloid emulsion or ?lm
, amount of copolymer mordant solution to whichhad been
product. The upper limit will therefore be determined
5
added chrome alum in an amount of 0.041 mol per 100
The results of Example I show that the process of metal
grams of mordant, the mixed polymer mordant chrome
alum solution having been aged for 24 hours at 75° F.
prior to incorporating into the emulsion. To the fourth
ion treatment and aging, as in coating Nos. 3 and 4, gives
a reduction in back transfer of, respectively, about 38.9%
and 95.2% over the untreated mordant. There has been
no deleterious aifect on the photographic properties of
part of emulsion was added an equal amount of polymer ;
mordant-chrome alum mixture as in part three, except the
mixture was aged at 140° F. for 21 hours prior to use. To
emulsion portions one and two there was then added an
amount of chrome alum which was equal to that contained
the emulsion. The slight indicated reduction in speed is
not critical in positive type emulsions and can be com
pensated for by means well known in the art.
in the mordant-chrome alum mixtures used in portions
three and four. The usual post-digestion additives of
stabilizers, coating aids, etc., were added to each portion
‘EXAMPLE n
In this example the reduction of back transfer as a
and the emulsions were coated on a thin cellulose acetate
function of variation of the aging time of polymeric
?lm support and dried in the customary manner.
mordant-metal ion mixtures at elevated temperature is
illustrated. To a 5% aqueous solution of diethylamino
Sample strips of each coating were then processed with
out exposure in a positive-type metol-hydroquinone de
ethylmethacrylate tertiary salt-diethylaminoethylmethacry
veloping solution and ?xed in a non-hardening type hypo
?xing bath to eliminate the silver halide.
late quaternary salt copolymer mordant was added chrome
alum as described in Example I. The copolymeric mor~
The ?lm samples were then dried and tested by an
imbibition transfer procedure for the degree of mordant 20 dant~chrome alum mixture was divided into seven equal
parts and each portion was subjected to the aging treat
migration which approximates the level of mordant back
ment indicated in Table II. A washed positive-type light
sensitive iodo-bromide gelatin photographic emulsion was
transfer that normally accrues during the commercial op
eration from 20 successive dye imbibition transfers from a
Single matrix. The aqueous‘ dye solution used was ad
justed to a pH of 2.4 to 3.0 and contained approximately
divided into seven equal portions after the customary sec~
ond digestion treatment. To each portion of emulsion was
then added one of the pro-aged mordant-chrome alum
mixtures. The quantities of various ingredients were so
1.6 grams of Pontacyl Carmine 6B Extra Concentrated
(Colour Index No. 57) magenta dyestuit per liter of water.
The spectral density of residual dye stain on the ?lm used
calculated that after combination each emulsion portion
contained 22.0 grams ‘of copolymer per 100 grams of
emulsion gelatin and 0.041 mol of chrome ‘alum per 100
grams of mordant. Equal quantities of the usual post
digestion adjuvants were added to each emulsion portion
and the emulsions were then coated and dried. Samples
to test the level of back transfer was read on a color 30
densitometer (as described in J.S.M.P.T.E., 56, page 23.
1951) at a wavelength of 540 millimicrons. The spectral
density of such residual dye stain is a direct measure of
the degree of back transfer. The greater the amount of
' of each coating were then tested for back transfer, and
sensitometric speed, gamma, and fog as described in Ex
' ample I. The mordant-chrome alum mixture pre-treat
ment and the results of the tests are given in Table II.
mordant adsorbed from the mordanted blank during the
imbibition transfer test, the greater is the density of resid
ual stain. For example, it a control ?lm containing no
mordant is used in place of the mordanted ?lm in the test
procedure described above, the spectral density of residual
dye stain as read at a wavelength of 540 millimicrons is
zero to within the accuracy of the density determination.
Table II
Sensitometric testing of the four light sensitive silver
halide emulsion coatings containing the mordants which
-
Ooating
had been variously treated as described above was carried
out as follows: Samples of each coating were given a Ib
gamma, and fog were carried out in the customary manner.
1_____
Density
Fresh test
dye
Speed Gamma Fog
of
residual
No.
sensitometric exposure and developed for 31/2 minutes in
a positive-type metol-hydroquinone developer at 68° F.
