Note: Descriptions are shown in the official language in which they were submitted.
~ CA 02207283 1997-06-06
W O96/18496 PCTrUS95tl6371
AQUEOUS INR R~ lV~i INR JET REC~ vlrlG MEDIUM
~ YIELDING A WATER RESISTANT INR JET PRINT
~ Field of the Invention
The present invention relates to an ink jet
receiving medium. In particular, the present invention
relates to an ink jet receiving medium which yields a
water resistant ink jet print and a process for
providing such a water resistant ink jet print.
Description of Related Art
Printers using sprayable inks, such as ink jet
printers, have become more popular in recent years due
to a number of desirable features. Specifically; these
systems operate quietly at high speed without the need
for external developing or fixation procedures.
Moreover, through the use of multiple ink jet heads
various colors may be obtained which are suitable for a
variety of applications. These printers typically
employ ink jet heads having small orifices that propel
ink droplets and are used in various electronic printing
applications. Various methods for ejecting droplets of
ink have been developed. These methods include the use
of an electrostatic attraction system, the use of a
piezoelectric element to impart mechanical vibration or
displacement to the ink, and pressurizing the ink by
heating. Thus, it is no wonder that such a recording
method which generates less noise and is capable of
performing high-speed printing and multi-color printing
is in great demand.
Ink jet systems are typically comprised of three
components: the printer, the ink and the receptor. The
printer controls the size, number and placement of the
CA 02207283 1997-06-06
W O96/18496 PCT~US95/16371
ink droplets and contains the transport system. The ink
provides the colorants which form the image, and the
receptor provides the medium which accepts and holds the
ink. The quality and stability of the resultant ink jet
print is a function of the system as a whole. However,
the composition and interaction of the ink and the
receptor material most affect the quality and stability
of the imaged product.
More specifically, it is desired that the ink be
absorbed as rapidly as possible, and that the spread of
ink droplets be adequate. The resultant image should be
excellent in storability, durability and water
resistance.
Ink compositions which are useful in ink jet
recording systems are well known and generally contain
water, organic solvents and dyes. European Patent
0,294,155 discloses an ink jet composition useful in ink
jet recording consisting of a water based vehicle
containing about 30-99% wt. water with the balance made
up of high boiling solvents such as glycol, glycol
ethers, pyrrolidones and amides. The inks contain
preferably acid or direct dyes. Optionally, a
polyhydric alcohol is added for the prevention of the
clogging of nozzles and improvement of ejection
stability.
Typically, ink jet systems fall broadly into two
categories; those that employ high organic solvent-water
based inks, and those that are essentially aqueous.
Aqueous inks normally contain up to 10% of a high
boiling solvent such as diethylene glycol, whereas high
organic solvent inks contain, in addition to water,
about 50% of a high boiling organic solvent such as
diethylene glycol. The resultant ink jet print using
either of these types of ink has poor water resistance
(i.e., the dye image leaches out or the image layer
CA 02207283 1997-06-06
W O96/lX496 PCT~US9~/16371
containing the dye dissolves when contacted with water).
Additionally, the dye image is prone to smudging.
Ink jet film compositions are normally sensitive to
water and the print can dissolve and leach out. Also,
under humid conditions, the print can bleed thereby
losing definition. This deterioration is accentuated
when the inks employ high boiling solvents, such as
glycols. Conventional ink jet prints often lack light
resistance and good file aging properties as well. A
solution to all the above shortcomings is required to
achieve acceptable print stability.
Polymeric films for use as recording media
represent a special problem in ink jet recording because
their surfaces are hydrophobic or quasi-hydrophobic.
Even when their surfaces are treated with special
coatings to accept and absorb the inks, it is difficult
to obtain the requisite qualities of image density and
resolution without incurring tack, smear, image bleed,
water solubilization of the ink receptive matrix, or
other undesirable properties.
