USOO8133556B2

(12) United States Patent (10) Patent No.: US 8,133,556 B2

Klemann (45) Date of Patent: Mar. 13, 2012
(54) DURABLE MULTILAYER INKJET RE28,533 E 8, 1975 Drawert et al.
RECORDING MEDIA TOPCOAT 3,931,087 A 1/1976 Baatz et al.
3,959,174 A 5/1976 Winyall et al.
(75) Inventor: Bruce M. Klemann, Shorewood, WI (Continued)
(US) FOREIGN PATENT DOCUMENTS
EP O704560 A1 4f1996
(73) Assignee: Brady Worldwide, Inc., Milwaukee, WI
(US) (Continued)
OTHER PUBLICATIONS
(*) Notice: Subject to any disclaimer, the term of this
patent is extended or adjusted under 35 W.R. Grace—Coatings Product Overview; http://web.archive.org/
U.S.C. 154(b) by 358 days. web/200705240531307 http://www.grace.com/Engineered Mate...;
Sep. 11, 2010.
(21) Appl. No.: 12/540,004 (Continued)
(22) Filed: Aug. 12, 2009 Primary Examiner — Betelhem Shewareged
(74) Attorney, Agent, or Firm — Whyte Hirschboeck Dudek
(65) Prior Publication Data SC
US 2011 FOO39043 A1 Feb. 17, 2011
(57) ABSTRACT
(51) Int. C. Two-layer receiver coatings particularly well adapted for use
B4LM 5/240 (2006.01) in inkjet printing comprise:
(52) U.S. Cl. ............... 428/32.21; 428/32.24; 428/32.25; A. A base layer comprising:
428/32.26; 428/32.34; 428/32.35: 428/32.37 1. First pigment particles having (a) a number average
(58) Field of Classification Search ............... 428/32.21, particle size of 3-25 microns (um), and (b) at least one
428/32.24, 32.25, 32.26, 32.34, 32.35, 32.37 of (i) an oil absorption value of at least 150 g oil/100
See application file for complete search history. particles, and (ii) a pore volume of at least about 1.2
cubic meters per gram (cm/g); and
2. Water-insoluble binder resin having a surface energy
(56) References Cited greater than 40 dyne per centimeter (dyn/cm);
U.S. PATENT DOCUMENTS
the first pigment particles and water-insoluble binder
resin present at a weight ratio of 0.75 to 2; and
2,252,554 A 8, 1941 Carothers B. An imaging layer comprising:
2,285,009 A 6, 1942 Brukaker 1. Second pigment particles having (a) a number average
2,320,088 A 5/1943 Leekley particle size of 0.01-4 (lum) aggregated to form an
2.388,035 A 10, 1945 Frosch
2,393,972 A 2f1946 Cairns inter-particle region of Submicron pores, and (b) a
2.450,940 A 10, 1948 Cowan et al. pore volume of 0.4 to 2.2 (cm/g); and
3,157,681 A 11, 1964 Fischer 2. Water-insoluble binder resin having a surface energy
3,256,304 A 6, 1966 Fischer greater than 40 (dyn/cm);
3.258,443 A 6, 1966 Cantor
3,380,844 A 4, 1968 Menikheim et al. the second pigment particles and water-insoluble binder
3,394,029 A 7, 1968 MacArthur resin present at a weight ratio of 0.75 to 2.
3,579,485 A 5/1971 Folzenlogen et al.
3,637,550 A 1/1972 Sprauer 16 Claims, 1 Drawing Sheet

10
BASE LAYER-HOLDS LIQUID
COMPONENTS OF INK

(OPTIONAL) PRIMER LAYER

... SUBSTRATE: ......

 US 8,133,556 B2
Page 2

U.S. PATENT DOCUMENTS 2004/O109959 A1 6, 2004 Xu et al.

2006, OO68133 A1 3, 2006 Khoultchaev et al.
4.012,560 3, 1977 Baatz et al. 2007/0211097 A1 9, 2007 Yamazaki et al.
4,014,645 3, 1977 Chancler et al. 2007/0235.119 A1* 10, 2007 McManus et al. .............. 156,60
4,070.421 1, 1978 Etter, Jr. 2008/0261021 A1* 10, 2008 Haenen et al. ............. 428,319.1
4,080405 3, 1978 Agouri et al.
4,097,677 6, 1978 Emmons et al. FOREIGN PATENT DOCUMENTS
4,314.933 2, 1982 Berner
4,571,267 2, 1986 Drawert et al. EP O940427 A1 9, 1999
4,619,956 10, 1986 Susi EP 14.00366 A2 3, 2004
4,780.340 10, 1988 Takahashi et al. GB 1055676 A 1, 1967
4,818,325 4, 1989 Hiraiwa et al. GB 1177199 A 1, 1970
5,154,760 10, 1992 Miller, Jr. JP O1-218882. A 9, 1989
5,599,649 2, 1997 Shinkai et al. JP 2002-144551 A 5, 2002
5,882,388 3, 1999 Adair et al.
10, 2000 Nishimura OTHER PUBLICATIONS
6,132,039
6,261,669 T/2001 Yang et al. B. Klemann, Correlations between Xenon Arc accelerated weather
6,391427 5, 2002 Shaw-Klein et al.
6,428, 157 8, 2002 Wen ing tests and Outdoor Weathering, IS&T NIP 19 International Con
6,460,960 10, 2002 Mitsuhashi ference on Digital Printing Technologies, 296, 2003.
6,460.980 10, 2002 Hegedus et al. S. Walheim, et al., Structure Formation Via Polymer Demixing in
6,547.386 4, 2003 Bermel et al. Spin-Cast Films, Macromolecules, 30 (1997) 4995.
6,818,685 11, 2004 Chapman D. Reichel, et al., Anisotropic Porous Substrates for High Resolution
6,863,374 3, 2005 Yamazaki et al. Digital Printing, IS&T NIP16 International Conference on Digital
7,364,636 4, 2008 Kronzer Printing Technologies, (2000) 204-207.
2002fOOO4121 1, 2002 Branham et al. .............. 428,195 Seiji Munekata, Progress in Organic Coatings 16, 1998, 113-134.
2002/0039642 4, 2002 Inoue et al.
2003. O189626 10, 2003 Kataoka et al. * cited by examiner
U.S. Patent Mar. 13, 2012 US 8,133,556 B2