Fixing, washing, drying and determination of speed,
Mordant
treatment
stam
21 hrs. at 75° ______ __
2____. 15 Min. at 140° F.+
0
Duplicate samples of each coating were subjected to an
incubation treatment at a temperature of 120° F. and
65% relative humidity for 48 hours and processed together
with the non-incubated samples. For the incubated 55
samples, only the fog values were recorded. The data
20% hrs. at 75° F.
Mordant
treatment
No.
1..____
None ______________ -_
F. Without chrome
alum.
3_,____ Aged 21 hrs. at, 75°
F. with chrome
alum.
4_____ Aged 21 hrs. at 140°
F. with chrome
alum.
2. 86
.02
. 09
96
3. 04
.02
. 07
. 15
75
2.97
.02
.08
.08
68
3.26
. 02
. 11
75° F.
5_____ 5 hrs. at 140° F.
.06
68
2. 97
.02
.16
64
3.00
.02
20 hrs. at 75° F.
plus 18% hrs. at
plus 16 hrs. at
75° F.
0_____ 10 hrs. at 140° F.
.05
plus 11 hrs. at
.10
_
'
.05
‘
66
2. 93
. 02
.;11
60.
Density
of
residual
Fresh test
Incu
bated
test
dye
Speed Gamma Fog
Fog
stain
2_____ Aged 21 hrs. at 140°
100
. 33
3_____ 1 hr. at 140° F. plus
'7"-.. 21 hrs. at 140° F“.--
Ccatiug
. 44
75° F.
Table 1
Fog
4_____ 2% hrs. at 140° F.
a
are given in Table I.
Incu
bated
test
EXAMPLE III
65
1.26
100
3. 07
.01
. 13
1.19
102
3. 23
.01
. 13
.77
100
3.18
.01
.10
.06
06
3.18
.01
.06
.Thisexample serves to illustrate the effect of varying
both the time and the temperature of mordant-metal ion
solution aging treatment as a means of reducing the un
desirable eiiects of back transfer during imbibition dye
transfer printing operation.
70
To seven equal quantities of the tertiary-quaternary
copolymeric mordant compositions previously described
in Examples I and H were added equal amounts of
chrome alum at proper time intervals so that the varying
aging treatments noted in Table III could be carried out
75
immediately in _-advance of the emulsionpreparation,coat
3,075,841
%
mixed at such times that aging at varying time and tem
ing and drying operations. A washed positive-type light
sensitive iodo-bromide gelatin photographic emulsion
perature conditions as outlined in Table 1V were com—
pleted immediately before the carrying out of the ?nal
emulsion preparation. One of the above pretreated mor
was given a customary second digestion treatment and
divided into seven equal portions. One or" the pro-aged
polymeric mordant-chrome alum mixtures Was added to 5 dant~chrorne alum mixtures was then added to a portion
each of the emulsion portions. The quantities of ingredi-
of washed positive-type light-sensitive iodo-bromide gela
ents were such that each of the ?nal emulsion portions
tin photographic emulsion which had been given a cus
contained 22.0 grams of copolymeric mordant per 100
tomary second digestion treatment. The remaining oper
grams of gelatin and 0.041 mol of chrome alum per 100
ations of addition of post-digestion adjuvants, coating,
grams of mordant. After addition of the usual post di- 10 drying, test for back transfer, sensitometric test, etc.,
gestion adjuvants, the seven emulsions were coated and
dried in a manner similar to that employed in Examples
I and H. Samples of each coating were then tested for
back transfer and sensitometric values as described in
Example 1. Details of the mordant-chrome alum mix- 15
were carried out as described in the preceding Examples.
The concentrations of chrome alum employed, the condi
tions of the aging treatment, the nature of the mordant
chrome alum mixture treatment and the results of the
etsts are presented in Table IV.
Table IV
Mols 0t
Chrome
alum per
100 g. of
Coating
N o.
Density
of re-
Moment-chrome
alum treatment
sidual
dye stain
mordant
0. 041
0.0015
0. 041
0.0015
0 041
24hr .at 80° F
24 hrs. at 80°F
24hrs.at 95°F
24 hrs. at 95°F
48 hl'S. at 05° F__
0. 0015
0. 041
48 hrs. at 95° 1111 days at 45°
ture aging used in each case and results of the tests are 30
shown in Table III.
