Note: Descriptions are shown in the official language in which they were submitted.
- 1057994
The present invention relates to novel polymeric
compounds which are good mordants for dyes used in photo-
graphic systems and to photographic systems using such
compounds.
- It is known in the photographic art to use various
polymeric materials as mordants in integral negative receiver
elements comprising a support and a layer containing a
.
silver halide emulsion to prevent the migration of dyes.
Among the various polymers suggested as dye mordants are
- 10 those formed by quaternizing a polymer containing tertiary
;,
nitrogen atoms with an alkylating or aralkylating agent such
as described in Cohen et al U.S. Patent 3,709,690 issued
January 9, 1973.
Such prior mordants typically are water-soluble
and thus, the presence of water in the system can adversely
affect the quality of the resultant image. That is, if
moisture is present in a photographic system containing a
water-soluble mordant there is a tendency for the image dyes
, to migrate into non-image areas. This migration of dye ~-
caused by failure of the mordant to hold the dye results in
poor image qualtiy and decreased density. The search for
the mordant polymers having an ability to receive and strongly
hold transferred dye images has been quite extensive.
According to the present invention, water-soluble polymeric
mordants are provided to which image dyes are strongly
attracted and held, thereby resulting in mordanted dye
images of increased density.
The polymeric mordants of the present invention
' comprise repeating units at least 1/3 of said units having
the following formula:
-2-
,
1057999L
,~.. ' -- ,Rl--.
I. _ C'H2 ~ ~ - _
., . ~
CH2
R5 - ~ - R3
- R4
X~3,
w~erein R1 and R2 are hydrogen atoms or lower alkyl groups
containing from 1 to 6 carbon atoms such as methyl, ethyl,
propyl~ butyl, pentyl, hexyl; R3, R4 and R5 are alk.yl groups
containing from 1 to about 20 carbon atoms such as methyl,
ethyl, propyl, isopropyl, butyl, pentyl, hexyl, benzyl, octyl,
decyl; and ~ is an anion including such monovalent negative
salt forming ionic radicals or atoms as a halide (e.g.,
bromine,-chlorine),.an alkyl sulfate, an alkane or arene sul-
fonate (for example, a p-toluenesulfonate) and a diall~yl
: phosphate, characterized in that said mordant is rendered in-
soluble by (a) the total number of carbon atoms in R3, R4 and
R5, (b) the amount of ethylenically unsaturated hydrophobic
comonomer present, if any, or (c) a combination of (a) and
(b).
It is understood that the present polymeric mordants
can be homopolymers or copolymers with at least one other
ethylenically unsaturated hydrophobic monomer so long as at
least 1/3 of the repeating units of the copolymer constitute
..... . . .
those having the forrnula I described above and the resulting
hornopolymer or copolymer is ~7ater-insoluble. In the case of
honopolyrners,
1~
~` 3
10579g4
the total number of carbon atoms in R , R and R5 should be
greater than 15 in that the homopolymer poly(N,N,N-tripentyl-
N-vinylbenzylammonium chloride) is soluble. In the case of
copolymers, the hydrophobic comonomer typically is present in
at least about 30 mole percent in order to impart insolubility.
- The minimum amount of comonomer necessary to render the co-
polymer insoluble, of course, is dependent upon the total
number of carbon atoms in R3, R4 and R . In preferred
embodiments, the total number of carbon atoms in R3, R4 and
10 R5 is at least 12 and can range from 12 to about 30. Preferably,
the cationic moiety of the polymeric mordant is substantially
free of carboxyl (COOH) groups. The presence of carboxyl
groups in the polymer may interfere with effective dye
mordanting.
Thus, in accordance with the present teachings, a
photographic element is provided which comprises a support and
at least one layer comprised of an insoluble homopolymeric
mordant or copolymeric mordant with at least one other
ethylenically unsaturated monomer. The mordant comprises
repeating units with at least one third of the units having
the formula: Rl
'' [~
CH
R5 - N42- R3
1 2 R4 X~
wherein R and R are hydrogen or an alkyl containing from 1
to 6 carbon atoms, R3, R4 and R5 are each alkyl groups contain-
ing from 1 to 20 carbon atoms with the total number of carbon
atoms in R , R and R being at least 12 and X is an anion.
