WATER RESISTANT INK JET PRINTABLE SHEET

FEUILLE IMPRIMABLE PAR JET D'ENCRE RESISTANT A L'EAU

English Abstract

A water resistant coating composition for ink jet recordable substrates having
a pH of less than 7, which includes: (a) an aqueous polyurethane dispersion;
and (b) an aqueous solution of a nitrogen-containing polymeric dye fixative
compound. When applied to a suitable substrate, the coating composition allows
for the recording of sharp, water-fast images. A coated ink jet recordable
substrate is also disclosed, which includes a substrate having at least one
side and at least one side of the substrate has a coating layer derived from
the above described coating composition.

French Abstract

L'invention concerne une composition de revêtement résistant à l'eau destinée à des substrats imprimables par jet d'encre possédant un pH inférieur à 7 qui comprend: (a) une dispersion de polyuréthanne aqueux; et (b) une solution aqueuse d'un composé fixatif de colorant polymère contenant de l'azote. Lorsqu'elle est appliquée à un substrat adapté, la composition de revêtement permet une impression de dessins bien nette et résistant à l'eau. Un substrat imprimable par jet d'encre revêtu est également décrit, lequel comprend au moins un côté et au moins un côté du substrat étant revêtu d'une couche dérivée de la composition de revêtement décrite ci-dessus.

Claims

-74-
In the claims:
1. An ink jet recordable substrate coating composition
having a pH less than 7 comprising:
(a) an aqueous polyurethane dispersion; and
(b) an aqueous solution of a nitrogen-containing
polymeric dye fixative compound.
2. The ink jet recordable substrate coating composition
of claim 1 wherein the polyurethane is selected from the group
consisting of anionic polyurethanes, cationic polyurethanes,
nonionic polyurethanes and mixtures thereof.
3. The ink jet recordable substrate coating composition
of claim 2 wherein the aqueous anionic polyurethane dispersion
comprises one or more anionic polyurethanes selected from the
group consisting of aromatic polyether polyurethanes,
aliphatic polyether polyurethanes, aromatic polyester
polyurethanes, aliphatic polyester polyurethanes, aromatic
polycaprolactam polyurethanes, and aliphatic polycaprolactam
polyurethanes.
4. The ink jet recordable substrate coating composition
of claim 2 wherein the aqueous anionic polyurethane has one or
more acid groups selected from the group consisting of
carboxylic acid, sulfonic acid and mixtures thereof.
5. The ink jet recordable substrate coating composition
of claim 1 wherein the aqueous solution of a nitrogen-
containing polymeric dye fixative compound comprises a polymer
comprising monomer residues derived from one or more nitrogen-
containing monomers selected from the group consisting of:

-75-
<IMG>
wherein R1 is selected independently for each occurrence in
each structure from the group consisting of H and C1 to C3
aliphatic; R2 is independently for each structure a divalent
linking group selected from the group consisting of C2 to C20
aliphatic hydrocarbon, polyethylene glycol and polypropylene
glycol; R3 is independently for each occurrence in each
structure selected from the group consisting of H, C1 to C22
aliphatic hydrocarbon and a residue from the reaction of the
nitrogen with epichlorohydrin; Z is selected from the group
consisting of -O- and -NR4-, where R4 is selected from the

-76-
group consisting of H and CH3; and X is selected from the group
consisting of halides and methylsulfate.
6. The ink jet recordable substrate coating composition
of claim 1 wherein the aqueous polyurethane dispersion is
present at from 10 to 70 percent by weight of the ink jet
recordable substrate coating composition and the aqueous
solution of a nitrogen-containing polymeric dye fixative
compound is present at from 30 to 90 percent by weight of the
ink jet recordable substrate coating composition.
7. The ink jet recordable substrate coating composition
of claim 1 prepared by mixing the nitrogen-containing
polymeric dye fixative compound (b) into the aqueous
polyurethane dispersion (a).
8. A method of coating an ink jet recordable substrate
comprising:
(a) providing an ink jet recordable substrate
having a top surface and a bottom surface;
(b) providing a coating composition having a pH
less than 7 comprising:
(i) an aqueous polyurethane dispersion; and
(ii) an aqueous solution of a nitrogen-
containing polymeric dye fixative compound;
(c) applying the coating composition to at least
one side of the ink jet recordable substrate.
9. The method of claim 8 wherein the ink jet recordable
substrate comprises a microporous substrate having a top
surface and a bottom surface and comprising:
(a) a matrix comprising a polyolefin;
(b) a finely divided particulate siliceous filler
distributed throughout the matrix; and

-77-
(c) a network of interconnecting pores
communicating throughout the microporous substrate, said pores
constituting at least about 35 percent by volume of said
microporous substrate.
10. The method of claim 9 wherein the polyolefin
comprises one or both selected from the group consisting of a
linear high molecular weight polyethylene having an intrinsic
viscosity of at least 10 deciliters/gram and a linear high
molecular weight polypropylene having an intrinsic viscosity
of at least 5 deciliters/gram.
11. The method of claim 9 wherein the siliceous filler
constitutes from 50 percent to 90 percent by weight of the
microporous substrate.
12. The method of claim 8 wherein the aqueous
polyurethane dispersion in (b)(i) comprises a polyurethane
selected from the group consisting of anionic polyurethanes,
cationic polyurethanes, nonionic polyurethanes, and mixtures
thereof.
13. The method of claim 12 wherein the anionic
polyurethane is selected from the group consisting of aromatic
polyether polyurethanes, aliphatic polyether polyurethanes,
aromatic polyester polyurethanes, aliphatic polyester
polyurethanes, aromatic polycaprolactam polyurethanes, and
aliphatic polycaprolactam polyurethanes.
14. The method of claim 12 wherein the aqueous anionic
polyurethane has one or more acid groups selected from the
group consisting of carboxylic acid, sulfonic acid and
mixtures thereof.