MICROPOROUS IMAGE-DEFINING LAYER

10
BASE LAYER-HOLDS LIQUID
COMPONENTS OF NK

(OPTIONAL) PRIMER LAYER

; ::::::::::::: SUBSTRATE::::::::::::...is
 US 8,133,556 B2
1. 2
DURABLE MULTILAYERNKJET B. An imaging layer comprising:
RECORDING MEDIA TOPCOAT 1. Second pigment particles having (a) a number average
particle size of 0.01-4 (lum) aggregated to form an inter
FIELD OF THE INVENTION particle region of Submicron pores, and (b) a pore Vol
ume of 0.4 to 2.2 (cm/g); and
This invention relates to inkjet recording media. In one 2. Water-insoluble binder resin having a surface energy
greater than 40 (dyn/cm);
aspect, the invention relates to a recording media topcoat the second pigment particles and water-insoluble binder
while in another aspect, the invention relates to labels and resin present at a weight ratio of 0.75 to 2.
signs that incorporate the recording media topcoat. 10 In one embodiment the two-layer receiver coating is an inkjet
receiver coating. In one embodiment the first pigment par
BACKGROUND OF THE INVENTION ticles are silica particles and the second pigment particles are
at least one of silica and alumina particles. In one embodi
Inkjet printers are a well known means for creating black ment the first silica particles have a Mohs hardness of 4-5. In
and white and color images on a recording medium. The one embodiment the water-insoluble binder resin is
15 crosslinked. In one embodiment at least one of the base and
images are created by generating Small droplets of ink which
are propelled onto the recording medium. The ink generally imaging layers further comprises a UV-stabilizer. In one
contains a water-based dye or dispersed pigment and the embodiment the base layer has a coating weight of 8-32
recording medium is often paper, but it may also be a coated grams per square meter (g/m). In one embodiment the imag
polymeric film, e.g., transparencies for overhead projectors. ing layer has a coating weight of 0.5-1.2 g/m.
Advantages with this type of printing include the ability to The base layer contains large pigment particles with high
create high-resolution, full-color images rapidly and in large pore volume which allows the inkjet media to absorb and hold
large quantities of ink. The imaging (top) layer contains Small
formats using digitally generated and stored images. It is also pigment particles and is microporous. This microporosity
quiet, environmentally friendly and safe. Inkjet printing, layer acts as a sieve that keeps the ink pigments on the top of
however, is not without certain difficulties 25 the media while allowing the ink liquids to penetrate into the
In inkjet printing, the ink has to be absorbed as quickly as base layer. This maximizes color density and image definition
possible by the recording medium in order to allow the of the printed images and this, in turn, allows for the printing
recording medium to be handled soon after the ink has been of linear and 2-dimensional (2-D) bar codes which are not
applied without the ink diffusing or spreading too farthrough obtainable for most inkjet media.
and into the recording medium. Such diffusion and spreading 30
Both layers contain water-insoluble binder resins that may
works against the production of images having photographic be crosslinked. The binder resin imparts excellent resistance
quality resolution. to water and organic solvents. The binder resins have a high
Other difficulties withinkjet printing are that the image can Surface energy which facilitates rapid ink absorption. This
lack water and abrasion resistance. These two problems, produces images that are dry to the touch almost immediately
along with the lack of light fastness of the dyes that are 35 after printing.
commonly used in inkjet inks, can hinder the application of The inkjet media of this invention is suited to use in both
inkjet printing to products which require outdoor weather industrial labels and outdoor signs. It has excellent image
ability. quality, high color density, bar code printability, strong Sol
These and other difficulties are successfully addressed by vent resistance, strong abrasion resistance and outdoor
the water-resistant, inkjet recording media topcoat composi 40 weathering performance.
tions taught in U.S. Pat. No. 5,882.388. The compositions of
this patent comprise (a) a binder composition comprising a BRIEF DESCRIPTION OF THE FIGURE
non-cationic, water-insoluble binder resin having a high Sur
face energy and dissolved or dispersed in an aqueous liquid The FIGURE is a schematic illustration of a two-layer
medium, and (b) hydrophilic pigment particles having a num 45 receiver coating over an optional primer which in turn is
ber average particle size in the range from 1-25 microns and layered over a substrate.
an oil absorption of at least 60 grams of oil perhundred grams
of particles (g oil/g 100 particles). While the use of the record DETAILED DESCRIPTION OF THE INVENTION
ing media topcoats of this patent produce commercial quality
images, a continuing interest exists in identifying recording 50 Unless stated to the contrary, implicit from the context, or
media topcoats that not only increase the color density of the customary in the art, all parts and percents are based on
images, but also increases the definition of the images. weight and all test methods are current as of the filing date of
this disclosure. For purposes of United States patent practice,
SUMMARY OF THE INVENTION the contents of any referenced patent, patent application or
55 publication are incorporated by reference in their entirety (or
In one embodiment the invention is a two-layer receiver its equivalent US version is so incorporated by reference)
coating comprising: especially with respect to the disclosure of synthetic tech
A. A base layer comprising: niques, definitions (to the extent not inconsistent with any
1. First pigment particles having (a) a number average definitions specifically provided in this disclosure), and gen
particle size of 3-25 microns (um), and (b) at least one of 60 eral knowledge in the art.
(i) an oil absorption value of at least 150 g oil/100 The numerical ranges in this disclosure are approximate,
particles, and (ii) a pore Volume of at least about 1.2 and thus may include values outside of the range unless
cubic meters per gram (cm/g); and otherwise indicated. Numerical ranges include all values
2. Water-insoluble binder resin having a surface energy from and including the lower and the upper values, in incre
greater than 40 dyne per centimeter (dyn/cm); 65 ments of one unit, provided that there is a separation of at least
the first pigment particles and water-insoluble binder resin two units between any lower value and any higher value. As
present at a weight ratio of 0.75 to 2; and an example, if a compositional, physical or other property,
 US 8,133,556 B2
3 4
Such as, for example, particle size, thickness, etc., is from 100 layer is coated on or otherwise applied to the base layer can be
to 1,000, then all individual values, such as 100, 101, 102, prepared using any conventional mixing or blending tech
etc., and sub ranges, such as 100 to 144, 155 to 170, 197 to nique and equipment.
200, etc., are expressly enumerated. For ranges containing The binder resin of each layer of the recording media
values which are less than one or containing fractional num- 5 topcoat can be used crosslinked or not crosslinked. For
bers greater than one (e.g., 1.1, 1.5, etc.), one unit is consid organic Solvent resistance and good mechanical performance
ered to be 0.0001, 0.001, 0.01 or 0.1, as appropriate. For and weatherability, typically the binder resin is at least par
ranges containing single digit numbers less than ten (e.g., 1 to tially crosslinked. The binder resin can be crosslinked using
5), one unit is typically considered to be 0.1. These are only any conventional technology, e.g., radiation, heat, moisture,
examples of what is specifically intended, and all possible 10 peroxide, etc. Crosslinking can occur before, during or after
combinations of numerical values between the lowest value printing.
and the highest value enumerated, are to be considered to be Base Layer
expressly stated in this disclosure. Numerical ranges are pro The high pore Volume of the large pigment particles, along
vided within this disclosure for, among other things, particle with a high pigment to binder ratio, allows the recording
size, layer thickness, component weight ratios and various 15 media topcoat to absorb and hold large amount of aqueous
process ranges. inkjet ink liquid. The high Surface energy of the binder resin
“Base layer and like terms mean the layer of the two-layer increase the speed of ink absorption (relative to a base layer
receiver coating that is beneath the imaging layer and above comprising a binder resin with a lower Surface energy) so that
the Substrate or, if present, the optional primer. prints dry quickly and without puddling or undesirable mix
“Imaging layer and like terms mean the layer of the two- 20 ing of colors. The binder resin component imparts water
layer receiver coating that is above the base layer and receives insolubility, crosslinking of the binder resin imparts organic
the ink from an ink-applicator, e.g., printer. Solvent insolubility, and the hard silica particles impart strong
Recording Media Topcoat abrasion resistance. The high pore Volume of the particles,
The recording media topcoats of this invention comprise particularly silica particles, allows the layer to hold a large
two layers, a base or bottom layer and an imaging or top layer. 25 amount of liquid from the inkjet inks which increases the
This is illustrated in the FIGURE in which imaging layer 11 reflected optical density of the prints. The incorporation of
of topcoat 10 is coated onto or otherwise adhered directly to UV stabilizers and the like impart good weatherability.
base layer 12. Base layer 12 of topcoat 10 is on top of and in Imaging Layer
direct contact with optional primer 13 which is on top of and The Small pigment particles are used to make the imaging
in direct contact with substrate 14. When an aqueous ink 30 layer microporous so that ink pigments cannot penetrate into
comprising pigment 15 and water 16 are brought in contact the base layer and thus avoid or minimize any contribution
with the top or exposed surface of imaging layer 1, pigment that they might make to the reflected optical density of the
15 remains on the Surface or gains only modest penetration printed image. Without this imaging layer, the reflected opti
into imaging layer 11 while water 16 passes through imaging cal density of the printed images would be reduced up to, and
layer 11 into base layer 12 as shown by arrow 17. The water 35 possibly exceeding 40 percent. Reflected optical density is
is absorbed and held in base layer 12. typically measured with a densitometer or spectrophotometer
The thickness of the recording media topcoat is such that it accordingly to ISO 5.
provides Sufficient absorption capacity. Topcoats that are too The Small pigment particles and microporosity of this layer
thick fail due to binder migration, i.e., the binder in each layer contribute to the image crispness and definition. This, in turn,