-
Incu
ba
tion
Speed
Gamma
Fog
test
.42
.32
.14
.12
.00
100
as
84
07
67
3.27
3.30
3.13
2. s7
3. 0s
.02
.01
.01
.01
.01
.10
.10
.10
.01
.00
.00
. 10
00
72
2. 77
3.17
.01
.01
.05
.07
It can be seen from the data in Table IV that varia
tion in the amount of chrome alum present in
polymeric mordant~chrome alum mixture within
range of the invention does not markedly aifect
35 e?icacy of the aging treatment. It is also apparent
Table HI
Dmsitv of
Coating N0.
Fresh test
Fresh test
a sizable reduction in back transfer can be accomplished
Mordant‘ehrome
residual
alum treatment
dye 5mm Speed Gamma Fag
_____,_.____._
by carrying out the polymeric mordant-metal ion mix
ture aging treatment of the invention even at tempera
_-_ Fresh solutions ____ __
the
the
the
that
tures substantially below ordinary room conditions as
0. 57
0.56
O 23
100
105
95
3 2s
3.37
3'41
.02 40 well as at elevated temperatures as described in this and
.02
- th e prece 6-mg eaamp
v
1 es.
_01
1n
0122
0.20
00
82
3.34
3.27
.01
.01
‘L15
a
'
'a
EXAMPLE V
4_
A 5% aqueous solution of diethylaminoethylmethac
a rylate tertiary salt-diethylaminoethylmethacrylate qua
It can ,be seen
from
the data .cpresented
in Table
Ill that
.
.
.1
.-
ternary
Salt copolymer.n?odra.nt as d?scnbed m. Example
I was prepared and divided into 8 equal portions. To
one days aging treatment or the polymeric mordant-
l,
chrome alum mixture at 95° F. e?ccts the same reduction
days’ aging at 75° F. It is also evident from the data
that 4 days’ aging tmatment at 95w 1:- is superim- to 5
days’ aging treatment at 75° F. insofar as reduction in
back transfer is concerned.
_.
v
V
EAAMPLIE I
_
N
pogwn F0‘
in back transfer as would occur for approximately three 50 10
1
was
nddod n 041
+ “
'.
1 f h
1
A
e
0'04
mo 0 C mm;d?‘ :m p“;
g- 0* mofdant’ "0 Porno“ No‘ 3 was a
H101 of potassfml aluminum Sulfate Per 100 g- of mo?‘
dant; to portion No. 5 was added 0.041 mol of ferric
ammOml-Im Sulfate per 190 g- of mofdant, and t0 Portion
No. 7 was added 0.041 mol of cupric sulfate per 100 g.
55 of mordant. Portions numbered 1 3 5 and 7 were then
’
’
. .
aged for 24 hours at 140° F. The remaining mordant
.
In this example illustration is made that reduction 1n
back transfer by fhe agmg?fe?ltmem of Polymeric mm"
portions numbered 2, 4, 6 and 8 were kept at 75° F.
without further addition or treatment. After a customary
dam and metal Ion combinations 0,3“ also be egected
second digestion, a Washed positive-type light-sensitive
'
"
7
.
1
-
.
.
-
.
-
by the map; t?mpemmre; subfstam‘lially bio“, or Him.“ 69 iodobromlde gelatln photographic emulsion was divlded
romp condltlons’ e'g"
C is 511m mlor nmiiyoietgig;
?ratlonpsystegli’ 9.‘? 1Y6 giveyo?dfngnprgglekond?ons
peratur‘is $1.5 am‘a y a
l
y-
l
i-
'
into eight equal portions and one of the eight mordant
compositions variously treated as described above was
combined with one of the emulsion portions. To emul
lliustration is also made- that metal ion
concentrations
sion-mordant
admixture
No. 2 was then added the
same
_
_
I
other
than those
serve equally
Wen. used in the preceding examples will 65
_
_
‘ been em
quantity
of chrome alum as had PTBVIOUSLY
Amounts of chrome alum were added to seven equal
Ployed “1 the: mordarft'chmme algin ,_Pre'ag1_ng treat‘
quantities of the tertiary-quaternary copolymer mordant
want {91' min-dam Portion N?‘ 1- mmuarly’ like molar
solutions as set forth in Examole I such that the concenquanti?es of Petassmm aluminum Sulfate’ fsmc ammo‘
{ration of chrome alum in the ?nal photographic 5mm- 70 nium sulfate, and cupric sulfate were added to emulsion
sion composition would correspond as indicated in Table
mofd‘am 36111115111"? NPS- 4, .6 and 8 respewvely- The
rv to either 0.041 mol or 0.0015 mol of chrome alum
addiuon of post dlsestwn adiuvants coating, drymg, test
per 100 grams of mordant and the amount of copolymer
for back transfer, sensitornetric test,‘ etc. was completed
'nordant would be 22.0 grams per 100 grams of emulsion
as described in the preceding examples. Test results are
gelatin.