-78-
15. The method of claim 8 wherein the aqueous solution
of a nitrogen-containing polymeric dye fixative compound
comprises a polymer comprising monomer residues derived from
one or more nitrogen-containing monomers selected from the
group consisting of:
<IMG>
wherein R1 is selected independently for each occurrence in
each structure from the group consisting of H and C1 to C3
aliphatic; R2 is independently for each structure a divalent
linking group selected from the group consisting of C2 to C20
aliphatic hydrocarbon, polyethylene glycol and polypropylene

-79-
glycol; R3 is independently for each occurrence in each
structure selected from the group consisting of H, C1 to C22
aliphatic hydrocarbon and a residue from the reaction of the
nitrogen with epichlorohydrin; Z is selected from the group
consisting of -O- and -NR4-, where R4 is selected from the
group consisting of H and CH3; and X is selected from the group
consisting of halides and methylsulfate.
16. The method of claim 8 wherein the aqueous
polyurethane dispersion is present at from 10 to 70 percent by
weight of the ink jet recordable substrate coating composition
and the aqueous solution of a nitrogen-containing polymeric
dye fixative compound is present at from 30 to 90 percent by
weight of the coating composition.
17. The method of claim 8 wherein the nitrogen-
containing polymeric dye fixative compound is a polyamide
amine reacted with epichlorohydrin.
18. The method of claim 8 wherein the coating
composition has a total resin solids of from 1 to 35 wt.%
based on the total weight of the coating composition.
19. The method of claim 8 wherein the aqueous
polyurethane dispersion in (b)(i) comprises an anionic
polyurethane and the coating composition is prepared by mixing
the nitrogen-containing polymeric dye fixative compound
(b)(ii) into the aqueous polyurethane dispersion (b)(i).
20. The method of claim 8 wherein the coating
composition is applied to both sides of the ink jet recordable
substrate.
21. A coated ink jet recordable substrate coated using
the method of claim 8.

-80-
22. A coated microporous substrate comprising:
(a) a microporous substrate having an upper
surface and a lower surface comprising:
(i) a matrix comprising a polyolefin;
(ii) a finely divided particulate siliceous
filler distributed throughout the matrix; and
(iii) a network of interconnecting pores
communicating throughout the microporous substrate, said pores
constituting at least about 35 percent by volume of said
microporous substrate; and
(b) a coating layer on at least one surface of the
microporous substrate, said coating layer comprising:
(i) a polymeric nitrogen-containing dye
fixative compound; and
(ii) one or more polyurethanes selected from
the group consisting of anionic polyurethanes, cationic
polyurethanes, nonionic polyurethanes, and mixtures thereof.
23. The coated microporous substrate of claim 22 wherein
the polyurethane is an anionic polyurethane, and the aqueous
anionic polyurethane has one or more acid groups selected from
the group consisting of carboxylic acid, sulfonic acid and
mixtures thereof.
24. The coated microporous substrate of claim 22 wherein
the polymeric nitrogen-containing dye fixative compound
comprises a polymer comprising monomer residues derived from
one or more nitrogen-containing monomers selected from the
group consisting of:

-81-
<IMG>
wherein R1 is selected independently for each occurrence in
each structure from the group consisting of H and C1 to C3
aliphatic; R2 is independently for each structure a divalent
linking group selected from the group consisting of C2 to C20
aliphatic hydrocarbon, polyethylene glycol and polypropylene
glycol; R3 is independently for each occurrence in each
structure selected from the group consisting of H, C1 to C22
aliphatic hydrocarbon and a residue from the reaction of the
nitrogen with epichlorohydrin; Z is selected from the group
consisting of -O- and -NR4-, where R4 is selected from the

-82-
group consisting of H and CH3; and X is selected from the group
consisting of halides and methylsulfate.
25. The coated microporous substrate of claim 22 wherein
the polyurethane is present at from 10 to 70 percent by weight
of the coating layer and the nitrogen-containing polymeric dye
fixative compound is present at from 30 to 90 percent by
weight of the coating layer.
26. The coated microporous substrate of claim 22 wherein
the nitrogen-containing polymeric dye fixative compound is a
polyamide amine reacted with epichlorohydrin.
27. The coated microporous substrate of claim 22 wherein
the polyolefin comprises one or both selected from the group
consisting of a linear high molecular weight polyethylene
having an intrinsic viscosity of at least about 10
deciliters/gram and a linear high molecular weight
polypropylene having an intrinsic viscosity of at least about
deciliters/gram.
28. The coated microporous substrate of claim 22 wherein
the siliceous filler constitutes from 50 percent to 90 percent
by weight of the microporous substrate.
29. The coated microporous substrate of claim 22 wherein
the coating layer penetrates into at least the first 1 micron
of the surface of the microporous substrate.
30. The coated microporous substrate of claim 22 wherein
the microporous substrate has a thickness of from 0.5 to 100
mils.
31. The coated microporous substrate of claim 22 wherein
the coat weight is from 0.001 g/m2 to 50 g/m2.