migrates to the Surface closest to the ink. This results in a 40 enables bar code printing. The base layer, like the topcoats of
non-uniform distribution of the binder in the respective layers most, if not all, commercially available inkjet media, is not
of the topcoat and this, in turn, results in poor printing per bar code printable, or can only be used to print relatively large
formance, low adhesion to the Substrate, and/or lack of bar codes, and this, in turn, makes most, if not all, of them
mechanical integrity. Accordingly, the thickness (expressed unsuitable for industrial label applications.
as coating weight) of the base layer is 8 to 32, preferably 12 to 45 Pigment Particles
30 and more preferably 15 to 25, g/m while the coating Since water-resistance is an objective of this invention, the
weight of the imaging layer is 0.5 to 12, preferably 1 to 8 and polymeric binder resins used in the practice of this invention
more preferably 1 to 6, g/m. The thicker the layers, typically do not dissolve in or absorb a significant quantity of water.
the slower the line speed. In general, the thinner the imaging Consequently, pigment particles with extensive pore struc
layer, the higher the optical density of the printed image. 50 tures are used to create porosity in the coating and capacity for
The topcoat can be applied to the Substrate or Support in holding the water and water-miscible components present in
any manner, conventional or otherwise. Typically the base the ink.
layer is applied to the Substrate, or a primer covering the If pigment particles are systematically added to a binder,
Substrate, by a conventional coating technique, e.g., wire or eventually a point is reached at which there is no longer
rod application, spraying, dipping and the like. After the base 55 enough binder to fill all of the space between the pigment
layer is affixed to the Substrate or primer, the imaging layer is particles. This is the critical pigment Volume concentration or
applied over the base layer, again typically by a conventional CPVC (T. C. Patton, Paint Flow and Pigment Dispersion, 2nd
coating technique. Alternatively, the base layer can first be ed., Wiley-Interscience, 1979), a key quantity well known to
cast or otherwise made as a film and then laminated to the those skilled in the art. As the ratio of pigment to binder
Substrate or primer. Likewise, the imaging layer can first be 60 increases above the CPVC, the amount of void space in the
made into a film and then laminated over the base layer. In yet coating increases. Thus, the coating must have Void space
another alternative, the imaging layer can first be affixed to above the CPVC in order to be absorptive if the binder is not
the base layer in any Suitable manner, and then the exposed absorptive. The pigment particle to binder resin ratio both in
side of the base layer can be affixed, e.g., laminated, to the the base and imaging layers of this invention is in the range of
substrate or primer. The mixture or blend from which the base 65 0.75 to 2. For the base layer, this ratio is preferably in the
layer is coated on or otherwise applied to the substrate or range of 0.85 to 1.2. For the imaging layer, this ratio is
primer, and the mixture or blend from which the imaging preferably in the range of 0.9 to 2.
 US 8,133,556 B2
5 6
Regarding the base layer, the pigment particles used in the ume, particles of fumed aluminum oxide, fumed silica and
practice of this invention have a large absorption capacity fumed mixed-oxide can be used in the practice of this inven
which is commonly defined by their oil absorption value. The tion. Fumed aluminum oxide, fumed silica and mixed-oxide
pigment particles have an oil absorption value greater than (>) particles for use in an imaging layer include, but are not
150, preferably >250 and more preferably >300, goil/100 g limited to, Aerodisp WK341, Aerodisp WK440, Aerodisp
pigment particles. In one embodiment the oil absorption WK630, Aerodisp WK7330 and Aerodisp WK7330N avail
value correlates to a specific pore Volume of at least 1.2, able from Evonik Degussa.
preferably at least 1.5 and more preferably at least 1.8, cm/g. One method for selectively producing high, e.g., 1.2 to 3.0
Generally, the higher the oil absorption, the more preferred cm/g, pore volume silica gel is described in U.S. Pat. No.
the pigment although as a practical matter, the oil absorption 10 3.959,174. The method uses alkaline gelation to control the
value does not exceed3 cm/g. The method for measuring the silicate concentration. It uses a de-solubilizing Substance
oil absorption value is set forth in ASTM D281-95. For the Such as ammonium hydroxide, Sodium Sulfate or other Such
imaging layer, the pigment particles can have a pore Volume salt to decrease the solubility of silica. The silica concentra
as Smallas 0.5 cm/g, preferably apore Volume in the range of tion is maintained at 3 to 15 percent, the silica to de-solubi
0.5 to 2.2 cm/g. 15 lizing agent ratio at 2 to 20, and the gelation pH at 10.6 to 11.2.
There are no other specific limitations on the pigment or The gelled silica is then aged, neutralized, filtered, optionally
other absorptive particles employed in the practice of this aged a second time, and washed. For use in this invention the
invention. Many different absorptive inorganic pigments are preferred values are in the range of 8 to 12 percent, more
identified in the paper coating literature. These materials preferably 10 percent, for SiO, and the SiO/NH ratio is in
include calcium carbonate, precipitated silica, fumed silica, the range of 4 to 8, preferably 6. After washing and filtering
silica gel, alumina, boehmite, pseudo-boehmite (U.S. Pat. and prior to re-slurrying, the silica is dried. This may be oven
No. 5,104.730), aluminum hydroxide, basic magnesium car drying or spray drying. This drying forms particle agglomer
bonate and amorphous magnesium carbonate. Sol-gel coat ates of greater than 25 microns. The agglomerated silica is fed
ings obtained by hydrolysis of alkoxides of silicon or alumi into a fluid energy mill, preferable of the micronizer orjet
num are another class of materials suitable for use in this 25 pulverizer type. When the particles are at a predetermined
invention. Preferred materials are sometimes referred to as size. e.g., 1 to 25 microns, they are collected from the mill.
“flatting agents'. For the pigment particles used in the base layer, the number
In one embodiment the pigment particles comprise silica. average particle size is 3 to 25, preferably 4 to 16, microns.
Silica particles for use in the base layer include, but are not For the pigment particles used in the imaging layer, the num
limited to, Syloid C803, Syloid C805, Syloid C807, Syloid 30 ber average particle size is 0.01 to 4, preferably 0.1 to 3.
C809, Syloid C812, Syloid C816, Sylojet P405, Sylojet P407, microns. Number average particle size is measured by
Sylojet P409, Sylojet P412, Sylojet P416, Syloid W300, dynamic light scattering over a range of 1 micronto hundreds
Syloid W500, Syloid 74, Syloid 234, Syloid 620, Syloid or thousands of microns using such equipment as the Horiba
4500, Syloid 5500, Syloid 6000 and Syloid 6500 all available LA-95OV2.
from W. R. Grace; Sylysia 250, Sylysia 250N, Sylysia 270, 35 Binder Resins
Sylysia 290, Sylysia 310P. Sylysia 320, Sylysia 350, Sylysia The binder resins of this invention have surface energies
370, Sylysia 380, Sylysia 390, Sylysia 420, Sylysia 430, greater than (>) 40, preferably >42, dyne/cm. As the surface
Sylysia 440, Sylysia 450, Sylysia 460, and Sylysia 470, all energy of the coating increases, the spreading coefficient,
available from Fuji Sylysia; and Gasil HP220, Gasil HP39, which may be defined as the decrease in free energy as the
and Gasil IJ45 available from Ineos Silicas. Preferred pig 40 surface is covered with a film of liquid (see S. Wu, Polymer
ments for the base layers include Syloid C805, Syloid C807, Interface and Adhesion, Marcel Dekker, 1982), increases.
Syloid C809, Syloid C812, Sylojet P405, Sylojet P407, Sylo Physically this means that the rate of ink spread on the sub
jet P409, Sylojet P412, Syloid W500, Sylysia 320, and Syly strate increases. The increase in coating Surface energy mani
sia 350. fests itself in color print density increases due to greater
Silica particles for use in the imaging layer include, but are 45 spread, or “dot gain, of the jetted ink droplets on the surface
not limited to, Sylojet A25, Sylojet C30, Sylojet 710A, Sylo and increases in the rate of ink absorption as the ink spreads
jet 710C, Sylojet C803, and Sylojet P403 available from W. R. more rapidly into the capillaries of the porous coating. Swift
Grace; and Sylysia 310P. Sylysia 320, Sylysia 350, Sylysia ink absorption not only allows the print to be handled as soon
420, Sylysia 530 available from Fuji Sylysia. Two particu as it comes off the printer, but for some wide-format inkjet
larly preferred pigments for the base layer are Syloid C812 50 printers the ink must dry within a few seconds or it will be
and Sylojet P412 which have an oil absorption value of 320 g Smeared by handling or by rollers in the paper feed systems
oil/100 g pigment particles and a mean particle size of 12 that may be only a few inches away from the print-head.
microns (measured by laser diffraction). Preferred pigments The surface energy of a flat film of binder resin is measured
for the imaging layer include Sylojet A25, Sylojet C30, Sylo by ASTM D2578-08. This test employs mixtures of forma
jet 710A, Sylojet 710C, Sylysia 310P. Sylysia 320, and Syly 55 mide and ethyl CELLOSOLVETM (ethylene glycol monoet
sia 350. In general, silicas with large particle size and narrow hyl ether available from The Dow Chemical Company) over
particle size distribution give coatings with more inter-par the range of 30-56 dyn/cm. Test kits are available from Diver
ticle void space and better ink absorption than silicas with sified Enterprises under the name Acculyne Test Surface
small particle size and/or broad particle size distribution. Tension Test Fluids.
In one embodiment the pigment particles of the imaging 60 Alcohol-Soluble Binder Resins
layer comprise alumina. The boehmite type of hydrated alu In one embodiment of this invention, the binder resin com
mina is particularly useful. Boehmite alumina particles for prises a non-cationic, alcohol-soluble, water-insoluble com
use in imaging layer includes, but is not limited to, Aeropal pound dissolved in an alcoholic liquid medium. In this
65, Dispal 8F4, Dispal 10F4, Dispal 11N7-80, Disperal 20, embodiment the binder resin is preferably soluble to a con
Disperal 40, Disperal 60, Disperal 18HP Disperal HP 14, 65 centration of at least 5 weight percent (wt %) in the alcohol or
Disperal HP 14/2 and Dispersal HP 18 available from Sasol. alcohol mixture used to prepare the recording media coating
Notwithstanding their lack any significant internal pore Vol composition.
 US 8,133,556 B2
7 8
The alcoholic liquid medium has a boiling point less than diamine, octamethylene diamine, nonamethylene diamine,
150° C., preferably less than 140°C., more preferably less decamethylene diamine, undecamethylene diamine, dodeca