The use of water/glycol ink systems presents a
special problem. At high humidities, a phenomenon
described as image bleed, occurs. The ink jet printer
applies small ink droplets in a selective pattern to
form the images. These droplets are absorbed into the
coating on the film surface to form dots. After initial
absorption, the dye continues to spread laterally. Some
post imaging spread is desirable to fill in the white
areas between the dots and obtain good image density.
At high humidities, however, this spreading continues
and causes the image to spread excessively, that is, to
bleed thereby losing image sharpness or resolution. Ink
vehicles which do not contain high boiling solvents such
as glycol do not exhibit this level of image bleed.
CA 02207283 l997-06-06
W O96/18496 PCTAUS95/16371
Various attempts have been made to solve these
problems in an effort to provide the optimal receptor.
Approaches to the problem of hydrophobic surfaces
include the use of polymers alone or in admixture as ink
receptive coatings; see for example, U.S. Patent Nos.
4,503,111; 3,889,270; 4,564,560; 4,555,437 and
4,578,285. Multiple coatings have also been employed in
trying to overcome the various problems associated with
the hydrophobic nature of recording media; illustrative
lo of these coatings are those described in U.S. Patent No.
4,379,804, Japanese Patent Number 01041589 and Japanese
Disclosure Numbers 86-132377; 86-074879 and 86-41549.
Additionally, the use of mordants to help fix the dye
and minimize bleed has been the subject of a number of
15 patents, including U.S. Patent Nos. 4,554,181; 4,578,285
and 4,547,405-
Moreover, there is a strong demand for a recording
medium having light transmissivity and a recording
medium having gloss on the surface. In these cases it
is essential that the surface of the recording medium be
non-porous. In this regard, in order to enhance ink
affinity and ink receptivity, it has been the practice
in the prior art to use a recording medium comprising a
non-porous ink-receiving layer formed by use of a water-
2 5 soluble polymer.
For example, U.S. Patent No. 4,503,111 assigned toTektronics discloses a recording medium having a non-
porous ink-receiving layer formed by using primarily a
polyvinylpyrrolidone. However, such a recording medium
has various problems. These problems include a recorded
image low in light fastness, or that due to the
stickiness of the surface of the inked receiving layer,
blocking is liable to occur when the printed media are
placed upon one another, or when paper is superposed on
the recorded surface.
-
CA 02207283 1997-06-06
W O 96/18496 PCT~US95/16371
U.S. Patent No. 5,206,071 to Atherton et al.
relates to film mediums useful in ink jet printing which
films comprise a transparent, translucent or opaque
substrate, having on at least one side thereof a water-
insoluble, water-absorptive and ink-receptive matrix
comprised of a hydrogel complex and a polymeric high
molecular weight quaternary ammonium salt.
U.S. Patent No. 4,877,680 to Sakaki et al. relates
to a recording medium comprising a substrate and a non-
porous ink receiving layer. The ink receiving layercontains a water-insoluble polymer containing a cationic
resin. The recording medium may be employed for
recording by attaching droplets of a recording liquid
thereon.
U.S. Patent No. 4,576,867 to Miyamoto relates to an
ink jet recording paper wherein by attaching a cationic
resin having a structure represented by the following
general formula (I) to at least the surface of an ink
jet recording paper, the water-resistance and the
sunlight fastness of the image formed on the ink jet
recording paper can be improved:
Cl~CH2--CH--O~nH (I)
(CH2)m
R~-Nffl-R3Y~
R2
wherein R~, R2 and R3 represent alkyl group; m represents
a number from 1 to 7; n represents a number from 2 to
20; and Y represents an acid residue.
European patent publication 0,500,021 A1 relates to
a recording method and recording film comprising a
transparent substrate, a porous alumina hydrate layer
-
CA 02207283 1997-06-06
W O96/18496 PCTrUS95/16371
formed on the substrate and an opaque porous layer
laminated on the alumina hydrate layer.