-83-
32. A multilayer article comprising an ink jet
recordable substrate at least partially connected to a
substantially nonporous material, said ink jet recordable
substrate at least partially coated with a substantially
water-resistant coating composition, and at least one of said
ink jet recordable substrate and substantially nonporous
material at least partially coated with a friction-reducing
coating composition.
33. The multilayer article of Claim 32 wherein said
substantially water-resistant coating composition comprises:
(a) an aqueous polyurethane dispersion; and
(b) a cationic nitrogen-containing polymeric dye
fixative material at least partially dissolved in an aqueous
medium.
34. The multilayer article of claim 32 wherein said
friction-reducing coating composition comprises a lubricant
and a resin.
35. The multilayer article of claim 32 wherein said
lubricant comprises polysiloxane.
36. The multilayer article of claim 32 wherein said
resin comprises styrene acrylic polymer.
37. A method for producing a multilayer article
comprising the steps of:
(a) providing a ink jet recordable substrate
having a top surface and a bottom surface;
(b) providing a substantially water-resistant
coating composition comprising a stable dispersion of:
(i) an aqueous polyurethane dispersion; and

-84-
(ii) a cationic nitrogen-containing polymeric
dye fixative material at least partially dissolved in an
aqueous medium;
(c) at least partially applying said coating
composition to at least one surface of said ink jet recordable
substrate;
(d) at least partially connecting said ink jet
recordable substrate of (c) to a substantially nonporous
material having a top surface and a bottom surface;
(e) providing a friction-reducing coating
composition; and
(f) at least partially applying said friction-
reducing coating composition to at least one
surface of at least one of said ink jet
recordable substrate and said substantially
nonporous material.
38. A multilayer article comprising an ink jet
recordable substrate, at least one substantially nonporous
material and a magnetizable material.
39. The multilayer article of claim 38 wherein said
magnetizable material is an oxide material.
40. The multilayer article of claim 39 wherein said
oxide material is selected from ferrous oxide, iron oxide,
and mixtures thereof.
41. The multilayer article of claim 38 wherein said
magnetizable material is a slurry.
42. The multilayer article of claim 38 wherein said
magnetizable material has a coercivity of from 200 to 5000.
43. The multilayer article of claim 38 wherein said
magnetizable material is at least partially connected to at
least one material selected from a protective material, a
carrier material or an adhesive material.
44. The multilayer article of claim 43 wherein said
protective material is selected from polyethylene
teraphthalate polyester and combinations thereof.

-85-
45. The multilayer article of claim 43 wherein said
carrier material is selected from polyethylene
teraphthalate, polyester and combinations thereof.
46. The multilayer article of claim 43 wherein said
adhesive material is selected from polyvinyl acetate,
starches, gums, polyvinyl alcohol, animal glues, acrylics,
epoxies, polyethylene-containing adhesives, and rubber-
containing adhesives.
47. The multilayer article of claim 43 wherein said
protective material is at least partially connected to said
magnitizable material, said magnetizable material is at
least partially connected to said carrier material, and said
carrier material is at least partially connected to said
adhesive material.
48. The multilayer article of claim 38 wherein said
magnetizable material is at least partially connected to
said ink jet recordable substrate.
49. The multilayer article of claim 38 wherein said
magnetizable material is at least partially connected to
said substantially nonporous material.
50. The multilayer article of claim 38 wherein said ink
jet recordable substrate is~ a microporous substrate.
51. The multilayer article of claim 38 wherein said
substantially nonporous material is polyvinyl chloride.
52. The multilayer article of claim 38 wherein said
magnetizable material is at least partially coated with a
substantially water-resistant coating composition.
53. The multilayer article of claim 52 wherein said
substantially water-resistant coating composition is the
coating composition of claim 1.
54. The multilayer article of claim 52 wherein at least
one surface of said ink jet recordable substrate is at least
partially coated with a substantially water-resistant
coating composition.

-86-
55. The multilayer article of claim 52 wherein at least
one surface of said substantially nonporous material is at
least partially coated with a substantially water-resistant
coating composition.
56. The multilayer article of claim 38 wherein at least
one surface of said magnetizable material is at least
partially coated with a friction reducing coating
composition.
57. The multilayer article of claim 56 wherein said
friction reducing coating composition further comprises at
least one lubricant and at least one resin.
58. The multilayer article of claim 38 wherein said ink
jet recordable substrate is at least partially coated with a
friction reducing coating composition.
59. The multilayer article of claim 38 wherein said
substantially nonporous material is at least partially
coated with a friction reducing coating composition.
60. The multilayer article of claim 38 further
comprising a release liner at least partially connected to
at least one surface of said multlayer article.
61. A multilayer article comprising a microporous
substrate at least partially connected to a first
substantially nonporous material; said first substantially
nonporous material at least partially connected to a second
substantially nonporous material; said second substantially
nonporous material at least partially connected to a third
substantially nonporous material; said third substantially
nonporous material comprising a magnetizable material.
62. A multlayer article comprising a magnetizable
material at least partially connected to an adhesive
material and said adhesive material at least partially
connected to a substantially nonporous material.
63. A multilayer article comprising a magnetizable
material at least partially connected to an adhesive