These mordant-chrorne alum mixtures were 75 presented in Table V.
3,075,841
Table V
Coating
No.
Metal salt added to mordant
Mordant aging
treatment
_
Metal salt added to emulsion
after mordant
Density
of resid
stain
Chrome
alum _ _ _ _ . .
_' Potassi
________________
on aluminum
__
L
_____________________
Cu ri" suliate-_
__
______________________ __
Fresh test
ual dye
_ _ _ _ _ . _ _ _ . _ _ . _ _ _ . _ _ _ . _ _ _ _ _ _ _ . _ -_
.
______________________________
Chrome alum.
.._
__
.7.
.
Speed Gamma Fog
10
44
2.30
r
. g2
Potassium aluminum sulfate"
.72
133 -
3. 51
______________________________ ._
. 39
95
2.91
______________________________
Ferric ammonium sulfate- _ _ _
___
.
15g
. 3%
_
3o
3. 52
Cupric sulfate _______________ -_
The data in Table V indicate that substantial reduction
in back transfer is effected by the use of any of a variety
of metal ions in the mord-ant treatment process of this
invention. It is also apparent that chromic ions are more
.62
.01
.
. 01
. 01
.
.01
dant companions. After the additions of post digestion
adjuvants, and the usual operations of coating, drying,
etc., tests for back transfer and sensitometric values were
made as previously described. The type of mordant used
e?icacious in the polymeric mordant-metal ion preaging 20 for each case, the mordant aging treatment and type of
treatment for minimizing back transfer than the other
hardening agent used, as well as back transfer and sen
metal ions illustrated and are therefore to be preferred.
sitometric results are given in Table VI. The fog values
EXAMPLE VI
reported for the incubated test were determined after sub
jection to 120° F. and 65% relative humidity for 48
5% aqueous solutions of each of diethylaminoethyl- 20 hours.
Table VI
Coating
'Mordant
Metal salt added to mordant
N 0.
1.
2.
34.
Copolymer 1
Chrome alum _______________ __
_
Mordant aging
treatment
Metal salt added to emulsion
after mordant
24 hrs. at 75° 11-.. Chrome alu
24 hrs.~at 14 F ______________ __
. at 75° F____ Chrome alum
5_
P21 Ie5VP 3-
. at 140° F ________________ -_
6.
P2l‘1lfe5VP 1L
. at 75° F__-_ Chrome alum._
7-
PZMeSVP 3_
8.
P2Me5VP -1_
9_
_
PMe2VP 2__
'Fresh test
stain
Speed Gamma Fog
24 hrs. at 140° F ________________ __
o1 ____ __
IeZVP 2__
.AQZVP i'._
10_____ PMe2Vl? 2__
Density
of
residual dye
at. 140° II‘ ____________________ __
. at 75° F."
Ferric ammonium sulf
. at. 140° F _________________________ __,__
. at 75° 11--- Potassium aluminum sulfate
. 08
.83
. 58
. 79
. 06
Incu~
bated
test
48
3. 21
. 01
.05
100
»97
110
3.18
3.32
3. 15
.03
. 01
. 03
.113
.03
.04
1. 70
.01
.18
1
1. 76
. 01
.02
‘ .43
10
13
1. 77
. 01'
.‘01
. O2
.92
6
1. 58
.01
.‘01
.56
138
3.33
. 03
.04
1. 48
130
3. 24
. 04
.‘04
1 Diethylaminoethylmethacrylate tertiary salt-diethylaminoethylmethacrylate quaternary salt copolymer.
1’ Poly-l-methyl-2-vinylpyridinium eyclohexanesulionate.
3 Poly-2-methyl-5-vinylpyridine hydrochloride.
methacrylate tertiary salt-diethylaminoethylmethacrylate
quaternary salt copolymer mordant, poly-l-methyl-Z
vinylpyridinium cyclohexanesulfonate mordant, and poly
2-methyl~5-vinylpyridine hydrochloride were prepared.