-3a-
~,
10~79S~4
Typical ethylenically unsaturated hydrophobic monomers
which can be used to forrn ethenic copolymers (including two,
three or more repeating units) according to this invention
include ethylene, propylene, l-butene, isobutene, 2-methyl-
pentene, 2-methylbutene, 1,1~4,4-tel;ramethylbutadiene, styrene,
alphamethylstyrene; monoethylenically unsaturated esters of
aliphatic acids such as vinyl acetate, isopropenyl acetate,
i allyl acetate, etc; esters of ethylenically unsaturated mono-
or dicarbo~ylic acrylate, diethyl methylenemalonate, etc; mono-
ethylenically unsaturated compounds such as a?crylonitrile,
allyl cyanide, and dienes such as butadiene and isoprene.
. A preferred class of ethylenically unsaturated hydrophobic
monomers which may be used to form the ethenic polymers of
this invention includes the lower l-alkenes having from 1 to
- 6 carbon atoms, styrene, and tetra-methylbutadiene and methyl-
methacrylate.
. It is.noted that the polymer must be water-insoluble.
Thus, although a homopolymer having a total of 12 carbon atoms
on the R3, R and X5 substituents may be water-soluble and are
not within the scope of this invention, a similar polymer co-
polymerized with styrene in the range of 10 to 40~0 by weight
,~ of the copolymer may be water-insoluble and can improve the
mol~danting properties desired. By "water-insoluble", it is
meant that less than one gram of polymer will dissolve per
100 cc of water at room temperatllre (25C).
The mordants of this invention are generally pre-
pared by quaternizing a polyrner comprising repeating units
at least 1/3 of whlch have th~ formula:
--4--
5799
,. . R1
~` II. - CH - C - _
. R2 [~
,' CH2
D
with a tertiary amine having the formula:
¦ R3
III. N-R4
, '' '
wherein Rl, R2, R3, R4 and R5 are as describéd above and D
is a halogen atom. Polymers of formula II which may be reacted
~ - with the tertiary amine include poly(vinylbenzyl chloride) and
-; copolymers of vinylbenzyl chloride with other ethylenically
unsaturated monomers such as styrene and methyl methacrylate
and the like. Typical suitable tertiary amines which may be
used in this process include tributylamine, trihexyla~ine, tri-
pentylamine, trioctylamine, diethyldodecylaminej dimethyltetra-
; decylamine, dimethyloctadecylamine, dimethyldodecylamine, tri-
isopentylamine and the like.
The vinyl polymer and tertiary amine may be reacted
by heating in the presence of a solvent comprising alcohols
boiling above 100C, particularly methoxyethanol, ethoxyethanol,
and benzyl alcohol. The reaction may be carried out at any
temperature but preferably is conducted at a temperature from
70 to 110C. The reaction may be carried out using substantially
equimolar amounts of the polymer, e.g., poly(vinylbenzyl halide)
or the like and tertiary amine. An exchange of anions may be
made, if desired, in order to produce polymeric, quaternary
nitrogen group containing mordants to be employed in certain
-5-
. . .
', ~' 1057C194
photographic supports such as dye-transfer systems. The
-exchange of anions merely involves reacting the polymer with
a salt such as silver acetate, silver p-toluenesulfonate or the
like containing the preferred anion.
:The polymers resulting from the above reaction may
additionally contain some recurri~g units of the structure:
IV. Rl
-CH - C-
:` ' ' R2
,' , v~ ,
: ~ CH2
- x6
wherein R6 is the residue of the alcohol solvent employed in
the reaction mixture. R6 may thus be an alkyl, alkaryl, aryl
. .. ~ ,
: 10 or alkoxyalkyl group such as methyl, ethyl, phenyl, benzyl,
.. methoxyethyl, ethoxyethyl or the like.
In an alternative embodiment, the vinyl polymer may
; be incompletely quaternized by reacting less than a stoichio-
metric amount of tertiary amine with the polymer. The pre-
i ferred mole percent quaternizatiGn (in the case of incompl.ete
quaternization) is from 80 to 97.5 percent. The excess halo-
alkyl groups in the polymer backbone are then further reacted
with a compound having more than one amine group such as poly-
amine. Examples of polyamines useful herein are gelatin,
1,4-butanediamine, i~idazole, pyrazine, and the like. The
amount of polyamine crossl.inking agent added may vary from
0 to 20~ by weigh~ of the polymer.