-87-
material and said adhesive material at least partially
connected to an ink jet recordable material.
64. A multilayer article comprising a magnetizable
material, an ink jet recordable substrate and a
substantially nonporous material wherein said ink jet
recordable substrate is at least partially coated with a
substantially water-resistant coating composition, and at
least one of said ink jet recordable substrate and
substantially nonporous material is at least partially
coated with a friction-reducing coating composition.
65. A multilayer article comprising an ink jet
recordable substrate, at least one substantially nonporous
material and a data transmittance/storage device.
66. The multilayer article of claim 65 wherein said data
transmittance/storage device comprises a carrier material.
67. The multilayer article of claim 66 wherein said
carrier material is polyvinylchloride.
68. The multilayer article of claim 65 wherein said data
transmittance/storage device comprises a barrier material.
69. The multilayer article of claim 68 wherein said data
transmittance/storage device can be at least partially
connected to said barrier material using an adhesive
material.
70. The multilayer article of claim 68 wherein at least
one surface of said barrier material is at least partially
coated with a coating composition selected from a
substantially water-resistant coating composition, or a
friction reducing coating composition or a combination
thereof.
71. The multilayer article of claim 68 wherein said
barrier material comprises a substantially nonporous
material.
72. A multilayer article comprising a microporous
substrate at least partially connected to a substantially
nonporous material, said microporous substrate at least

-88-
partially coated with a substantially water-resistant coating
composition, said coating composition comprising a stable
dispersion of:
(a) an aqueous polyurethane dispersion; and
(b) a cationic nitrogen-containing polymeric dye
fixative material at least partially dissolved in an aqueous
medium.
73. The multilayer article of claim 72 wherein said
microporous substrate comprises:
(a) a polyolefin;
(b) a particulate silica material; and
(c) a porosity wherein the pores constitute at
least 35 percent by volume of the microporous substrate.
74. The multilayer article of claim 73 wherein said
polyolefin is chosen from polyethylene, polypropylene, and
mixtures thereof.
75. The multilayer article of claim 74 wherein said
polyethylene comprises an essentially linear high molecular
weight polyethylene having an intrinsic viscosity of at least
deciliters/gram, and said polypropylene comprises an
essentially linear high molecular weight polypropylene having
an intrinsic viscosity of at least 5 deciliters/gram.
76. The multilayer article of claim 73 wherein said
particulate silica material comprises precipitated silica.
77. The multilayer article of claim 72 wherein said
aqueous polyurethane dispersion is chosen from aqueous
dispersions of anionic polyurethanes, cationic polyurethanes,
nonionic polyurethanes and mixtures thereof.

-89-
78. The multilayer article of claim 77 wherein said
anionic polyurethane is chosen from aromatic polyether
polyurethanes, aliphatic polyether polyurethanes, aromatic
polyester polyurethanes, aliphatic polyester polyurethanes,
aromatic polycaprolactam polyurethanes, aliphatic
polycaprolactam polyurethanes, and mixtures thereof.
79. The multilayer article of claim 72 wherein said
substantially nonporous material is chosen from substantially
nonporous thermoplastic polymers, substantially nonporous
metalized thermoplastic polymers, substantially nonporous
thermoset polymers, substantially nonporous elastomerics,
substantially nonporous metals and mixtures thereof.
80. A method for producing a multilayer article
comprising the steps of:
(a) providing a microporous substrate having a top
surface and a bottom surface;
(b) providing a substantially water-resistant coating
composition comprising a stable dispersion of:
a. an aqueous polyurethane dispersion; and
b. a cationic nitrogen-containing polymeric dye
fixative material at least partially dissolved in an
aqueous medium;
(c) at least partially applying said coating composition
to at least one surface of said microporous
substrate;
(d) at least partially connecting said microporous
substrate of (c) to a substantially nonporous
material.
81. A substantially water-resistant ink jet recordable
substrate coating composition comprising:
a. an aqueous polyurethane dispersion;

-90-
b. a cationic nitrogen-containing polymeric
dye fixative compound; and
c. an acrylic polymer,
wherein said coating composition has a pH of
7 or less.
82. The coating composition of claim 81 wherein said
polyurethane dispersion is chosen from anionic polymers,
cationic and nonionic polyurethanes dispersible in water.
83. The coating composition of claim 81 wherein said
polyurethane dispersion comprises a polyisocyanate and a
polyol.
84. The coating composition of claim 81 wherein said
cationic nitrogen-containing polymeric dye fixative
compound comprises polyamine and epichlorohydrin.
85. The coating composition of claim 81 wherein said
acrylic polymer comprises a cationic acrylic polymer.
86. The coating composition of claim 85 wherein said
cationic acrylic polymer is chosen from polyacrylates,
polymethacrylates, polyacrylonitriles and polymers having
monomer types selected from acrylonitrile, acrylic acid,
acrylamide and mixtures thereof.
87. A method of preparing a substantially water-
resistant ink jet recordable substrate coating
composition comprising the step of mixing a nitrogen-
containing polymeric dye fixative compound with an
aqueous polyurethane dispersion and an acrylic polymer to
produce a substantially homogeneous mixture having a pH
of 7 or less.

-91-
88. A substantially water-resistant ink jet recordable
substrate at least partially coated with a coating
composition comprising:
a. an aqueous polyurethane dispersion;
b. an aqueous solution of a cationic nitrogen-
containing polymeric dye fixative compound;
and
c. an acrylic polymer,
wherein said coating composition has a pH of 7 or
less.
89. The ink jet recordable substrate of claim 88 further
comprising bonding said substrate to at least one layer
of a substantially nonporous material.