EXAMPLE VII
A 5% aqueous solution of poly-1-methyl-2-vinylpyri
dinium cyclohexanesulfonate was prepared and divided
into six equal portions. To portions numbered 2, 3, 4
and 5 were added respectively 0.0068, 0.0205, 0.041 and
0.082 mol of chrome alum per 100 g. of vinylpyridine
Chrome alum, ferric ammonium sulfate or potassium
aluminum sulfate to the extent of 0.041 mol of metal
ion per 100 g. of polymer material was added to selected
polymer mordant. ‘No additions were made to portions
portions of these solutions followed by aging 'of ‘the
‘numbered 1 and 6. The ?rst ?ve portions of mordant
mordant-metal ion mixtures for 24 hours at 140° F.
Duplicate portions of the polymeric solutions were re 60 were .then aged for 24 hours at 140° F. and the sixth
portion which served as a control was aged for 24-hours
‘served as controls without metal ion admixture and held
at room temperature of 75° F. At the conclusion of
at 75° F. during the v24 ‘hour aging process of the treated
the aging treatment, the six resultant solutions were added
polymer materials. Details of the treatment followed
to separate identical amounts of a positive-type digested
‘for each case is tabulated in Table Vi. The treated and
emulsion similar to that described in the preceding ex
untreated polymer mordant solutions were then added to
amples. Additional chrome alum was then added to
equal quantities of a washed positive~type light-sensitive
emulsion-mordant admixtures containing the first three
iodobromide gelatin photographic emulsion which had
and the sixth mordant portions so as to bring the total
been given a customary second digestion treatment. To
amount of chrome alum to 0.041 mol per 100 grams of
those emulsion~mordant mixtures which contained the 70 vinylpyridine polymer. Emulsion portions numbered 4
and 5 already contained at least this amount of chrome
untreated mordant solutions controls, an amount of
alum introduced via the mordant treatment. After the
chrome alum, ferric ammonium sulfate, or potassium
usual additions of post digestion adjuvants, the six emul
aluminum sulfate, respectively, was added which was
sions were coated, dried and tested as described in the
equal to the amount of metal ion previously present in
examples. Test data for the experiment are
each of the respective treated and aged- polymeric mor 75 previous
given in Table VII.
Table VII
Coating
No.
Mols ch.
alumllOO g.
mordant
before
Idols ch.
alum/100 g.
mordant to
emulsion
Mordant aging
treatment
Fresh test
Density of
residual
dye stain Speed
Gamma
Foe
08
Incu
bated
test log
treatment
24 hrs. at l40° F“-..
3.27
.01
0. 70
103
97
3. 23
.01
.01
.03
._-
0. 74
106
3. 35
.01
.04
_ ............ __
____ _0. 0-11
0. 72
1. 39
l04
100
3. 20
3. 01
.01
. 03
.04;
.04
.1... 0 ________ -_
0. 0&1
0. 98
0.0342
0.73
0. 0205
_ ______ __
3. 21
. 04
.03
then added to each of live equal portions of a digested
positive-type silver halide emulsion such as has been de
scribed more fully in the preceding examples. The neces
ethylrnethacrylate tertiary salt-diethylaminoethylmeth
sary steps for completion of the emulsions and the test
acrylate quaternary salt copolyrner mordant solution were
operations of the completed ?lms were carried out in a
added respectively 0.041 mol of chrome alum, 0.0273 mol
manner analogous to that employed in Example VIII.
of potassium aluminum sulfate, 0.082 mol of potassium 20 The results of sensitornetric and back transfer tests are
aluminum sulfate, 0.0273 mol of ferric ammonium sulfate,
tabulated in Table IX.
and 0.082 mol of ferric ammonium sulfate respectively.