--6--
- 1057'~94
If the polyamine is also used as a binder material gre~ter than
20% by weight can be added. The process used to
obtain crosslinking with such polyamines may be carried out
in a solvent, such as water,, acetone, benzene, dimethyl-
forrnarnide, dimethylsulfoxide, dimethylacetamide, alcohols
such as methanol, ethanol, isopropanol, 2-ethoxyethanol, and
the like. Temperatures from 20 to 80~C are generally used.
Some polymers which illustrate the mordants of this
~: invention contain the following units wherein x is from 0 to
lO 66 2/3~ and y is lO0-x
H2-CH)X (CH~CH
. ,
,., I C~2
_ 'C6H13 - ~- C6~I13
C6El3 Cl~
;~ name = poly(styrene-co-N,N,N-trihexyl-N-vinylbenzyla~noni~n
....
chloride).
. . .
t CH2 - CH
,. CH2
C6H13- 1~- C6~I13
C6~1l3 Cl~
name = poly(N,N,N-trihexyl-N-vinylbenzyla11~onium chloride).
~CH2-C~I-) X ( CH2-.,C~
-,, CH2
C~Hg- ~-Cl~Hg
C41Ig Cl
name = poly(styrene-co-N,N,N-tributyl-N-vinylbenzylar1~lo
chloride).
t
1057994
,, .
, (CHz--CH)
\
CH
... , ~ 2
: C H - N9~ - C H ..
5 1 1 1 5 1 1 : -
C H C I
name = poly(N,N,N-tripentyl-N-vinylbenzylammonium chloride)
and the like.
,,
, Any of the methods known in the art to homopoly-
merizç the monomers or to copolymerize with other ethylenically
;;: . .
unsaturated monomers, such as mass, solution, or bead poly-
merization can be used to prepare the polymers of this
,, .
invention, and polymerization catalysts known to the art,
such as ultraviolet light treatment, peroxides, azo compounds
[i.e., 2,2'-azobis(2-methylpropionitrile)], and the like can
be employed.
The novel polymeric mordants o~ this invention can
be employed alone or together with organic binders in the
preparation of dye imbibition printing blanks, receiving
layers for color transfer processes, such as those described
in Land U.S. Patent 3,362,819 issued January 9, 1968.
Rogers U.S. Patent 2,983,606 issued May 9, 1961, Whitmore
U.S. Patent 3,227,552 issued January 4, 1966 and Whitmore et
al U.S. Patent 3,227,550 issued January 4, 1966, and in anti- -
halation layers such as those described in Jones et al U.S. Patent
3,282,699 issued November 1, 1966. Satisfactory binders used for
'chis purpose include any o~ the hydrophobic binders generally
employed in the photographic field, including, ~or example
poly(vinyl acetate), cellulose acetate butyrate, gelatin,
poly(vinyl alcohol) and the like. Exemplary materials are dis-
closed in Product Licensing Index, Volume 92, December, 1971,
-8-
"
.,
- lOS79 9 4
publication 9232, page 108. The amount of dye mordant to be
used depends on the amount of dye to be mordanted, the
mordanting polymers, the imaging chemistry involved, etc.
' and can be determined easily by one skilled in this art. It
is preferred that between 20 and 83% by weight of polymer be
used in the dye mordanting layers~
The dye image-receiving element can comprise a
support having thereon a layer including the polymeric
mordants of this invention. The element may also comprise
other layers, such as a polymeric acid layer, and can also
include a timing layer as taught in Land U.S. Patent 3,362,819
issued January 9, lg68 or a light reflective interlayer
comprising a light reflective white pigment, such as TiO2,
and a polymeric binder, in accordance with the teaching of
- Beavers et al U.S. Patent 3,445,228 issued May 20, 1969.
The mordanting compositions of this invention are
also especially useful in light-filtering layers, such as in
- antihalation layers of the type disclosed in Jones et al U.S.
~ Patent 3,282,699 issued November 1, Ig66. Here the light-
- 20 filtering layer preferably can comprise a binder and the
mordanting compositions of this invention. The layer is
adapted to contain a dye held or fixed by the mordanting
composition.