Description

CA 02531021 2005-12-22
WO 2005/023543 PCT/US2004/026892
SPIRO COMPOUNDS AND METHODS FOR THE MODULATION OF
CHEMOKINE RECEPTOR ACTIVITY
This application claims benefit of U.S. Provisional
Application Serial No. 60/501,407, filed September 10,
2003, the entire disclosure of which is hereby
incorporated by reference.
TECHNICAL FIELD.
The present invention relates to novel spiro compounds
and a method of modulating chemokine receptor activity
using these compounds. The present invention is also
directed to novel spiro compounds which are useful in the
prevention or treatment of diseases associated with the
modulation of CCR5 chemokine receptor activity. The
present invention is further directed to a method of
blocking cellular entry of HIV in a subject and to
compositions using these compounds.
BACKGROUND ART
Chemokines are chemotactic cytokines that are released by
a wide variety of cells to attract macrophages, T cells,
eosinophils, basophils and ~neutrophils to sites of
inflammation and they also play a role in the maturation
of cells of the immune system., Chemokines play an
important role in immune and inflammatory responses in
various diseases and disorders, including asthma,
rhinitis and allergic diseases, as well as autoimmune
1,

CA 02531021 2005-12-22
WO 2005/023543 PCT/US2004/026892
- 1 -
WATER RESISTANT INK JET PRINTABLE SHEET
BACKGROUND OF THE INVENTION
[0001] The present invention is directed to an ink
jet recordable substrate. In particular, the present invention
relates to a substantially water-resistant, at least partially
coated, ink jet recordable substrate. The present invention
is further directed to a multilayer article comprising the ink
jet recordable substrate at least partially connected to a
substantially nonporous material. Moreover, the present
invention is directed to a process for producing the
multilayer article. This application claims,priority to
10/654,377 filed on September 3, 2003; 10/654,119 filed on
September 3, 2003; and 10/654,433 filed on September 3, 2003.
[0002] It is known in the art to size paper with various
sizing components for the purpose of retarding or preventing
penetration of liquids into the structure. For example,
"internal sizing°' consists of introducing sizing materials
into the pulp during the paper making operation. The sizing
materials are precipitated onto the fibers primarily for the
purpose of controlling penetration of liquids into the final
dry paper. Further, "surface sizing" involves the application
of dispersions of film-forming substances such as converted
starches, gums, and modified polymers, to previously formed
,.' paper. Surface sizing imparts strength to the paper.
'[0003] The use of sized paper to print with an ink jet
printer containing predominantly water-based inks may yield
imaged papers which have a tendency to curl into tubes. The
use of un-sized paper may result migration of the image
through the sheet and interference with the image on the other
side, if one side of the imaged sheet comes into contact with
water.
[0004] Various attempts have been made in the art to
overcome the forgoing problems. For example, United States
Patent 5,709,976 discloses a paper substrate coated with a

CA 02531021 2005-12-22
WO 2005/023543 PCT/US2004/026892
_ 2 _
hydrophobic barrier material and an image-receiving layer.
United States Patent 6,140,412 teaches a process for coating
paper with an aqueous cationic polyurethane resin solution.
Japanese Patent (JP) 11216945 discloses a process for coating
paper with a composition that includes polyvinylpyrrolidone, a
polyurethane resin emulsion, polyvinyl alcohol and a cationic
resin. Further, United States Patent 6,020,058 discloses an
acrylic composition and United States Patent 6,025,068
discloses a urethane-acrylic co-polymer.
[0005] United States Patents 4,861,644 and 5,196,262
disclose a microporous material sheet which includes a matrix
of linear ultrahigh molecular weight polyolefin, a large
proportion of finely divided water-insoluble siliceous filler,
and interconnecting pores. U.S. Patent No: 6,025,068 teaches
a method of coating a microporous polyolefin substrate with a
coating composition which includes a binder dissolved or
dispersed in a volatile aqueous liquid medium.
[0006] Another coating composition for ink jet recording
materials is disclosed in Japanese Patent (JP) 2001-184881.
This reference discloses a coating composition that includes a
nonionic or anionic polyurethane and the,reaction product of a
monomeric secondary amine and epichlorohydrin. Japanese
Patents (JP) 11268406 and (JP) 2000153667 disclose cationic
polyurethanes useful in waterproofing coatings for ink jet
printing substrates.
[0007] There remains a need for an ink jet recording medium
that is durable, water-resistant and able to record sharp
images when an ink jet printing ink is applied thereto.
SUMMARY OF THE INVENTION
[0008] The present invention is directed to a substantially
water-resistant coating composition for an ink jet recordable
substrate. The coating composition has a pH of less than 7 and
includes:
(a) an aqueous polyurethane dispersion; and

CA 02531021 2005-12-22
WO 2005/023543 PCT/US2004/026892
- 3 _
(b) an aqueous solution of a nitrogen-containing
polymeric dye fixative compound.
[00097 In a non-limiting embodiment, the coating
composition of the present invention can further include an
acrylic polymer.
[0010] The present invention is also directed to a method
of at least partially coating an ink jet recordable substrate
in which the above-described coating composition is applied to
the substrate.
[0011] The present invention is further directed to an ink
jet recordable substrate wherein at least one side of the
substrate has at least a partial coating layer of the above-
described coating composition.
[0012] The present invention is also directed to a
multilayer article comprising a microporous substrate at least
partially connected to a substantially nonporous material,
said microporous substrate at least partially coated with the
above-described coating composition.
DETAILED DESCRIPTION OF THE INVENTION
[0013] Unless otherwise indicated, all numbers or
expressions referring to quantities of ingredients, reaction
conditions, etc. used herein are to be understood as modified
in all instances by the term "about."
[0014] Unless otherwise indicated, all references to
(meth)acrylic, (meth)acrylate and (meth)acrylamide monomers is
meant to include both the methacrylic and acrylic species.
[00157 Various numerical ranges are disclosed in this
._ patent application. Because these ranges are continuous, they
include every value between the minimum and maximum values.
Unless expressly indicated otherwise, the various numerical
' ranges specified in this application are approximations.
[00167 The coating composition of the present invention
includes an aqueous polyurethane dispersion and an aqueous