One of the major drawbacks of an ink jet print has
always been the lack of long term durability of the r
5 images. Ink jet prints have always been prone to W
light fade, and moisture sensitivity. Since the
majority of the ink jet inks currently used in desktop
and graphic arts applications are composed mainly of
water, the ink jet receiver coatings need to be water
10 receptive. The challenge is to develop a hydrophilic,
aqueous ink receptive coating that yields a water
resistant ink jet print.
Accordingly, an object of the present invention is
to provide a novel recording medium for ink jet
15 recording which is particularly excellent in ink
receptivity, sharpness and water resistance.
Another object of the present invention is to
provide a recording medium for ink jet recording which
is excellent in water resistance, even under highly
20 humid conditions, and also free from migration or
leaching of the print ink when water droplets contact
the surface of the recorded image, or when left to stand
under highly humid conditions.
Still another object of the present invention is to
25 provide a water resistant ink jet print and method
thereof.
These and other objects of the present invention
will become apparent upon a review of the specification
and the claims appended thereto.
SUMMARY OF THE lNv~.. ~loN
According to one aspect of the present invention,
there is provided a receiving medium comprising a
substrate and an ink receiving layer provided thereon,
CA 02207283 l997-06-06
W O96/18496 PCTAUS95/16371
said ink receiving layer comprising a random copolymer
of a vinyl amide and acrylic acid or methacrylic acid or
their esters, a cationic resin and a crosslinking agent.
Preferably, the random copolymer is a copolymer of
vinylpyrrolidone and acrylic acid or acrylamide and
acrylic acid. Upon drying the ink receiving layer
subsequent to coating onto the substrate, the random
copolymer is preferably crosslinked.
According to another aspect of the present
invention, there is provided a recording medium
comprising a substrate and an ink receiving layer
provided thereon, said ink receiving layer comprising a
75% vinyl pyrrolidone/ 25% acrylic acid random
copolymer, 10% by weigh~ of a cationic resin and 3 to 4
by weight of a crosslinking agent based on the
copolymer. In another aspect, there is provided such a
recording medium where the copolymer is an
acrylamide/acrylic acid random copolymer.
According to a further aspect of the present
invention, there is provided a process for providing a
water resistant ink jet print by attaching droplets of a
recording liquid on a recording medium, said recording
liquid containing a water-soluble dye, water and an
organic solvent, said recording medium comprising an ink
receiving layer provided on a substrate, with the ink
receiving layer comprising a crosslinked vinyl amide
acrylic acid or methacrylic acid or ester thereof random
copolymer and, a cationic resin.
DETAILED DESCRIPTION OF PREFERRED EMBODIMENTS
The present invention relates to an ink jet
recording medium. The ink jet recording medium of the
present invention comprises a receiving layer which is
water resistant and includes a vinyl amide/acrylic acid
or methacrylic acid or esters thereof random copolymer,
-
CA 02207283 1997-06-06
W O96/18496 PCTIUS9~/16371
a cationic resin and a crosslinking agent. The ink
receiving layer is generally coated on a suitable
substrate and dried to effect crosslinking of the
copolymer. r
Applicants have found experimentally that suitable
vinyl amide/acrylic acid or methacrylic acid or esters
thereof random copolymers, when properly crosslinked,
form the backbone of a water resistant ink jet coating.
This coating can be applied to, but is not limited to,
the following substrates: a clear film, a polyethylene
clad paper (photobase), adhesive backed vinyl, paper and
canvas.
The vinyl amide monomer used in preparing the
random copolymer can be derived from either an N-vinyl
amide or a vinyl amide such as acrylamide. The most
preferred N-vinyl amide is vinyl pyrrolidone.
Acrylamide is another preferred monomer for use in
preparing the random copolymer used in the present
invention.