EXAMPLE VIII
To live equal portions of a 5% aqueous diethylamino
Table 1X
Coatin
Metal salt added per 100 g. moi-dent before
- 0.
treatment
Mordant treatment
Density of
residual
dye stm'n
0.041 mol chrome alum ______________________ -_ 24 hrs. at 140° F
_ 0.273 mol potassium aluminum sulfate- .____d0____
_ 0.082 mol potassium aluminum sulfate ____________ __do_
0.0273 mol ferric ammonium sulfate
_____(lo_
0.082 mol ferric ammonium sulfate ________________ __do _ _ _ _ . _
. _ _ _-
Fresh test
Speed
[neu
bated
test
fog
Gamma Fog
0. 21
0.36
0.13
0.19
100
111
111
78
1.95
1.96
2. 01
1.76
0. 05
78
1. 66
.01
.01
. 01
. 01
.01
.01
.01
. 01
.01
. 01
EXAMPLE X
These ?ve mordant solutions thus treated were then aged
at 140° F. for 24 hours. A sixth control solution of
A 5% aqueous solution of diethylaminoethylmeth
mordant received no additions and was retained at 75° F. 00 acrylate tertiary salt-diethylaminoethylmethacrylate qua
for 24 hours. After completion of the aging process, the
ternary salt copolymer mordaut was prepared and divided
?ve treated and the sixth untreated mordant solutions
into six equal portions. To portions numbered 3, 4, 5
were added to equal portions of a digested positive-type
and 6 were added respectively 0.0068, 0.0205, 0.041 and
silver halide emulsion as described in the preceding exam
0.0615 mol of chrome alum per 100 g. of copolymer
ples. To the sixth control emulsion containing the un 45 mordant. Portion No. 1 served as a room temperature
treated mordant was then added chrome alum in the
aged (75° F.) untreated control and portions numbered
amount of 0.041 mol per 100 g. of copolymer mordant.
2 through 6 were aged at 140° F. for 24 hours. At the
The remaining operations of addition of post digestion
conclusion of the aging treatment, the sir. mordant solu
adiuvants, coating, drying, etc. were carried out and the
tions were added to a 5.5 % aqueous gelatin solution such
usual tests made on the ?lms thus prepared. The results
of the tests are given in Table Vill.
‘*0 that each gelatin solution-rnordant admixture contained
F
.
.
.
-
Table VIII
Coat.
ing Metal salt added per 100 g. mordant before
No.
treatment
Mordant treatment
Metal salt added to emulsion per 100 g. mordant
Density of
residual
dye stain
Fresh test
Speed
Gamma
Incu
bated
test 191;
Fog
0.041 mol chrome alum __________________ __ 24 hrs. at 140° F...
0. 08
95
3. 12
.01
. 12
0.0273 mol potassium aluminum sulfate"- .____do_
0. 28
102
3. e0
. 01
.20
0.082 mol potassium aluminum sulfate ________ -_d
0.0273 mol ferric ammonium sulfate ________ __
0.19
0. 2g
105
98
46
5. 20
. 01
.01
. 17
. 13
0. lo
0. 42
04
100
3. ‘28
3. 41
. 01
. o1
0.082 mol ferric ammonium sulfate
_______ __do
e ____ __, __________________________________________ __
_
l
EXAMPLE IX
__________________________ __
0.041 mol chrome alum-_ ._
l
. 14
. 19
22.0 g. of niordant per 100 g. of gelating. To each of the
gelating solutions containing mordant portions numbered
1, 2, 3 and 4 su?icicnt chrome alum was added to make
the concentration 0.041 mol of chrome alum per 100 g.
mordant.
?ve equal portions. To these were added respectively 70 of The
usual coating aids were added to each of the above
0.041 mol of chrome alum, 0.0273 mol of potassium alu
six gelatin-mordant compositions and coatings were made
minum sulfate, 0.082 mol of potassium aluminum sulfate,
from each and dried. Since these coatings were not light
0.0273 mol of ferric ammonium sulfate, and 0.082 mol
sensitive and contained no silver halide, back transfer tests
of ferric ammonium sulfate. The ?ve mordant-rnetal ion
could be made immediately. '1‘ he same procedure for back
admixtures were then aged for 24 hours at 140° F. After 75 transfer test was followed as was used in the earlier
aging treatment, one of the treated mordant solutions was
A 5% aqueous solution of poly-Z-methyl-S-vinyl
pyridine hydrochloride was prepared and divided into
8,075,841
13
14
examples, except that ‘the silver halide bearing samples
underwent‘suitable development, ?xation, etc., prior to
An additional advantage of the invention is that it
provides improved non-di?using and non-migrating poly
the actual back transfer test operation. The results are
shown in Table X.
meric acid dye mordants which can be incorporated in
-
light-sensitive silver ‘halide emulsions and in photographic
elements containing light-sensitive silver halide without
deleterious effect on the photographic properties of the
light-sensitive material. Still other advantages will be
apparent from the above.