CA 02531021 2005-12-22
WO 2005/023543 PCT/US2004/026892
- 4 -
solution of a nitrogen-containing polymeric dye fixative
compound.
[0017] Suitable polyurethanes for use in the present
invention can include any polyurethane that is substantially
' dispersible in water. Non-limiting examples of aqueous
polyurethane dispersions for use in the present invention can
include any known water-dispersible nonionic polyurethanes,
anionic polyurethanes, cationic polyurethanes, and mixtures
thereof.
[0018] The mixing of an anionic polymer and a cationic
polymer can result in a polysalt which is often insoluble in
water and other solvents. In the present invention, it has
been found that the addition of an aqueous solution of a
cationic nitrogen-containing polymer to an aqueous anionic
polyurethane dispersion results in a stable dispersion which
is useful as a coating composition for an ink jet recordable
substrate. However, a reversal in the order of addition such
that the anionic polyurethane dispersion is added to the
aqueous solution of a cationic nitrogen-containing polymer,
can result in the formation and precipitation of a polysalt
from the aqueous solution.
[0019] In a non-limiting embodiment of the present
invention, an aqueous dispersidn of polyurethane resin
comprising particles of a polyurethane polymer dispersed in an
aqueous medium can be used in the present invention.
[0020] The polyurethane for use in the present invention
can be prepared by a variety of methods known in the art. For
example, a polyisocyanate can be reacted with a polyol to form
a prepolymer, such as an isocyanate-terminated prepolymer. As
used herein and the claims, the term "polyisocyanate" refers
to a compound with more than one isocyanate group, such as but
not limited to a diisocyanate. Non-limiting examples of
suitable diisocyanates for use in the present invention ,
include can include but are not limited to toluene
diisocyanate, hexamethylene diisocyanate, isophorone

CA 02531021 2005-12-22
WO 2005/023543 PCT/US2004/026892
- 5 -
diisocyanate and dicyclohexyl methane diisocyanate. Non-
limiting examples of suitable three or more functional
isocyanates can include but are not limited to the reaction
products of diisocyanates with polyols such as trimethylol
propane, glycerol and pentaerythritol. In a non-limiting
embodiment, the polyisocyanate for use in the present
invention can include Desmodur which is commercially available
from Bayer Corporation.
[0021] As used herein and in the claims, the term "polyol"
refers to a compound with more than one hydroxyl group. Non-
limiting examples of suitable polyols for use in the present
invention can include polyols such as but not limited to those
from which the polyisocyanate can be prepared, polyester
polyols and polyether polyols.
[0022] The reaction of the polyisocyanate and polyol can be
carried out in the presence of an organic solvent. Suitable
organic solvents can include but are not limited to n-methyl
pyrrolidone, tetrahydrofuran and glycol ether.
[0023] In a non-limiting embodiment, the prepolymer can be
reacted with a di-hydroxyl compound having an acid group, such
as dimethylol propionic acid, to produce a polyurethane with
at least one pendant acid group. The acid group can include a
carboxylic acid group or a sulfonic acid group. The
polyurethane having a pendant acid group can then be reacted
with a base to produce an anionic polyurethane.
[0024] An aqueous dispersion of an anionic polyurethane
resin for use in the invention can include particles of an
anionic polyurethane polymer dispersed in an aqueous medium.
The polyurethane polymer can have at least one pendent acid
group which may be neutralized in the presence of a base to
form anionic group(s), which can stabilize the dispersion.
The base can be selected from the group consisting of an
inorganic base, ammonia, amine and mixtures thereof.
[0025] The anionic polyurethane for use in the invention
can be prepared by methods known in the ax~t. In a non-

CA 02531021 2005-12-22
WO 2005/023543 PCT/US2004/026892
- 6 -
limiting embodiment, (i) a polyisocyanate, (ii) a polyol,
(iii) a compound having an acid group, and optionally (iv) a
chain-extending compound such as a polyamine or hydrazine, can
be reacted to produce an anionic polyurethane.
[0026] In a non-limiting embodiment, the isocyanate-
terminated prepolymer can be dispersed in water in the
presence of a base, and then chain extended by adding the
polyamine. In a further non-limiting embodiment, the
prepolymer is chain extended in an organic solvent solution
and then the polyurethane polymer is dispersed in water in the
presence of the base.
[0027] Suitable anionic polyurethanes for use in the
present invention can include anionic polyurethanes based on
aromatic polyether polyurethanes, aliphatic polyether
polyurethanes, aromatic polyester polyurethanes, aliphatic
polyester polyurethanes, aromatic polycaprolactam
polyurethanes, and/or aliphatic polycaprolactam polyurethanes.
In a non-limiting embodiment, an anionic polyurethane
dispersion for use in the present invention can be
commercially obtained from Crompton Corporation under the
trade name WitcoBond~.
[0028] In alternate non-limiting embodiments, the aqueous
anionic polyurethane dispersion of the present invention can _
contain up to 70 wt.o, or up to 65 wt.%, or up to 60 wt.o, or
up to 50 wt.o of the anionic polyurethane. In further
alternate non-limiting embodiments, the aqueous anionic
polyurethane dispersion includes at least 1 wt.%, or at least
wt.o, or at least 10 wt.o, or at least 20 wt.% of the
anionic polyurethane. The amount of anionic polyurethane in
the aqueous anionic polyurethane dispersion is not critical.
In general, the amount should not be so much as to cause the
dispersion itself or the mixture with the nitrogen-containing
polymer to be unstable, or so little that the coating
composition cannot provide sufficient water and rub
resistance, or causes the dispersion itself to be unstable.