In addition, the novel mordants of this invention
can also be employed in integral negative-receiver photo-
graphic elements such as those described in Belgian Patent
Nos. 757,959 and 757,965 both assigned to Eastman Kodak
Company and both dated April 23, 1971 and Land U.S. Patent
: 3,415,644 issued December 10, 1968. In general, these
.,
, _g_
- ~0579~4
- integral photographic elements comprise a support having
thereon a layer containing one or more of the novel mordants
described herein and at least one photosensitive silver halide
emulsion layer, the silver halide Ob~ which has contiguous
thereto a dye image-providing materlal.
The mordants can also be ~sed for fixing the dyes,
and particularly acid dyes, used in the preparation of photo-
graphic filter, antihalation and gelatinous silver halide
emulsion layers. Such layers can be coated on conventional
-~ 10 photographic supports, such as flexible sheet!supports (e.g.,
cellulose acetate, polyester films, polyvinyl resins, etc) or
paper, glass, etc.
- More than one of the polymeric mordants of this
invention can be used together, in a single layer or in two
` - or more layers. The polymeric mordants of this invention
-can also be used in admixture with other mordants in the
same layer or in separate layers of the same element.
~ hether the polymeric mordants are employed in a
single layer or in two layers, it is preferred that the total
; 20 coverage of the mordant be from 5 to 55 mg/dm2.
.
;.
;~ ' The polymeric mordants of this invention are useful
for receiving a variety of acid dyes from, for example, a
hydrophilic colloid relief image according to prior art
techniques.
This invention is further illustrated by the following
examples.
: Example 1
A reactor was charged with 15 grams of poly(styrene-
co-vinylbenzyl chloride) in a 1:1 mole ratio of styrene to vinyl-
'
--10--
~ lOS7994
benzyl chloride wherein 60~ of the vinylbenzyl chloride is
.~ the meta isomer and 40% is the para isomer in 150 ml. benzyl
alcohol and 16 g. of tris (n-pentyl)amine. The mixture was
heated on a steam pot for about 16 hours, cooled, and poured
into diethyl ether to precipitate the pro~uct. The solid was
collected, washed with ether, and vacuum dried to produce 18.5 g. ;~
of poly(styrene-co-N,N,N-tripentyl-N-vinylbenzylammonium
chloride).
Example 2
.: l
A mixture of 40 g. of methyl methacrylate, 61 g. of
vinylbenzyl chloride, 500 mg. of potassium persulfate, 200 mg.
o~ sodiurn bisulfite, 4 ml. of the sodium salt of an alkyl-
`~ aryl poly(ether sulfate) comrnercially available under the
trademark Triton 770 from Rohm and Haas Company and 200 ml.
- of water was heated at 60C for 3 hours in a nitrogen atmos-
phere. The mixture was then held at -20C overnight ~nd r
allowed to come to room temperature. The solid was filtered
and washed with water and methanol. The white powder was
dried under vacuum at room temperature. The resulting
polyrner had an inherent viscosity in acetone of 0.87.
A reactor was charged with a rnixture of 12.5 g.
of poly(methyl methacrylate-co-vinylbenzyl chloride) prepared
above, 21 g. o~ trihexylamine and 200 ml. of ethoxyethanol and
heated at 80 to 90C for 3 days in a nitrogen atmosphere. The
pol~ner was precipitated from the resulting viscous solution
in hexane, filtered, washed and dried in a vacuurn oven at 40C.
The polymer was dissolved in methanol, and precipitated in
a mixture c~ hexane-ether (1:1 by volume). The resulting
copoly(methyl methacrylate-co-N,N,N-tri-n-hexyl-~-vinylbenzyl- ~ ¦
~0 arf:monium chloride) had an inherent viscosity in methanol of
8.~5 at 25C ar.d at a concentration o~ 0.25 g/dl.
~ L~ _ ,
!
.
- , : .
; - lOS7g94
Example 3
The process of Example 2 was carried out with the
substitution of tri-n-butylamine for tri-n-hexylamine. Poly-
~nethyl methacrylate-co-N,N,N-tri-n-butyl-N-vinylbenzylammonium
chloride) resulted.