Table X
’
Mols chrome
Coating alum per 100
No.
,
Mordant aging
g. mordant
treatment
’ Mols chrome‘
alum per
Density
100 g. Inor- ‘
of resid
before treat-
dant added
ual dye
ment
to mordont- '
stain
gelatin
admixture
The invention claimed is:
10
24 hrs. at 75° F ____ __
0. 041
.45
24 hrs. at 140° 'F_____
0. 041
.50
d
.
.24
.08
. 06
.10
_
1. The process for reducing in a dye transfer receiv
ing element the back transfer tendencies of a water
soluble, photographic polymeric acid dye mordant se
lected from the group consisting of (a) vinyl copolymers
of monoethylenically unsaturated compounds having ter
15 tiary amine salt groups and monoethylenically unsatu
rated compounds having quaternary ammonium salt
groups, (b) vinyl copolymers of said unsaturated com
pounds with up to 50% by weight of another mono
ethylenically unsaturated compound, and (c) quaternary
EXAMPLE XI
Example X was repeated except that the mordant used 20 salts of polyvinylpyridine, which comprises admimng said
mordant in aqueous ‘solution with from 0.006 to 0.085
was poly-1-methyl-2-vinylpyridinium cyclohexane'sulfo
mol per 100 grams of mordant of polyvalent metal ions
mate. The results are shown in Tale XI.
selected from the group consisting of chromic, cupric,
aluminum and ferric ions, subsequently aging said solu
Table XI
Mols chrome
Coating alum per 100
No.
g. mordant
Mordant aging
treatment
betore treatmerit
25 tion at a temperature of from 45° F. to ‘212° F. for a
period of at least 21/2 hours, the temperature and time of
said aging treatment being selected so that the back
Mols chrome
alum per
Density
100 g. mor-
of resid
dant added
to mordant-
ual dye
stain
gelatin
admixture
transfer tendencies of said mordant are reduced by more
than about 40% and coating said aged solution on said
30 dye transfer receiving element.
2. A process as de?ned in claim 1 wherein said aged
solution is impregnated into said dye transfer element.
24 hrs. at 75° F ____ u
0. 041
24 hrs. at 140° F_____
O. 041
.36
_-_._do _____________ _,
0. 0342
.14
.
-
3. The process set forth in claim 1 wherein the solu
tion is aged at a temperature in the range from 75° F.
.38
. 11
.15
. 06
35
to 140° F.
' _
4. The process of making a ?lm element comprising
admixing in solution (1) a Water-soluble, photographic
polymeric acid mordant selected from the group con
Among the acid dyes which can be mordanted by
means of the polymeric mordants having the improved
ditlusmg characteristics according to this invention are:
Anthracene Yellow GR (400% pure Schultz No. 177)
Fast Red S Conc. (Colour Index 176)
Pontacyl Green SN EX. (Colour Index 737)
Acid blue black (Colour Index 246)
Acid Magenta 0 (Colour Index 692)
Naphthol Green B Conc. (Colour Index 5)
Brillsigpt Paper Yellow Ex. Conc. 125% (Colour Index
3
Tartrazine (Colour Index 640)
Metanil Yellow Conc. (Colour Index 138)
Pontacyl Carmine 68 Ex. Conc. (Colour Index 57)
Pontacyl Scarlet R Cone. (Colour Index 487)
Pontacyl Rubine R Ex. Conc. (Colour Index 179)
An advantage of the invention is that it provides a new
sisting of (a) vinyl copolymers of monoethylenically
40 unsaturated compounds having tertiary amine salt groups
and monoethylenically unsaturated compounds having
quaternary ammonium salt groups, (.5) vinyl copolymers
of said unsaturated compounds with up to 50% by
weight of another monoethylenically unsaturated com
pound, and (c) quaternary salts of polyvinylpyridine,
and (2) polyvalent metal ions selected from the group
consisting of chromic, cupric, aluminum and ferric ions,
aging said solution of mordant and metal ions at a tem
perature of from 45° F. to 212° F. for a period of at
50 least 21/: hours, the temperature and time of said aging
treatment being selected so that the back transfer ten
dencies of said mordant are reduced by more than about
40%, after said aging admixing with said solution a
water-permeable colloid to form an emulsion, and coat
ing said emulsion onto a ?lm support.