The monomer copolymerized with the v-inyl amide is
an acrylic acid or methacrylic acid, or an ester of
acrylic acid or methacrylic acid. Among the more
preferred acrylates and methacrylates are the
methylacrylate, ethylacrylate and methylmethacrylate
esters. It is most preferred, however, that acrylic
acid be copolymerized with either vinyl pyrrolidone or
acrylamide for purposes of the present invention, as
these two copolymers have been found to be most easily
available and most useful.
International Specialty Products of Wayne, New
Jersey manufactures a line of suitable vinyl
pyrrolidone/acrylic acid random copolymer products under
the trade name Acrylidones. The following table
summarizes various characteristics of commercially
CA 02207283 1997-06-06
W O 96/18496 PCTrUS95/16371
available vinyl pyrrolidone/acrylic acid random
copolymers.
TABLE 1
VP/AA RATIO MOLECULAR ACID NUMBER
WEIGHT
ACP-1001 75:25 250,000 170-210
ACP-1004 50:50 250,000 365-405
ACP-1005 25:75 250,000 560-600
ACP-1033 75:25 80,000 170-210
ACP-1041 50:50 80,000 365-405
ACP-1042 25:75 80,000 560-600
A preferred resin for overall imaging properties
contains 75% vinyl pyrrolidone (for example, see ACP-
1001 and ACP-1033 above). As the % vinyl pyrrolidone
decreases, it has been found that the ink receptivity
decreases, generally resulting in poor print quality and
long ink dry times. More specifically, it has been
found that grades containing 75% vinyl pyrrolidone work
the best for print quality and ink dry time, while
grades containing 50% vinyl pyrrolidone and 50% acrylic
acid are marginal, and grades containing 25% vinyl
pyrrolidone and 75% acrylic acid do not receive ink at
all.
The preferred acrylamide/acrylic acid copolymers
are also commercially available. Suitable copolymers
can be obtained, for example, from Cytec Industries Inc.
-25 of West Patterson, N.J. under the trademark CYANAMER.
Conventional crosslinking agents are suitable for
~use in the present invention. However, the aziridine
class of polyfunctional crosslinkers is most preferred
for the purposes of the present invention. Suitable
CA 02207283 1997-06-06
W O96/18496 PCTrUS95/16371
aziridine crosslinkers are commercially available, for
example, such as crosslinkers CX-100 available from
Zeneca Resins of Wilmington, Mass.; XAMA-7 and XAMA-2,
both available from Cordova Chemical Co. of North
Muskegeon, Michigan. Such polyfunctional crosslinkers
generally have a functionality greater than 2, and more
preferably in the range of from 2.5 to 3.5.
In general, the amount of crosslinking agent
present is an amount sufficient to crosslink the
copolymer so as to achieve a water resistance that
allows the print to be immersed in water while still
maintaining the integrity of the coating, and hence the
print. It was determined empirically that from about 3
to about 13% of an aziridine crosslinker, based on the
weight of random copolymer, is a preferable amount in
terms of print quality and water resistance. More
preferably is an amount of from 3 to 5 wt. %, and most
preferably from 3 to about 4 wt. %. If too little
crosslinker is used, the coatings can be very tacky and
not water resistant at all. If too much crosslinker is
used, the coating is generally not very receptive to the
aqueous inks, and the resulting prints are poor, with
much ink pooling and long ink dry times.
Other conventional crosslinkers such as zirconium
carbonates can also be used with good results.
The crosslinking of the random copolymer is
preferably accomplished during the drying step, for
purposes of convenience. It may also be accomplished in
a separate step, if preferred.
Although the crosslinked copolymers work well as a
good water resistant backbone for the coating, they are
preferably used in combination with a cationic
substance. When prints on a coating containing only the
crosslinked resin are immersed in water, the coatings
themselves are water resistant, but the ink begins to
-- 10 --
CA 02207283 1997-06-06
W O96/18496 PCTrUS9S/16371
bleed and leach out of the coating matrix. Since ink
~ jet dyes typically are anionic in nature, a cationic
substance is required to "lock" the dyes in the coating
matrix.