than 120° C., and has a viscosity of up to 100 MegaPascals methylene diamine, tridecamethylene diamine, and octa
(MPa), preferably up to 50 MPa. The alcohols are not a decamethylene diamines. Suitable polymethylene diacids for
solvent for the support or substrate to which the coating preparing suitable polyamides include adipic, pimelic,
composition is applied, although they may swell the Support Suberic, azelaic, sebacic, dodecanedioic, brassylic, tetrade
to some extent. Suitable alcohols include hydrocarbon com candioic and octadecanedioic acids. Suitable amino acids
pounds having at least one carbon atom and at least one include 6-aminocaproic, 7-aminoheptanoic, 8-aminoca
hydroxy group. They can have a wide range of carbon atoms prylic, 9-aminononanoic, 10-aminodecanoic, 11-aminoun
and hydroxy groups. Preferably, however, the alcohol has less 10 decanoic, 17-aminoheptadecanoic, and the like.
than 15 carbon atoms and less than 4 hydroxy groups. These By “dimerized fatty acid of 16 to 48 carbons' is meant
alcohols may have other hetero atoms besides those contrib dimers derived from fatty acids of 8 to 24 carbons. These
uted by the hydroxy group(s), and these groups can be pri dimerized fatty acids are commercially available materials
mary, secondary or tertiary to the hydrocarbon moiety such as which have been fully described in the literature including
their valence allows so long as it does not become a solvent 15 U.S. Pat. Nos. 3,157,681 and 3,256,304. These dimerized
for the support. fatty acids are obtained by catalytic or non-catalytic polymer
Due to the polar nature of most binder resins, polar hydro ization of ethylenically unsaturated fatty acids.
carbon liquids with hydroxyl groups are preferred alcoholic The method of forming polyamides by melt-condensation
liquid media. Straight chain primary and secondary alcohols is well known to those skilled in the art. This polymerization
ranging from 1 to 6 carbonatoms in length, Such as methanol, reaction is described, for example, in U.S. Pat. Nos. 2.252,
ethanol, propanol, n-butanol, 2-butanol, isopropanol, and so 554 and 2,285,009 and British Patent 1055 676. The reaction
forth, are preferred. Tertiary alcohols such as diacetone alco is carried out by polyamide-forming derivatives, and, if
hol are also appropriate. Glycol ethers such as diethylene desired, amino acids or their polyamide-forming derivatives
glycol monobutyl ether, ethylene glycol monobutyl ether and at temperatures of about 150 to 300° C. while driving off
propylene glycol monomethyl ether may also be included in 25 water and continuing the reaction until the desired molecular
the composition as alcoholic liquid media. The solvent com weight is obtained. The resulting polyamide contains Sub
position of the coating composition may include up to 40 stantially equimolar amounts of carbonyl groups and imine
percent water and minor amounts of other organic solvents. groups. The polymer end groups are carboxylic acid and
One preferred class of suitable alcohol-soluble binder res amine, one of which may be in slight excess depending upon
ins are alcohol-soluble polyamides. Typical alcohol-soluble 30 which reactant was present in excess. Preferably the polymer
polyamides and methods of obtaining them are disclosed in contains at least as many amine ends as carboxyl ends.
U.S. Pat. Nos. 2,285,009; 2,320,088; 2.388,035: 2,393,972: These polyamides and their method of manufacture are
2,450,940 and 3,637.550. Preferred alcohol-soluble polya described in more detail in U.S. Pat. No. 3,637.550. Specific
mides include alcohol-soluble melt-polymerized polyamides examples of this type of polyamide include ELVAMIDER)
consisting essentially of recurring carboxamido groups and at 35 nylon terpolymer resins available from E.I. DuPont de Nem
least two different species of recurring hydrocarbylene ours, Inc., and custom nylon terpolymer resin Solutions avail
groups selected from the group consisting of aliphatic and able from General Plastics Corporation. Preferred binder res
alicyclic groups of 2 to 40 carbonatoms as integral parts of the ins include ELVAMIDE 8023, ELVAMIDE 8061,
main polymer chain, and having at least 3 different recurring ELVAMIDE 8061A, ELVAMIDE 8061M and ELVAMIDE
polyamide repeat units. 40 8066. Particularly preferred binder resins are solutions of
Preferred among Such polyamides are those in which (a) ELVAMIDE(R) 8063 nylon terpolymer in blends of low
33-100 mole percent (mol%) of the imine groups are derived molecular weight aliphatic alcohols and water.
from polymethylene diamine of 6 to 20 carbons, (b) 5-65 mol Additional preferred alcohol-soluble polyamides are those
% of the carbonyl groups are derived from dimerized fatty prepared by condensing a monocarboxylic acid, diamine and
acids of 16 to 48 carbonatoms, (c) 8-65 mol% of the carbonyl 45 dimerized fatty acid as described in U.S. Pat. No. Re.28,533;
groups are derived from polymethylene diacid of 6 to 18 those prepared by condensing an acid component of dimer
carbon atoms, and (d) 8-65 mol % of the carbonyl groups are ized fatty acids, at least one aliphatic unbranched monocar
derived from monomers selected from the group consisting of boxylic acid, and at least one aliphatic branched monocar
(1) polymethylene diacid of 6 to 18 carbon atoms which is boxylic acid with ethylene diamine and hexamethylene
different from diacid (c), and (2) polymethylene omega 50 diamine as the amine component as described in U.S. Pat. No.
amino acid of 6 to 18 carbon atoms. These polyamides have 4,571.267; and those polyamide resin compositions that com
an annealed heat of fusion of 5 to 18 calories per gram, are prise the condensation reaction product of a Ce dimerized
quenchable to the amorphous state at a cooling rate of 100° C. fatty acid, at least one dibasic acid, at least one C alkyl
per minute, and have an upper glass transition temperature in diamine and at least one piperazine-like diamine, the equiva
the amorphous state of less than 30°C. 55 lents of amine groups being Substantially equal to the equiva
One particularly preferred class of polyamides includes lents of carboxyl groups, where 30 to 50 equivalent percent of
those in which (1) 98-100 mol % of the imine groups are the carboxyl groups are contributed by the dibasic acid com
derived from hexamethylene diamine, (b) 15-55, and prefer ponent and 73 to 93 equivalent percent of the amine groups
ably 25-55, mol % of the carbonyl groups are derived from are contributed by the piperazine-like diamine component as
dimerized fatty acid of 36 carbon atoms, (c) 10-45, and pref 60 described in U.S. Pat. No. 5,154,760. Specific examples of
erably 15-45, mol % of the carbonyl groups or derived from this type of polyamide resin include the UNI-REZR) fatty acid
adipic acid, and (d) 15-55, and preferably 15-45, mol% of the dimer-based polyamides developed by Union Camp Corpo
carbonyl groups are derived from polymethylene diacid of 10 ration.
to 12 carbon atoms. Most preferably, these polyamides have Dispersed Binder Resins
a minimum flow temperature of 160 to 210°C. 65 In one embodiment of this invention, the binder resin com
Suitable polymethylene diamines for preparing suitable position is a dispersion of a non-cationic water-insoluble
polyamides include hexamethylene diamine, heptamethylene binder resin in an aqueous or alcoholic liquid medium. The
 US 8,133,556 B2
9 10
alcoholic medium may be selected from among those from Cytec Industries: RESIMENER 717,718,741,745, and
described above as solvents for the resins which are soluble in 747 partially alkylated melamines from Ineos Melamines:
alcoholic liquid media. The aqueous or alcoholic medium BAYHYDUR 302,303, 304, 305, 401-70, BL5335, VPLS
may be a mixture of an alcoholic medium with an aqueous 2150 BA, VPLS 2306, VPLS 2310, XP 2487/1, XP 2547, XP
media, and it may further comprise minor amounts of non 5 7165 isocyanates from Bayer Material Science; and
alcoholic organic Solvents. In one embodiment the binder BASONAT HB 100, HI 100, HB 175 MP/X, and HB 275 B
resin is an aqueous dispersion of a non-cationic water-in isocyanates from BASF. In some cases the melamine form
soluble polyamide. Aqueous polyamide dispersions that are aldehyde resins may require an acid catalyst Such as p-toluene
useful in this invention include custom nylon terpolymer Sulfonic acid. In some cases, the isocyanates may require the
dispersions available from General Plastics Corporation 10 use of organometallic catalysts for initiation Such as dibutyl
under the GENTON trademark, and MICROMID fatty acid tin dilaurate.
dimer-based polyamide dispersions available from Arizona Topcoat Additives
Chemical. The topcoat formulation can include one or more additives
Polyamides Suitable for making aqueous dispersions that impart beneficial properties to the topcoat. These prop
include polymerized fatty acid polyamide resins which have 15 erties may be particularly preferred when the image-bearing
been prepared so as to have a low acid and low amine number. recording media is exposed to environmental conditions that
The dispersion is typically prepared by heating the polyamide are deleterious to the integrity of the image.
resin to a temperature at or above its melting point. The One such environmental condition is exposure to short
liquefied polymerized fatty acid polyamide resin is then wavelength radiation, such as the ultraviolet radiation con
blended with a predetermined amount of water which is tained in Sunlight. Ultraviolet radiation is known to cause
heated to a temperature such that the resulting blend will have photochemical damage to coatings and color images, such as
a temperature above the melting point of the polyamide resin. structural damage and fading or darkening of colors. Addi
A Surfactant, which may be anionic, nonionic or cationic, tives which are known to protect against degradation by ultra
preferably nonionic, and which will promote the emulsifica violet radiation are generally classified as UV absorbers, light
tion of the polyamide resin in water, is included in the mix 25 stabilizers and antioxidants. These additives are used in the
ture. The resulting mixture is then subjected to sufficient manner and amounts as is well known in the art.
comminuting forces to form an emulsion in which droplets of Examples of UV absorbers include compounds classified
the polyamide resin have a Volume average size distribution as derivatives of hydroxybenzotriazole, hydroxybenzophe
of 20 microns or less in diameter and preferably 5 microns or none, and triazines, such as hydroxylphenyl-s-triazines. Spe
less. The resulting emulsion is then cooled to a temperature 30 cific examples include TINUVINTM 1130 from Ciba (a mix
below the melting point of the polyamide resin causing the ture of poly(oxy-1.2 ethanediyl)..C.-(3-(3-(2H-benzotriazol
emulsified droplets of the polyamide resinto solidify as finely 2-yl)-5-(1,1-dimethylethyl)-4-hydroxyphenyl)-1-
divided particles which are dispersed uniformly through the Oxopropyl)-()-hydoxy and poly(oxy-1.2 ethanediyl), C.-(3-
aqueous phase. The resulting aqueous dispersion is stable. (3-(2H-benzotriazol-2-yl)-5-(1,1-dimethylethyl)-4-