5. A photographic element comprising a water-perme
able colloid emulsion containing a light-sensitive silver
halide and mordanting amounts of a solution prepared
and simple process for reducing the diffusing tendencies
of polymeric acid dye mordants useful in dye imbibition
and dye transfer printing operations. Premordanted ?lms
by admixing in aqueous solution a water-soluble photo
containing the improved polymeric mordants along with 60 graphic polymeric acid dye mordant selected from the
a light-sensitive silver halide may be exposed and processed
group consisting of (a) vinyl copolymers of mono
before dye transfer so that the ?lm will bear records of
silver, e.g., an optical sound track.
ethylenically unsaturated compounds having tertiary
amine salt groups and monoethylenically unsaturated
A further advantage of the invention is that the im
compounds
having quaternary ammonium salt groups,
proved polymeric mordants do not fog silver halide layers 65 (b) vinyl copolymers of said unsaturated compounds
and can be incorporated directly therein. A still further
with up to 50% by weight of another monoethylenically
advantage is that the improved mordants in the dye
unsaturated compound, and (c) quaternary salts of poly
imbibition blank or image receiving layer produces dye
vinylpyridine, and metal ions in an amount of from
images of increased sharpness. Another advantage of the
0.006 to 0.085 mol per 100 grams of mordant, said metal
70
invention is that a large number of satisfactory prints can
ions selected from the group consisting of chromic, cuprie,
be made from the same matrix in routine dye transfer
aluminum and ferric, and subsequently aging said solu
printing. Yet another advantage is the reduction in ob~
tion at a temperature of from 45° F. to 212° F. for a
jectionable dye density in high light areas of the ?nal
period of at least 21/2 hours, the temperature and time
print.
75 of said aging treatment being selected so that the back
spanner
1%
transfer tendencies of said mordant are reduced by more
than about 40% .
6. A dye imbibition transfer element comprising a
support and a water-permeable colloid layer which coin
prises a water-permeable colloid emulsion containing in
rnordanting amounts a solution prepared by admixing
in aqueous solution a water-soluble photographic poly
meric acid dye niordant selected from the group con
sisting of (a) vinyl copolymers of monoethylenically un
saturated compounds having tertiary amine salt groups 10
and monoethylenically unsaturated compounds having
quaternary ammonium salt groups, (b) vinyl copolyrners
of said unsaturated compounds with up to 50% by weight
of another monoethylenically unsaturated compound, and
(c) quaternary salts of polyvinylpyridine, and metal ions
in an amount of from 0.006 to 0.085 mol per 100 grains
of mordant, said metal ions selected from the group con
sisting of chromic, cupric, aluminum and ferric, and
subsequently aging said solution at a temperature of
References Cited in the ?le of this patent
UNITED STATES PATENTS
2,182,794
2,215,196
2,256,356
2,474,612
2,527,223
2,527,260
2,548,575
2,635,535
2,675,316
2,753,263
2,768,079
2,813,845
2,821,455
2,839,401
2,857,372
2,897,200
from 45° F. to 212° F. for a period of at least 21/2 20
hours, the temperature and time of said aging treatment
being selected so that the back transi'er tendencies of said
mordant are reduced by more than about 40%.
1939
1940
1941
i949
Kern ______________ __ Oct. 24, 1950
Hart et al. __________ __ Oct. 24, 1950
Weyerts ____________ __ Apr. 10, 1951
Jennings ____________ __ Apr. 21, 1953
Carroll et al. ________ __ Apr. 13, 1954
Gray ________________ __ July 3, 1956
Russell ____..v _______ __ ()ct. 23, 1956
Wesp et al. _________ .. Nov. 19, 1957
Delangre ___________ .. Jan. 28, 1958
Gray et al. _________ __ June 17, 1958
Straley et al. ___> _____ __ Oct. 21, 1958
Meader et a]. _______ __ July 28, 1959
Dawson ____________ __
ec. 12,
Schlack _____________ __ Sept. 17,
Russell et al. ________ _- Sept. 16,
Barney ____________ __ June 28,
FOREIGN PATENTS
330,199
344,365
Great Britain ________ __ June 12,
Great Britain _________ __ Mar. 12,
1930
1931