Example 4
The process Or Example 2 was repeated with the sub-
stitution of triisopentylamine for tri-n-hexylamine. Poly-
~ethyl methacrylate-co-N,N,N-triisopentylarnine-N-vinylbenzyl-
ammoniuri chloride) resulted.
Examples 5 to 10
,:' 1.
Compounds 5 through 10 designated in Table I were
prepared using the procedure described in Example 1 using the
so}vent indicated and with the substitution of the appropriate
- trialkylamine. The resulting polymers have substituted on
~ .
~ the nitrogen atom the alkyl substituents designated in Tab]e I
-- as R3, X~ and R5, all corresponding to the groups shown pre-
viously in Forrnula I. The elemental analyses for the carbon, f
hydrogen, nitrogen and chlorine of these compounds are shown
; 20 in Table I with the calculated values shown above the actual
-~ experimental values found. The inherent viscosities of these
~ compounds are also sho~n.
.,
: ~ ff
., I
., ~
ff
t
~r t
-12-
"
... . ..
~ 105799~
:.,
. a~ o~D CO CO 1~ r~ ~D
S V~1 0 0 r-l _I O
,
--~1 OD er ~ O ~ ~
U - .. .. .. .. ..
~1
g ~ z I ~ ~ a~ ~ ~ o L~
. ~ ~ ~) N ~~`1 ~t~ ~ ~`I '~
~'. U
o o ~ 1--~ ~~n ~ 1~ ~ 1~ ~t
~:1o o o 1~o oo .~ o o
.- ~co ~ r ~~ ~ ~ o
.. .. .. .. .. ..
~ So
H ~1I --I ~O O_I ~ I I I ~ ~a
a~ o ~ o.c ~:~ o ~ o
~N ~ N ~ dN .C N ~: ~ ~ a)
a)~ o s~ O ~ O s: O I ~ ~ N
a) o ~ ual u z; ~
o~m ~ m ~ m ~ m _l ~ au ~ a~
U~ ~ Z
;
..
.. ~
m
U U y y y y
..,
,`, ,~1 y y iU y y y
':
~1 ~ In 1`
Y Y Y Y Y Y
,,.'
~ Z
In ~ o
~ o
.,' U
"
. --13--
~ - 10579~4
- '` .
The inherent viscosities were measured in benzene
at 25C at a concentration of 0.25 g/dl. of solution.
Exam~les 11 to 25 ~
This is a comparative exarnple.
- The polymers of the present invention were tested
for mordanting properties in relationship to a, control which
- i~ a dye mordant somewhat similar to those described herein,
~poly(styrene-co-N-benzyl-N,N-dimethyl-N-(3 maleimidopropyl)-
, ammonium chloridej but not within this invention. This is the
10 mordant of Example XIV of U. S. Patent 3,709,6,90.
Competition tests were run to determine competitive
constant K (defined below); These tests were run by forming
" a structure as shown below in which a yellow dye and a magenta
dye were dissolved in fluid containing 40 g/l of hydroxy ethyl
cellulose in one molar KOH at a pH of 14 and sandwiched between
'' a mordant layer containing the control mordant and a layer con-
taining a test mordant as follows:
- 1 View
Tést hordar~
TiO2 ~~
.. . ..
Fluid and Dye
,. TiO2
' Star2dard Mordant ' .
t ~TieTr
: ' The re~lection densitometry at timed inter-~Jals on
both faces of the sandwich ~h~as used to 2nonitor the appeararce
of dye in each mordant layer. Dens:ity readings were taken at
24 hours to detern2ine to which mordant the dye di.ffused to a
greater degree. The ~alue K is ~etermilled by dividing t!le test
mordant reflection density hy the st~rdard ~.ordant re-f'lectlor
-14-
' :
1057994
- density. This provides a ratio of mordanting ability of the
tested mordant versus the standard or control mordant.
The following Table 2 indicates the various competi-
tion values for homopolymers and copolymers containing the
repeating unit:
: .
:' V. --CH2-CH-
.. ~ CH2
R5 _ ~ - R3
R4 Clq
. . .
for both the magenta dye ~Ym) and yellow dye (Ky)~ In
Controls A-E and Examples 11-20 and 22, the mordants are
~; copolymers with styrene as the comonomer. Example 21 and
,; 10 Control F are homopolymers. Examples 23-25 are copolymers,
. ~ ...
with the comonomer having the following structure:
~ , .