CA 02531021 2005-12-22
WO 2005/023543 PCT/US2004/026892
_ 7 _
The anionic polyurethane can be present in the aqueous anionic
polyurethane dispersion in any range of values inclusive of
those stated above.
[0029] The cationic polyurethane dispersion for use in the
present invention can include a wide variety of known water-
dispersible cationic polyurethanes. Non-limiting examples can
include but are not limited to those cationic polyurethanes
which are commercially available from Crompton Corporation
under the trade name Witcobond, such as, Witcobond W-213 and
W-215 formulations.
[0030] The cationic polyurethane can be prepared by various
methods known in the art. United States Patent 3,470,310
discloses the preparation of a water dispersion of
polyurethane which contains salt-type groups bonded into the
polyurethane. United States Patent 3,873,484 discloses an
aqueous dispersion of polyurethane prepared from quaternized
polyurethane prepolymer prepared by reacting alkoxylated diol,
N-alkyl dialkanolamine, organic diisocyanate and quaternizing
with dialkyl sulfate quaternizing agent. United States Patent
6,221,954 teaches a method for making polyurethane prepolymer
in which N-monoalkanol tertiary amine is reacted with alkylene
oxide in the presence of a strong acid to form a polyol salt,
which is further reacted with an excess amount of organic
polyisocyanate and chain extended with an active hydrogen-
containing compound.
[0031] In alternate non-limiting embodiments, the aqueous
cationic polyurethane dispersion for use in the present
invention can contain up to 70 wt.o, or up to 65 wt.%, or up
to 60 wt.o, or up to 50 wt.% of the cationic polyurethane. In
further alternate non-limiting embodiments, the aqueous
cationic polyurethane dispersion can include at least 1 wt. o,
or at least 5 wt.%, or at least 10 wt.%, or at least 20 wt.%
of the cationic polyurethane. The amount of cationic
polyurethane in the aqueous cationic polyurethane dispersion
is not critical. In general, the amount should not be so much

CA 02531021 2005-12-22
WO 2005/023543 PCT/US2004/026892
- g _
as to cause the dispersion itself or the mixture with the
nitrogen-containing polymer to be unstable, or so little that
the coating composition does not provide sufficient water and
rub resistance, or cause the dispersion itself to be unstable.
The cationic polyurethane can be present in the aqueous
cationic polyurethane dispersion in any range of values
inclusive of those stated above.
[0032] The nonionic polyurethane dispersion for use in the
present invention can be selected from a variety of known
water-dispersible nonionic polyurethanes. The nonionic
polyurethane can be prepared by various methods known in the
art. For example, Szycher (i.e., "Szycher's Book of
Polyurethanes" by Michael Szycher, CRC Press, New York, NY,
1999, pages 14-10 through 14-15)~ describes the preparation of
water dispersions of polyurethanes, which contain hydrophilic
polyether-type groups either branching off or terminating on
the main polyurethane chains. Polyethylene oxide units
(having a molecular weight (MW) of from 200 to 4,000) can be
used as dispersing sites. In alternate non-limiting
embodiments, nonionic polyurethanes can be prepared using
diols or diisocyanate comonomers bearing pendant polyethylene
oxide chains.
[0033 In alternate non-limiting embodiments, the aqueous
nonionic polyurethane dispersion for use in the present
invention can contain up to 70 wt.%, or up to 65 wt.%, or up
to 60 wt.%, or up to 50 wt.% of the nonionic polyurethane. In
further alternate non-limiting embodiments, the aqueous
nonionic polyurethane dispersion can include at least 1 wt. o,
or at least 5 wt.%, or at least 10 wt. o, or at least 20 wt.%
of the nonionic polyurethane. The amount of nonionic
polyurethane present in the aqueous nonionic polyurethane
dispersion is not critical. In general, the amount should not
be so much as to cause the dispersion itself or the mixture
with the nitrogen-containing polymer to be unstable, or so
little that the coating composition does not provide