Conventional cationic resins are suitable for use
in the coating of the present invention. Quaternary
ammonium compounds are preferable, of these, the higher
molecular weight compounds are most preferable and
provide the best overall print quality and water
resistance properties. CPS Chemical Company of Old
Bridge, New Jersey manufactures several lines of
cationic polymers by the trade name of Agefloc, which
are suitable for use in the present invention. Of
these, a high molecular weight poly (hydroxyalkene
dimethyl ammonium chloride) called Agefloc A-50HV is
most preferable with respect to the overall results for
print quality and water resistance. Other high
molecular weight cationic resins include the Agefloc A-
50 and A-40HV.
The amount of cationic material used is generally
an amount sufficient to preclude bleeding of the ink
when the print is immersed in water, i.e., an ink
migration precluding amount. It was empirically
determined that preferred print quality and water
resistance results are obtained with the use of a
formulation containing about 5 to about 10~ of the
quaternary ammonium resin, as based on the ~ solids
(wt.) of the random copolymer resin. If too little of
the quaternary resin is used, the print quality is poor,
and the dye runs when immersed in water. If too much of
the quaternary resin is used, the initial print quality
is poor, and the coatings are tacky.
The receiving layer of the present invention can be
coated onto a substrate using any conventional coating
process. The coating must generally be dried
-- 11 --
-
CA 02207283 1997-06-06
W O96/18496 PCTrUS9~/16371
sufficiently to assure proper crosslinking. For
example, it is generally preferred that the coatings be
dried at a minimum of 260~F for about 2 minutes to
ensure that the crosslinking cures properly.
The present invention also includes a process for
providing a water resistant ink jet print. The process
includes coating a suitable substrate with a vinyl amide
acrylic acid or methacrylic acid or ester thereof random
copolymer, a cationic resin and a crosslinking agent;
curing the coating; and applying droplets of a recording
liquid on the coating.
The invention will be illustrated in greater detail
by the following specific examples. It is understood
that these examples are given by way of illustration and
are not meant to limit the disclosure or the claims that
follow. All percentages in the examples, and elsewhere
in the specification, are by weight unless otherwise
specified.
EXAMPLE 1
Syloid 620- -------0.06g
Deionized water1.80g
10% Acrylidone ACP-100187.70g
28~ Ammonium hydroxide3.75g
Xama 7 0.33g
2-Pyrrolidone-- ---1.09g
50~ Agefloc A-50HV----- 1.75g
The above mix was prepared by mixing the Syloid 620
and water on a magnetic stirring plate for 1 minute.
The Acrylidone and ammonium hydroxide were added and the
mixture was stirred on the magnetic stirrer for an
additional minute. The final three ingredients (2-
pyrrolidone, Agefloc A-50HV, Xama 7) were added, and the
mixture was stirred for a final five minutes on a
magnetic stirring plate.
CA 02207283 1997-06-06
W O96/18496 PCT~US95116371
The composition was then coated onto 380 gauge
Melinex 534 with a gapped number 70 Mayer rod to achieve
a coating thickness of about 0.40 mils. The coating was
dried in a laboratory Blue M convection oven for 5
minutes at 260~ F. This drying step also resulted in
the crosslinking of the Acrylidone copolymer.
The sample was then printed on a Canon BJC600 ink
jet printer using a full color block test pattern.
Visual densities of cyan, magenta, yellow, black, red,
green and blue were run using an XRITE 938 color
densitometer. The print was allowed to air dry for 1
hour, then it was completely immersed in water for 10
minutes. The visual densities were repeated after the
immersion, and calculations were performed to get the %
retained density. The results are summarized in Table 2
below.