This type of binder resin composition is described in U.S. Pat. 35 hydroxyphenyl)-1-oxopropyl)-()-(3-(3-(2H-benzotriazol-2-
No. 5,109,054. yl)-5-(1,1-dimenthylethyl)-4-hydroxyphenyl)-1-
Dispersions of many other binder resins with surface ener oxopropoxy); TINUVIN 384 from Ciba, benzenepropanoic
gies greater than 42 dyn/cm are also useful in the practice of acid, 3-(2H-benzotriazol-2-yl)-5-(1,1-di-methylethyl)-4-hy
this invention. These resins include ethylene-acrylic acid droxy-, C7-9 branched an linear alkyl esters: TINUVIN 400
(EAA) copolymers, ionomers, copolymers of poly-2-ethyl 40 from Ciba, a mixture of 2-4-(2-hydroxy-3-dodecyloxypro
2-oxazoline and acrylates, and polyurethanes. Preferred res pyl)oxy-2-hydroxyphenyl-4,6-bis(2,4-dimethylphenyl)-1,
ins include EAA copolymer dispersions sold by Michelman, 3,5-triazine and 2-4-(2-hydroxy-3-tridecyloxypropyl)oxy
Inc under the MICHEM PRIME trademark, EAA copoly 2-hydroxyphenyl-4,6-bis(2,4-dimethylphenyl)-1,3,5-
mers sold by The Dow Chemical Company under the PRI triazine; TINUVIN 460 from Ciba, 2,4-bis(2-hydroxy-4-
MACOR trademark, EAA copolymer ionomer dispersions 45 butoxyphenyl)-6-(2,4-bis-butoxyphenyl)-1,3,5-triazine;
sold by Michelman, Inc under the MICHEM PRIME trade Tinuvin 477DF hydroxyl-phenyl-triazine from Ciba; CYA
mark, and polyurethanes sold under the WITCOBOND trade SORBTM UV 24 from Cytec (a hydroxybenzophenone UV
mark. Particularly preferred resin dispersions include absorber); and CYASORBTMUVI164 also from Cytec (a UV
MICHEMPRIME 48.525 ionomer, MICHEMPRIME 4893R absorber of the substituted s-triazine class).
EAA copolymer, MICHEM PRIME 4893-40R EAA copoly 50 The UV stabilizers are typically hindered amine light sta
mer, MICHEM PRIME 489345N ionomer, MICHEM bilizers (HALS). Specific examples include TINUVINTM
PRIME 4990R copolymer, WITCOBOND W-213 polyure 123, 292 and 770 and CHIMASSORBTM. 119 and 944FL, all
thane, and WITCOBOND W-240 polyurethane. from Ciba.
Crosslinking Agents The antioxidants which are useful in the topcoat formula
In one embodiment, the binder resins are crosslinked in 55 tions of the present invention may be selected from a wide
order to improve solvent resistance. For some of the binder range of compounds, such as the phenolic antioxidants, e.g.,
resins useful in this invention, crosslinking may also improve hindered mono-phenols, diphenols, and poly-phenols, and
water resistance. For polyamide resins, one preferred class of phosphites and phosphonites. Examples of the phenolic anti
crosslinking agent is aziridine. One particularly preferred oxidants include the IRGANOXTM series from Ciba, such as
crosslinking agent is XAMAR-7 tri-functional aziridine from 60 IRGANOXTM 1098, and an example of the phosphite type
BASF. Preferably the EAA copolymer and ionomer resins, antioxidant is IRGAFOS 168, also from Ciba. Interactions of
copolymers of poly-2-ethyl-2-oxazoline and acrylates, and the antioxidants with other components of the formulations
polyurethanes are crosslinked with aziridine, isocyanate or may, however, form colored compounds in reactions with
melamine formaldehyde resin in order to obtain sufficient many crosslinkers, and thus may be unsuitable for certain
Solvent resistance. Preferred crosslinking agents for these 65 formulations.
resins include XAMAR-7 tri-functional aziridine from Further examples of UV absorbers, stabilizers and antioxi
BASF, CYMEL(R) 385 and 373 partially alkylated melamines dants that may be used as additives to the topcoat composi
 US 8,133,556 B2
11 12
tions according to this invention may be found in Chapter 2 of resin and polyethylene are taught in U.S. Pat. No. 4,070,421
Oxidation Inhibition in Organic Materials (CRC Press, 1990, for use as primers and paint and ink additives for improving
J. Pospisil et al., eds., pp. 29-162), entitled “Photo-oxidation adhesion of coatings to polyolefin. Chlorinating carboxyl
of Polymers and its Inhibition” by Francois Gugumus; Mod group-containing polyolefins to form primer coatings for
ern Plastics Encyclopedia Handbook (McGraw Hill, 1994); untreated polyolefin substrates is taught in U.S. Pat. No.
“UV Stabilizer” by Pyong-Nae Son, pp. 119-120: European 3,579,485. Still further, U.S. Pat. No. 3,380,844 teaches the
Patent Application 0704,560; and U.S. Pat. Nos. 4,314.933 coating of polyolefin film by a polymer of vinylidene chlo
and 4,619,956. ride, a (meth)acrylate ester and (meth)acrylic oritaconic acid.
Polyamide-based topcoats, when UV-stabilized with an Polymers other than chlorinated polymers have also been
additive package, are especially suitable for applications 10
adhered to polyolefins. U.S. Pat. No. 4,080,405 teaches a
requiring outdoor weatherability in which a high degree of process for chemical modification of polyolefins by grafting
water-resistance is required. Additives appropriate to polya polar monomers onto the polyolefin by means of a free radical
mides include s-triazine and hydroxy benzotriazole UV generating material to produce a polyolefin Surface having
absorbers, hindered amine light stabilizers, and phenolic and
phosphite antioxidants. Best results are usually obtained 15 improved wettability. U.S. Pat. No. 3,394,029 teaches the
when a combination of UV absorbers and hindered amines, coating of polyolefin Surfaces by polymers of certainterpene
are used as the combinations are often synergistic. acrylates and N-terpene acrylamides for improved adhesion
An advantage of inkjet media with the polyamide-based of conventional lacquer topcoats. U.S. Pat. No. 4,014,645
topcoats of this invention relative to the prior art is that no teaches the enhancement of dye receptivity of polyolefin
over-lamination, heating, exposure to UV light or an electron materials used in fabric manufacture by coating the polyole
beam, or other post-treatment is required after printing as the fin with a self-curing polymeric binder containing a quater
media has strong resistance to UV light, water and a large nary ammonium salt. U.S. Pat. No. 4,097.677 discloses cer
range of solvents. However, the porous media will lack stain tain radiation curable coatings, useful to coat some
resistance, so it may still be desirable for Some applications to polyolefins; the coatings comprising monomeric unsaturated
apply a clear coating or pressure-sensitive over-laminate to 25 esters of glycol monodicyclopentenyl ethers. In British
impart stain resistance. Of course, many of the clear coatings Patent. 1177 199 nonwoven webs are disclosed containing a
and over-laminates will also enhance the weathering perfor major amount of polypropylene fibers bonded with binder
mance and abrasion resistance of this inkjet media. The comprising vinyl acetate, ethylene and an unsaturated N-me
polyamides may be coated either from Solution in alcohols thylol amide or an alkyl ether of it. U.S. Pat. No. 3.258,443
and alcohol/water mixtures or in the form of aqueous disper 30
describes a latex which may be used to deposit a pressure
sions.
Supports sensitive adhesive on polyethylene and polypropylene. The
The coating compositions of this invention can be used on latex is prepared from 1 to 45% vinyl acetate, 50 to 98% of an
a variety of supports, including paper, polymer-coated paper, alkyl acrylate having an alkyl group of between 4 and 10
synthetic paper, polymer-coated fabric or mesh, vinyl (Such 35 carbon atoms (several acyclic alkyl groups are named) and 1
as cast vinyl or calendared vinyl), polyethylene, polypropy to 5% of an unsaturated carboxylic acid. U.S. Pat. Nos. 3.931,
lene, polyester (Such as polyethylene terephthalate), polysty 087 and 4.012,560 teach the use of copolymers of a sulfonic
rene, etc. The advantages of this invention are particularly acid and esters of acrylic or methacrylic acids as pressure
pronounced with regard to Supports having low Surface sensitive adhesives which are adherent to a number of Sur
energy, low porosity and/or a generally poor ability to absorb 40 faces including polyethylene and polypropylene.
and adhere to inkjet inks. Supports that have good weather U.S. Pat. No. 4,818,325 describes a useful primer which
ability are preferred in those applications in which weather comprises at least one organometallic compound and at least
ability is a criterion. one organic polymer and is used in bonding non-polar or
The Surface of a low Surface energy Support, such as nearly highly crystalline resin Substrates together or bonding
any of the commercially manufactured polymer Supports 45 another material to the resin substrate with the use of a 2-cy
mentioned above, is often treated to raise its surface energy anoacrylate.
and provide polar groups which can hydrogen bond to attain Polyurethane resins may also be used as primers. The poly
good adhesion between the support and the binder. To render urethane resins include thermoplastic polyurethane resins
these Support materials improved in adhesiveness, Surface and thermosetting polyurethane resins. In addition, the poly
treating methods are known which comprise Subjecting the 50 urethane resins include modified polyurethane resins as far as
Substrates to flame treatment, corona discharge treatment, it mainly comprises polyurethane resins. However, in order to
irradiation treatment or oxidizing treatment with a bichro give a high adhesive capacity and a high elasticity to a paint
mate, Sulfate or the like so as to produce polar groups such as film, thermoplastic polyurethane resins having a mean num
a carbonyl group on the Surface of the Substrates. However, ber average molecular weight (Mn) of 2,000 to 10,000, pref
Such treatments need special equipment and are complicated 55 erably 4,000 to 7,000, are used. Such resins are described in
to carry out. U.S. Pat. No. 4,780,340 for making additional primers.
Another approach is to coat the Support with a primer Alternative Uses
which comprises a polar polymer having a Surface energy The recording media topcoat of this invention works espe
intermediate between that of the support and that of the coat cially well as a recording media for inkjet printing with aque
ing composition. Acrylic polymers, polyurethane polymers 60 ous-based inks of labels, signs and wide-format graphics, but
and mixtures of acrylic and polyurethane polymers are pre it is capable of receiving and absorbing many different forms
ferred, particularly when they are in the form of an aqueous of liquid inks in various printing processes. Other liquid inks
dispersion. A primer may be applied at low coat weights, such include nonaqueous-based or mixed aqueous and nonaque
as in the range of 1 to 4 g/m dry weight. ous-based inks and UV-curable inks, any or all applied by
Certain chlorinated polymers can also be employed as 65 water-borne flexo-printing or letterpress. The recording
primers to enhance the bonding of materials to untreated media topcoat of this invention can also be used in thermal
polyolefin surfaces. Chlorinated mixtures of a hydrocarbon transfer printing.
 US 8,133,556 B2
13 14
The invention is described more fully through the follow TABLE 4-continued
ing examples. Unless otherwise noted, all parts and percent
ages are by weight. 26% ELVAMIDE (R) 8063 Resin Solution