CH3
` VI. -CH2-C-
,.~; ' '' C=O
.. ~ O
~ CH3
''"'
.'~ . ' -':
;' :'
-
:'~
;;~
.. ~
.
: 10579C~4
,.. ~
o ~
O O SI h S~ h
,'' ~ U ~ ~ ~ ~ ~ ~1 ~ ~ ~ ~ ~ ~ ~ ~ ~ O O
,,' U O O ''
I ooooooooooo~ooOO
, .
.~ ~ O ~ ~ U~ ~
i~ ~ _ r-l ~) N ~ ~ D 1~ ~ ~r er ~1
O a~ CO _I ~D ~ Ll~ O ~1 ~ ~1 ~D ~D ~ t~ ~D OD
H ~; ~ D el~ ~1 r-l 1~ 1~1 el~ In ~r In O
H --I ~1 ~ ~ ~ ~ ~1 ~.1
.' ~ ,,
,,,. ~
-, ~ m ~1 ~ ~ ~ N ~1 -
m ~ m m _
m m m m m m ~ m m ~ ~ m m
; [~3U U U U U U U~l UU) uL~ ~D ~1 ~ D ~
~ '
m ma' m'' m~ m-' m~ ~ m~ m'' m~ ~ ~ m~ m
m m ~ ~ ~ D CO t~ m 10 n ~D m m ~D ~r
,, ,
m~ m ma` m-' m-' m~ mU' ~ m m~ m~ ~ ~ m~ m
m m ~ ~ ~ D CO t~l m ~ ~ ~D m m ~D ~r
. .
D i~ 00 a~ O _I
~ ~: m O ~ ~ ~ ~ ~ ~ ~ 1 ~ N ~
O O O O O ~'1 1~1 r~l r-l r-l r~l r~l _1 1~l r~l ~1 0
X ~ (15 0 (~
O c~ c) O X X ~ XX X ~ X X cO~
4 -16-
1057994
,:'
~, ~
.- ~
--1 0 H H H
lJ
--I O, ~ ~ ~1
,.......... ~n ~ a
O O
.- ~ U ~
. ~ i ~ O O O
c~ dP Ul 1~
's ~ OP ~P dP o`~
.,, ,~ r` o o o
~ ' ~ Ln 1~1 11~
,.,
, .
:
:- _ ~ a~ r~ r` In
- ~ E3
aJ ~ ~1
~1
';' ,1
,~ .
O ,_ U~
. ' O
,, _ _ ~ r~l cO
. . H
a3 " '
~ 11~
~: ~c m o
; ~
m
o
~ O O ~
tc
., ~ In
o
er ~D ~ Ul
C~ C~ U rl
', a
a) a.) a~
~1 ~ ~ _I
X
X x x x
-1 6a-
.
357'~9~
It is noted that Examples 11 to 25 are all water-
insoluble polymers and controls A to F are water-soluble.
It is thus seen that surprisingly superior mordanting proper-
ties are obtained using water-insoluble polymers wherein R3,
R4 and R5 contain a total of at lea;,t 12 carbon atoms. This
example shows that it is not sufficient for the mordant to
have a total of at least 12 carbon atoms in R3, R4 and R5,
but the mordant must also be water-insoluble. The insolubility
being brought about by (a) the size of R3, R4 and/or R5 or
(b) the amount of hydrophobic comonorner or a!combination of
(a) and (b).
Example 26
.~ ,
A reactor was charged with 50 grarns of poly(styrene-
c~-vinylbenzyl chloride), 0.16 mole of tri-n-hexy]amine and
- gbo ml. of 2-methoxyethanol and the mixture was stirred for
24 hours at 95C. The solution was cooled and 15 ml. of con-
centrated HCl were added. The mixture was poured into water,
with stirring, to precipitate the polymer and the polyrner was
- washed with water and dried in vacuum to produce 80 g. of the
polymer poly(styrene-co-N,N,N-tri-n-hexyl-N-vinylbenzylammonium
chloride) which was 80~ quaternized.
,:
The invention has been described in considerable
. detail with reference to pre~erred ernbodiments thereof, but
;- it willbe understood that variations and modifications can
be effected within the spirit and scope of the invention.
"'-
..