EXAMPLE 2
Syloid 620-------------------0.06g
Deionized water--------1.80g
10% Acrylidone ACP-1001----78.93g
28% Ammonium hydroxide-----3.75g
Xama 7 --- 0.33g
2-Pyrrolidone-- ---1.09g
50% Agefloc A-50HV -1.75g
10% Airvol 325 8.77g
The above mixture was prepared in the same manner
as described in Example 1. The Airvol 325 was added
after the Agefloc A-50HV and then the mixture was
stirred for the final five minutes. The coating,
printing, and water immersion were performed in the same
manner as in Example 1. The results are summarized in
Table 2 below.
d
- 13 -
CA 02207283 1997-06-06
W O 96/18496 PCTrUS95/16371
EXAMPLE 3
Mix B:
10% Gohsenal N-300-20.00g
10% PVP K90 -------5.00g
40% 2Onyl FSJ------------ -0.22g
Water------ ------37.00g
Example 3 uses two mixes. The first mix (Mix A)
was prepared with the same composition as that in
Example 1 and applied to the substrate in the same
manner as in Example 1. The second mix (Mix B) was
prepared in the following manner:
The Gohsenal N-300 and PVP K90 solutions were
blended and mixed for 30 seconds on a magnetic stir
plate. The Zonyl FSJ and water were added, and stirred
for 5 minutes on a magnetic stir plate.
Mix B was then applied as a topcoat onto the
coating of that previously prepared according to Example
1 with a wire wound number 10 Mayer rod. The sample was
then dried at 240~ F in a Blue M convection oven for 2
minutes.
The sample was then printed, tested, and evaluated
in the same manner as in Example 1. The results are
summarized in Table 2 below.
COMPARATIVE EXAMPLE 1
Syloid 620 -----0.06g
Deionized water 1.80g
10% Acrylidone ACP-1001 -87.70g
28% Ammonium hydroxide-----------3.75g
2-Pyrrolidonc 1.09g
3050% Agefloc A-50HV 1.75g
..
The above mixture was prepared in the same manner
as described in Example 1. The coating, printing, and
water immersion were performed in the same manner as in
Example 1. The results are summarized in Table 2 below.
- 14 -
CA 02207283 1997-06-06
W O96118496 PCTrUS95/16371
COMPA~UaTIVE Ea~iMPLE 2
Syloid 620------------- 0.06g
Deionized water --------1.80g
10~ Acrylidone ACP-1001 87.70g
28~ Ammonium hydroxide-----------3.75g
Xama 7-- -------- 0.33g
2-Pyrrolidone ---------1.09g
The above mixture was prepared in the same manner
as described in Example 1. The coating, printing, and
water immersion were performed in the same manner as in
Example 1. The results are summarized in Table 2 below.
Reagents for the above Examples are commercially
available according to the following description:
1) Amorphous silica is available from W.R. Grace,
Baltimore, MD as Syloid 620.
2) Vinylpyrrolidone/acrylic acid copolymer is
available from International Specialty Polymers of
Wayne, NJ as Acrylidone ACP-1001.
3) Aziridine crosslinker is available from Cordova
Chemical of North Muskegeon, MI as Xama 7.
4) Poly (Hydroxyalkene Ammonium Chloride) is
available from C.P.S. Chemicals of Old Bridge, NJ
as Agefloc A-50HV.
5) Fully hydrolyzed polyvinyl alcohol is available
from Air Products of Allentown, PA as Airvol 325.
6) Prebonded white polyester is available from ICI
Films of Hopewell, VA as Melinex 534.
7) Fully hydrolyzed polyvinyl alcohol is available
from Nippon Gohsei Ltd. of Japan as Gohsenal N-300.