Component Weight (g)

EXAMPLES
n-Butanol 10
Example 1 Di-ionized Water 14.8
26% ELVAMIDE (R) 8063 Polyamide 26
Terpolymer Resin
Materials
10 TOTAL 100
White, 2-mil MELINEXR 329 polyester film available 26% ELVAMIDE (R. 8063 polyamide terpolymer resin is available from E. I. DuPont de
from DuPont Teijin Films was used as the substrate. It was Nemours, Inc.
coated at a coat weight of 3.2 g/m with the primer formula
tion reported in Table 1. TABLE 5
15
TABLE 1. UW Stabilizer Subformula
Primer Formulation Component Weight (g)
Component Weight (g) Methanol 39.4
n-Propanol 39.4
NeoRez R-967 Polyurethane Dispersion 34 TINUVIN 1130 Benzotriazole 17
Joncryl 617 Acrylic Emulsion 34 CHIMASSORB944 4.2
Di-ionized Water 32
TOTAL 100
Total 100
% Solids 29.1 25 TINUWINR 1130 benzotriazole is a UW absorber available from Ciba,
CHMASSORB (R944 is a hindered amine stabilizer available from Ciba.
NeoRez R-967 polyurethane dispersion is available from DSM NeoResins.
Joncryl 617 acrylic emulsion is available from BASF. The base layer was coated with an imaging layer by a #8
The primer was coated with a base layer by a slot die at a dry Mayer rod at a dry coat weight of 2.2 lb/ream (3.6 g/m). The
coat weight of 11 lb/ream (17.9 g/m). The formulation of the 30
formulation of the base layer is reported in Table 6.
base layer is reported in Table 2.
TABLE 6
TABLE 2 Imaging Layer Formulation
Base Layer Formulation 35 Component Weight (g)
Component Weight (g) Methanol 1946
n-Propanol 1946
C812 Silica Dispersion (Table 3) 54.08 Di-ionized Water 9.72
26% ELVAMIDE (R) 8063 Solution (Table 4) 4.O.S Fuji Sylysia SY 310 Silica Gel 9.19
UV Stabilizer Subformula (Table 5) 4.95 ELVAMIDE (R) 8063 Solution (Table 4) 32.12
Xama-7AZiridine Crosslinker O.47 40
UV Stabilizer Subformula (Table 5) 4.95
Xama-7AZiridine Crosslinker O.S1
TOTAL 100 Methanol 3.67
% Solids 21.7 Di-ionized Water O.92
Pigment:Binder Ratio O.90
TOTAL 100
Xama-7 aziridine crosslinker is available from BASF. 45 % Solids 18.7
Pigment:Binder Ratio 1.OS
TABLE 3
18.4% Syloid C812 Silica Dispersion Example 2
50
Component Weight (g)
The same Substrate, primer layer and base layer were used
Methanol
n-Propanol
32
32
as in Example 1. For the imaging layer, the formulation in
Di-ionized Water 16 Table 7 was used. The methanol was added very slowly with
Syloid C812 Silica Gel (92% Solids) 2O 55
stirring to the Sylojet 710Aaqueous silica dispersion to avoid
precipitation. The ELVAMIDE(R) 8063 resin solution and UV
TOTAL 100
Stabilizer Subformula were then stirred in, and the Xama-7
Syloid C812 Silica Gel is available from W. R. Grace. crosslinker was added just before the formulation was coated
with a #6 Mayer rod for a dry coating weight of 1.5 g/m.
60
TABLE 4 TABLE 7
26% ELVAMIDE (R) 8063 Resin Solution Imaging Layer Formulation 2
Component Weight (g) Component Weight (g)
Methanol 24.6 65 Sylojet 710A silica dispersion 24.80
n-Propanol 24.6 Methanol 51.42
 US 8,133,556 B2
15 16
TABLE 7-continued The base layer was then coated with the Imaging Layer
Formulation 4 shown in Table 10. Imaging Layer Formula
Imaging Layer Formulation 2 tion 4 was drawn down with a #4 Mayer rod and cured for 2
Component Weight (g) min in a forced-air oven at 120° C. to give a dry coating
5 weight of 2.6 g/m.
ELVAMIDE (R) 8063 Solution (Table 4) 1864
UV Stabilizer Subformula (Table 5) 4.94
Xama-7AZiridine Crosslinker O.2O TABLE 10
TOTAL 100 Imaging Layer Formulation 4
% Solids 10.1 10
Pigment:Binder Ratio 1.OS Component Weight (g)
Sylojet 710A silica dispersion (20.5%) 65.24
MICHEM PRIME 4990R ethylene/acrylic acid 33.26
Example 3 copolymer dispersion
TINUVIN 477 DW triazine UW absorber OSO
15 Xama-7AZiridine Crosslinker OSO
The substrate, primer layer, and base layer of Example 1 TOTAL 100
were used. The imaging layer formulation is detailed in Table % Solids 25.3
8. The methanol was added very slowly with stirring to the Pigment:Binder Ratio 1.2O
Sylojet 710A aqueous silica dispersion to avoid precipitation.
The ELVAMIDE(R) 8063 resin Solution and UV Stabilizer
Subformula were then stirred in. Dispal 11N7-80 boehmite
alumina powder was added while the mixture was stirred with Example 5
a Cowles blade at high speed for 30 min. The Xama-7
crosslinker was added just before the formulation was coated 25 Example 5 illustrates the inapplicability to this invention of
with a #6 Mayer rod to give a dry coating weight of 1.8g/m. a binder resin with a surface energy of less than 40 dyn/cm.
For the formulations of both the base and imaging layers, the
TABLE 8 silica was first mixed with DI water to form a slurry. The
Imaging Layer Formulation 3 binder resin was added next, and the aziridine crosslinker was
30 added just before the coating was drawn down. The base layer
Component Weight (g) (Table 11) was drawn down onto 3 mil white Melinex 329
Sylojet 710A silica dispersion (20.5%) 24.80
PET with a #34 Mayer rod; the imaging layer was drawn
Methanol 48.88 down onto the base layer with a #6 Mayer rod. Both layers
ELVAMIDE (R) 8063 Solution (Table 4) 1864 were cured for 2 min at 130°C. in a forced-air oven.
UV Stabilizer Subformula (Table 5) 4.94 35
Xama-7AZiridine Crosslinker O.2O TABLE 11
Dispal 11N7-80 alumina 2.54
TOTAL 100
Base Layer Formulation 5
% Solids 12.1 Syloid W500 silica gel 12.30
Pigment:Binder Ratio 1.47 40 DI water 49.16
NeoCryl A-1049 36.05
Dispal 11N7-80 is a boehmite alumina powder available from Evonik Degussa. Xama-7 2.49