- - -
CA 02207283 1997-06-06
W O96/18496 PCTrUS95/16371
T ~ LE 2
PRINT PRINT AVE. % COLOR COMMENTS
QUALITY TACK DENSITY
RETENTION
EXAMPLE l Very Good Moderate 99.9% Vibrant
colors/Good
wet rub
resistance
EXAMPLE 2 Very Good Low 98.8% Vibrant
colors/Good
wet rub
resistance
EXAMPLE 3 Very Good Very Low 99.0~ Vibrant
Colors/
Gl05Sy
Finish/Very
low print tack
COMPARATIVE Good Very High O ~ Coating Washed
EXAMPLE l Off
COMPARATIVE Poor Moderate 107~ High High color
EXAMPLE 2 to High bleed causes bleed/High Ink
increased coalescence
retention
Examples 1 and 2 both had very good print quality
lo and excellent water resistance properties. When a small
amount of a fully hydrolyzed polyvinyl alcohol is added,
as in Example 2, the print tack is reduced
significantly. The print tack can be reduced even
further, and the colors can be made very glossy, by
adding a thin PVP/fully hydrolyzed polyvinyl alcohol
topcoat as seen in Example 3. In general, the addition
or use of small amounts of additional resins, such as
polyvinyl alcohol or an acrylic resin, can be employed
to improve print quality.
When no crosslinker is used, as in Comparative
Example 1, the resulting coating is very tacky, and is
easily dissolved in water. When the high MW quaternary
ammonium resin is eliminated from the mix, as in
Comparative Example 2, the print quality is poor
- 16 -
CA 02207283 1997-06-06
W O96/18496 PCTrUS95/16371
indicating a high amount of bleed and ink pooling.
Thus, to achieve an ink jet recording medium which
exhibits excellent water resistance and a freedom from
-~ migration or leaching, the combination of the random
copolymer together with the crosslinker and the cationic
resin is important.
EXAMPLE 4
Syloid 620 ~ 0.06g
Deionized water - 62.92g
lo Cyanamer P-21 ---------- 6.99g
28% Ammonium hydroxide ----- 2.93g
CX - -- ---- 0.29 g
2-Pyrrolidone --- 0.85g
50% Agefloc A-50HV - O.75g
50% Fluorad FC-135 -- 0.14g
20% Gafquat 755N 25.08g
The above mixture was prepared by mixing the Syloid
620 and water on a magnetic stirring plate for 1 minute.
The Cyanamer was slowly added, and stirred for 15
minutes. The ammonium hydroxide was added and the
mixture was stirred for a final fifteen minutes on a
magnetic stirring plate.
The composition was then coated onto 380 gauge
Melinex 534 with a gapped number 70 Mayer rod to achieve
a coating thickness of about 0.40 mils. The coating was
dried in a laboratory Blue M convection oven for 5
minutes at 260 F.
The samples were then printed on a Canon BJC600e
ink jet printer, and an Encad NovaJet ink jet printer
using a full color block test pattern. The print was
allowed to air dry for 1 hour, then it was completely
immersed in water for 10 minutes. The print quality,
evaluated as in Example 1, water immersion and wet rub
resistance were all very good.
CA 022072X3 1997-06-06
W O96/18496 PCTrUS95/16371
The reagents used in the foregoing Example are
commercially available and may be generally described as
follows:
Syloid 620 -- amorphous silica from W.R. Grace,
Baltimore, Md.
Cyanamer P-21 -- acrylamide/acrylic acid copolymer
from Cytec Industries Inc. of West Patterson, N.J.
CX-100 -- aziridine cross linker from Zeneca Resins
of Wilmington, Ma.
Agefloc A-50HV -- poly(Hydroxyalkene ammonium
chloride) from C.P.S. Chemicals of Old Bridge, N.J.
Fluorad FC-135 -- cationic fluorosurfactant from 3M
of St. Paul, Minnesota
Gafquat 755N -- quaternized copolymer of
vinylpyrrolidone and dimethylaminoethyl
methacrylate from International Specialty Products
of Wayne, N.J.
Melinex 534 -- prebonded white polyester from ICI
Films of Hopewell, Va.
While the invention has been described with
preferred embodiments, it is to be understood that
variations and modifications may be resorted to as will
be apparent to those skilled in the art. Such
variations and modifications are to be considered within
the purview and the scope of the claims appended
thereto.
- 18 -