TOTAL 1OOOO
Example 4 % Solids 27.1
45
Pigment:Binder Ratio 1.OO
Melinex 329 white polyethylene terephthalate (PET) 2 mil
in thickness was used. The formulation in Table 9 was mixed
with an overhead mixer, drawn down with a #34 Mayer rod TABLE 12
onto the PET, and cured for 2 min in a forced-air oven at 90°
C. to give a dry coating weight of 22.6 g/m. 50 Imaging Layer Formulation 5
Syloid W300 silica gel 12.30
TABLE 9 DI water 49.16
NeoCryl A-1049 36.05
Base Layer Formulation 4 Xama-7 2.50

Component Weight (g) 55 TOTAL 1OOOO

% Solids 27.1
20% dispersion of Syloid C812 in 80/20 methanol/DI water 61.98 Pigment:Binder Ratio 1.OO
MICHEM PRIME 4990R ethylene/acrylic acid copolymer 37.02
dispersion
TINUVIN 477 DW triazine UW absorber OSO
Xama-7 Aziridine Crosslinker OSO 60
Example 6
TOTAL 1OO
% Solids 26.2
Pigment:Binder Ratio 1.00 The formulation in Table 13 illustrates the effects of the use
ofa water-soluble polymeras the binder resin for the top layer
MICHEMPRIME
Inc.
4990R is an ethylene acrylic acid copolymer available from Michelman, 65 of an inkjet receiver coating This formulation was drawn
TINUWIN 477DW is a triazine UW absorber available from Ciba, down with a #12 Mayer rod over the base layer of Example 1
for testing.
 US 8,133,556 B2
17 18
TABLE 13 swab). Thirteen solvents were tested: deionized water, iso
propanol, methyl ethylketone, acetone, toluene, mineral spir
Imaging Layer Formulation 6 with Water-Soluble Polymer its, gasoline, JP-8 jet fuel, brake fluid, Skydrol 500B-4
Sylojet A25 silica gel 53.60 hydraulic fluid, SAE 20 wtoil, 3% aqueous Alconox solution,
Viviprint200 44.40 and a 10% sulfuric acid solution. For each of the solvents, the
RESIMENE 717 2.OO
amount of damage to the printed image was graded as one of
TOTAL 100.00 the following: no visible effect (3 points), slight effect (2
% Solids 28.7 points), moderate effect (1 point), or severe effect (0 points).
Pigment:Binder Ratio 1.O
10
The grades for the thirteen solvents were added up and aver
aged. As a metric, these numerical averages were converted to
grades according to the following scale: >2.24=A, 2.00
Example 7 2.24=B; 1.75-199=C; 1.50-1.74=D: <1.50=F.
Accelerated Weathering
The formulation in Table 14 illustrates the effects of the use Color blocks of the primary (cyan, magenta, yellow, black)
of non-absorptive silica in the top layer of an inkjet receiver were printed at 100% ink laydown in Corel Draw 11. Color
coating. This formulation was drawn down with a #12 Mayer blocks of the secondary colors (red, green, blue), were also
rod over the base layer of Example 1 for testing. printed in this software application. When possible, for the
different printers, color management was turned off to maxi
TABLE 1.4 mize the ink laydown. The reflected optical densities of the
Imaging Layer Formulation with Non-Absorptive Pigment blocks were measured using a Gretag Macbeth D19C densi
tometer with ANSI Status T filters. For the primary colors,
Sylojet 4000C silica dispersion 26.43 only a single density was measured. For the secondary colors,
26% Elvamide 8063 Resin Solution (Table 4) 40.65 two densities were measured (magenta and yellow for red,
UV Stabilizer Subformula (Table 5) 5.50
Methanol 21.14 25 cyan and yellow for green, cyan and magenta for blue). For
Deionized water
Xama-7 aziridine
S.28
1.00
each material, an overall average density for all seven colors
was computed. Samples with printed color blocks were
TOTAL 100.00 placed in an Atlas Ci5000 Xenon Arc Weather-Ometer and
% Solids 23.1
30
tested using ASTM G155, Cycle 1. The reflected optical
Pigment:Binder ratio 1.O
densities of the color blocks samples were monitored for 800
hr, which is believed to be approximately equivalent to one
Test Methods and Grading of Samples year outdoors in Milwaukee, Wis., USA (Reference: B. Kle
Reflected Optical Density of Prints mann, "Correlations between Xenon Arc accelerated weath
Color blocks of the primary (cyan, magenta, yellow, black) 35 ering tests and Outdoor Weathering, IS&T NIP 19 Interna
were printed at 100% ink laydown in Corel Draw 11. Color tional Conference on Digital Printing Technologies, 396,
blocks of the secondary colors (red, green, blue), were also 2003.) For each color, the ratio of the average reflected optical
printed in this software application. When possible, for the density after 800 hr to the initial reflected optical density was
different printers, color management was turned off to maxi calculated. The averages were graded according to the fol
mize the ink laydown. The reflected optical densities of the 40 lowing scale: >0.849–A: 0.700-0.849–B: 0.550-0.649–C:
blocks were measured using a Gretag Macbeth D19C densi 0.400-0.549=D: <0.400=F.
tometer with ANSI Status T filters. For the primary colors, Abrasion Resistance
only a single density was measured. For the secondary colors, Ablackpatch 10 cmx10 cm in size was printed at 100% ink
two densities were measured (magenta and yellow for red, laydown. The patch of printed media was then mounted on an
cyan and yellow for green, cyan and magenta for blue). For 45 aluminum plate and tested on a Taber Abraser, using a CS-10
each material, an overall average density for all seven colors abrasive wheel with 500 g weights hung from the two arms
was computed. The numerical averages were converted to attached to the abrasive wheels. The black reflected optical
grades according to the following scale: >1.30 A; 1.20 density was measured periodically at eight points around the
1.29=B; 1.10-1.19=C; 1.00- 1.09=D: <1.00=F. circular patch that was ground into the media with the abra
Linear Bar Code Printing 50 sive wheels. The test was terminated when the average black
Code 39 linear bar codes were printed at element sizes on reflected optical density of the eight points was reduced to
an Epson Stylus C88+ set for Text & Image mode (720 dots 70% of the initial average black reflected optical density. The
per inch or dpi). The bar codes were then Scanned using a number of cycles to the endpoint were graded according to the
Quick Check 800 barcode verifier. Codes receiving an overall following scale: >500A; 250-499-B; 100-249–C:
ANSI grade of A or B, with modulation excluded, were con 55 50-99=D; <50=F.
sidered to pass. When printed at 720 dpi, the bar code quality Test Results and Comparisons
for many types of inkjet media degrades when the number of The materials of the examples cited above are compared to
dots per element (narrow bars) is about six, so the data tables several types of commercially-available wide-format inkjet
below compare bar code grades for six-dot bar codes (at 720 graphics media and photo media in Table 15. The material
dpi, this is equivalent to a narrow bar width of 8.3 mil). 60 from U.S. Pat. No. 5,882,388 is also included, to show the
Solvent Resistance increase in performance due to the presence of the imaging
Printed blocks of primary and secondary colors were sub layer in this invention. Examples 1-4 illustrate the perfor
jected to the following solvent dip and rub test: Four cycles of mance benefits when this invention is practiced according to
10 minimmersion followed by 30 min removal; one last cycle the limits described in the claims. Examples 5-7 illustrate
of 10 min immersion, followed immediately by 10x double 65 how the performance deteriorates when an inappropriate
rub test with cotton swab soaked in the solvent (double binder resin or absorptive pigment is employed in the coating
rub-rub back and forth with light pressure applied to the formulation.
 US 8,133,556 B2
19 20
TABLE 1.5

Print Quality and Durability of Inkjet-Printed Media

Optical Linear Bar Solvent Accelerated Abrasion
Density Code Resistance Weathering Test
No. Material Printer Grade Grade Grade Grade Grade

1 U.S. Pat. No. 5,882,388 Epson Stylus C88+ F C C B C

2 Example 1 Epson Stylus C88+ C B A. B A.
3 Example 2 Epson Stylus C88+ A. A. A. C A.
lab sample
4 Example 2 Epson Stylus C88+ B A. A. C A.
Production
equipment
5 Example 3 Epson Stylus C88+ C B A. C A.
6 Example 4 Epson Stylus C88+ C C A. B A.
7 Example 5 Epson Stylus C88+ F F A. NT A.
8 Example 6 Epson Stylus C88+ C C F
9 Example 7 Epson Stylus C88+ C F C C C
O Competitive Epson Stylus C88+ A. C D C D
Wide-Format
Media A
1 Competitive Epson Stylus C88+ A. B D D
Wide-Format
Media B
2 Competitive Epson Stylus C88+ A. C D B D
Wide-Format
Media C
3 Competitive Epson Stylus C88+ A. B D
Photo Media D
4 Competitive Epson Stylus C88+ A. B
Photo Media E
5 U.S. Pat. No. 5,882,388 Epson PX-6250S* F NT C B C
6 Example 1 Epson PX-6250S* D NT A. A. A.
7 Example 2 Epson PX-62SOS* B NT A. B A.
lab sample
8 Example 2 Epson PX-62SOS* C NT A. B A.
Production
equipment
9 Example 3 Epson PX-62SOS* D NT A. B A.
20 Example 4 Epson PX-62SOS* C NT A. A. A.
21 Competitive Epson PX-62SOS* C NT D C D
Wide-Format
Media A
22 Competitive Epson PX-62SOS* C NT D D
Wide-Format
Media B
23 Competitive Epson PX-62SOS* B NT D B D
Wide-Format
Media C
24 Competitive Epson PX-62SOS* A. NT D F
Photo Media D
25 Competitive Epson PX-62SOS* B NT F F
Photo Media E
26 Example 1 LexmarkX9350 C NT A. C A.
27 Example 2 LexmarkX9350 B NT A. D A.
Production
equipment
28 Competitive LexmarkX9350 B NT D F
Photo Media F
29 Example 1 Epson Stylus C88+ B B A. A. A.
30 Example 2 Epson Stylus C88+ A. B A. A. A.
Production
equipment
31 Example 3 Epson Stylus C88+ C NT A. A. NT
32 U.S. Pat. No. 5,882,388 Canon i550 (dye- B NT F F A.
based ink)
*Epson DURABrite Ultra cyan, magenta, and black inks, with non-commercial yellow ink
# Stain-resistant coating from co-pending patent application applied at coating weight of 3.7 g/m'.
NT = not tested
 US 8,133,556 B2
21 22
As seen from Table 15, the materials of this invention black reflected optical density was also quite high for the dot
(Examples 1-4) perform well in all of the tests. Their printed matrix print test. These results indicate that this invention
optical density and barcode grades are Superior to those of the may be used to create a multi-technology digital imaging
material from U.S. Pat. No. 5,882.388. In comparison, the recording topcoat.
competitive wide-format inkjet samples are observed to lack Although the invention has been described with certain
Solvent resistance, weathering performance, and abrasion detail through the preceding specific embodiments, this detail
resistance, and some have weak bar code performance. The is for the primary purpose of illustration. Many variations and
competitive photo media samples have excellent print density modifications can be made by one skilled in the art without
and image acuity, but are completely lacking in solvent resis departing from the spirit and scope of the invention as
tance, weathering performance, and abrasion resistance. 10 described in the following claims.
The performance of the materials of this invention can be What is claimed is:
improved further by the post-print application of a stain 1. A two-layer receiver coating comprising:
resistant overcoat. Printed image density, weathering perfor A. A base layer comprising:
mance, and abrasion resistance can all be increased. 15 1. First pigment particles having (a) a number average
The inkjet inks used have significant effects on the perfor
mance of the printed media. The ink set used with the Epson particle size of 3-25 microns (um), and (b) at least one
PX-6250S printer is the most lightfast, while the ink set for of (i) an oil absorption value of at least 150 g oil/100
the Lexmark X9350 is the least lightfast. All three of the ink particles, and (ii) a pore Volume of at least about 1.2
sets used above are aqueous, pigmented inkjet inks. In order cubic centimeters per gram (cm/g); and
to realize the high performance illustrated above for the 2. Water-insoluble binder resin having a surface energy
media of this invention, the use of pigmented inks is preferred greater than 40 dyne per centimeter (dyn/cm);
since dyes are soluble and are less lightfast than pigments. the first pigment particles and water-insoluble binder
Line 32 in Table 15 is indicative of the general performance resin present at a weight ratio of 0.75 to 2; and
level obtainable with dye-based inkjet inks. B. An imaging layer comprising:
Suitability for Other Printing Technologies 25 1. Second pigment particles having (a) a number average
The media of this invention may be used with more than particle size of 0.01-4 (lum) aggregated to form an
just aqueous inkjet inks. Since the resistance to organic Sol inter-particle region of Submicron pores, and (b) a
vents and glycol ethers is strong, solvent-based and UV cur pore volume of 0.4 to 2.2 cm/g; and
able inkjet inks do not damage these topcoats, and can be used 2. Water-insoluble binder resin having a surface energy
for printing. 30 greater than 40 (dyn/cm);
In addition to inkjet printers, the media of this invention the second pigment particles and water-insoluble binder
may be used to record images produced by other printing resin present at a weight ratio of 0.75 to 2.
technologies. It is receptive to electrophotographic toners 2. The receiver coating of claim 1 in which the first and
used in laser printing and to the inks used to impregnate dot second pigment particles are at least one of silica and alu
35 mina.
matrix ribbons. Test results with these technologies are shown 3. The receiver coating of claim 1 in which the first pigment
in Table 16. The grades for reflected optical density of color particles are silica.
prints are for the same test procedure and grading scheme as
outlined above for inkjet print testing. For the monochrome 4. The receiver coating of claim3 in which the first pigment
printers, the black density alone has been graded on the same particles have a Mohs hardness of 4-5.
scale. 40 5. The receiver coating of claim 1 in which the water
insoluble binder resin of the base layer is the same as the
TABLE 16 water-insoluble binder resin of the imaging layer.
6. The receiving coating of claim 1 in which the water
Tests Results from Alternative Printing Technologies insoluble binder resin in both the base and imaging layers is
45 crosslinked.
Average Optical 7. The receiver coating of claim 1 in which at least one of
Optical Density
Density - Grade - the base and imaging layers further comprises a UV stabilizer.
Number Material Printer Colors Black 8. The receiver coating of claim 1 in which the base layer
33 Example 2 - Lexmark T644 A.
has a coating weight of 8-32 g/m.
Production Equipment Monochrome
50 9. The receiver coating of claim 1 in which the imaging
Laser layer has a coating weight of 0.5-1.2 g/m.
34 Example 2 - Lexmark C920 O.87 A. 10. The receiver coating of claim 1 in which the pigment
Production Equipment Color Laser particles of the imaging layer comprise at least one of a
35 OfficeMax Copy Lexmark C920 O.89 B
Paper SKU# 06000374 Color Laser boehmite type of hydrated alumina.
36 Example 2 - Brady SLV-DAT- A. 55 11. The receiver coating of claim 1 in which the water
Production Equipment PTR Dot soluble binder resin of both the base and imaging layers
Matrix with comprises a non-cationic, alcohol-soluble, water-insoluble
R5000 ribbon
compound dissolved in an alcoholic liquid medium.
12. The receiver coating of claim 1 in which the water
For both the monochrome and color laser printers, the edge 60 soluble binder resin of both the base and imaging layers
acuity was sufficient to print readable text with an 8 pt Times comprises an alcohol-soluble, melt-polymerized polyamide
New Roman font. The reflected optical densities of images consisting essentially of recurring carboxamido groups and at
were excellent for black blocks. For color blocks printed on a least two different species of recurring hydrocarbylene
Lexmark C920 Color Laser, the reflected optical densities groups selected from the group consisting of aliphatic and
were lower than those obtainable in inkjet printing, but were 65 alicyclic groups of 2 to 40 carbonatoms as integral parts of the
approximately equal to the densities obtained when the same main polymer chain, and having at least 3 different recurring
file was printed onto a standard grade of copy paper. The polyamide repeat units.
 US 8,133,556 B2
23 24
13. The receiver coating of claim 1 in which the water- mer-coated fabric or mesh, vinyl, polyethylene, polypropy
soluble binder resin of both the base and imaging layers is an lene, polyester and polystyrene.
aqueous dispersion of a non-cationic, water-insoluble polya- 16. The receiver coating of claim 1 bearing an image
mide. printed by at least one of an aqueous inkjet, solvent inkjet,
14. The receiver coating of claim 1 on a Support. 5 UV-curable inkjet, laser and dot matrix printer.
15. The receiver coating of claim 14 in which the support is
one of paper, polymer-coated paper, synthetic paper, poly- k . . . .