CA 02531021 2005-12-22
WO 2005/023543 PCT/US2004/026892
- 9 -
sufficient water and rub resistance, or cause the dispersion
itself to be unstable. The nonionic polyurethane can be
present in the aqueous nonionic polyurethane dispersion in any
range of values inclusive of those stated above.
[0034] In alternate non-limiting embodiments of the present
invention, the aqueous solution of a nitrogen-containing
polymer for use as a dye fixative in the coating composition,
can have a pH of less than 7, or less than 6, or less than 5.
A pH value within this range allows for at least a portion of
the nitrogen atoms to carry at least a portion of a charge.
In further alternate non-limiting embodiments, the resulting
coating composition can have a pH of less than 7, or less than
6, or less than 5. Further, on selected substrates the
wetting action of the coating composition can be improved when
the pH is within the aforementioned ranges. In a non-limiting
embodiment, a coating composition for use in commercial
applications can have pH greater than 2.
[0035] As used herein and in the claims, "aqueous solution"
means that the nitrogen-containing polymer is at least
partially soluble in a liquid medium such as water.
[0036] A dye fixative is generally used to fix dyes to a
substrate to preclude the dyes from bleeding or migrating out
of the substrate when the substrate is contacted with water.
[0037] A known cationic nitrogen-containing polymer in
which at least a portion of the nitrogen atoms carry at least
a portion of a cationic charge within the above-mentioned pH
range of the coating composition, can be used in the present
invention as a dye fixative. Suitable cationic nitrogen-
containing polymers can include cationic polymers having one
or more monomer residues derived from one or more of the
following nitrogen-containing monomers:

CA 02531021 2005-12-22
WO 2005/023543 PCT/US2004/026892
- 10 -
/ R1
CHz C\
~C~
Z
2
R3-
13
R1
CH2 C\
~C~
Z
z
Rs- ~ X_
\Rs
R3
H2C \ / CH2
\CR1 RZC/
CHz CH2
~N
13 , and
H2C \ / CH2
\CR1 R1C/
CH2 CH2
~N~ X_
R R3
wherein R1 represents independently for each occurrence in each
structure, H or C1 to C3 aliphatic; RZ represents independently
for each structure a divalent linking group selected from Cz to
C2o aliphatic hydrocarbon, polyethylene glycol and
polypropylene glycol; R3 represents independently for each
occurrence in each structure H, C1 to C2~ aliphatic hydrocarbon
or a residue from the reaction of the nitrogen with
epichlorohydrin; Z is selected from -O- or -NR4-, where R4 is H
or CH3; and X is a halide or methylsulfate.

CA 02531021 2005-12-22
WO 2005/023543 PCT/US2004/026892
- 11 -
[0038] Non-limiting examples of nitrogen-containing
monomers or resulting monomer residues for use in the present
invention can include dimethyl aminoethyl (meth)acrylate,
(meth)acryloyloxyethyl trimethyl ammonium halides,
(meth)acryloyloxyethyl trimethyl ammonium methylsulfate,
dimethyl aminopropyl (meth)acrylamide, (meth)acrylamidopropyl
trimethyl ammonium halides, aminoalkyl (meth)acrylamides where
the amine is reacted with epichlorohydrin,
(meth)acrylamidopropyl trimethyl ammonium methylsulfate,
diallyl amine, methyl diallyl amine, and diallyl dimethyl
ammonium halides.
[0039] In a non-limiting embodiment, the nitrogen-
containing polymers can contain additional monomer residues.
The additional monomer residues can be obtained from a variety
of polymerizable ethylenically unsaturated monomer that, when
copolymerized with the nitrogen-containing monomers, allows
the resulting polymer to be at least partially soluble in
water. As used herein and the claims, "partially soluble"
refers to at least 0.1 gram of the polymer dissolving in water
when ten (10) grams of the polymer is added to one (1) liter
of water and mixed for a period of 24 hours.
[0040] Non-limiting examples of monomers that can be
copolymerized with the nitrogen-containing monomers include
(meth)acrylamide, n-alkyl (meth)acrylamides, (meth)acrylic
acid, alkyl esters of (meth)acrylate, glycol esters of
(meth)acrylic acid, polyethylene glycol esters of
(meth)acrylic acid, hydroxyalkyl (meth)acrylates, itaconic
acid, alkyl ethers of itaconic acid, malefic acid, mono- and
di-alkyl esters of malefic acid, malefic anhydride, maleimide,
aconitic acid, alkyl esters of aconitic acid, allyl alcohol
and alkyl ethers of allyl alcohol.
[0041] In alternate non-limiting embodiments, the nitrogen-
containing polymer can be a homopolymer of a nitrogen-
containing monomer, or a copolymer of one or more nitrogen-
containing monomers. In another embodiment, the nitrogen-

CA 02531021 2005-12-22
WO 2005/023543 PCT/US2004/026892
- 12 -
containing polymer can be a copolymer of one or more
polymerizable ethylenically unsaturated monomers and one or
more nitrogen-containing monomers. When the nitrogen-
containing polymer includes any of the aforementioned
additional polymerizable ethylenically unsaturated comonomers,
the nitrogen-containing polymer can include not more than 70
mol%,'or not more than 50~mo1%, or not more than 25 mol%, or
not more than 10 mol% of the nitrogen-containing monomer. The
amount of nitrogen-containing monomer can depend on the
polyurethane used in the present coating composition. In
general, when. the amount of the nitrogen-Containing monomer
used in the nitrogen-containing polymer is too much, an
unstable mixture of the nitrogen-containing polymer and
polyurethane dispersion can result. It can be difficult to
properly apply an unstable mixture to an ink jet recordable
substrate.
[0042] In alternate non-limiting embodiments, when the
nitrogen-containing polymer includes any of the aforementioned
additional polymerizable ethylenically unsaturated comonomers,
the nitrogen-containing polymer can include at least 0.1 mol%,
or at least 1.0 mol%, or at least 2.5 mol%, or at least 5.0
mol% of the nitrogen-containing monomer. In further alternate
non-limiting embodiments, when the, amount of nitrogen-
containing monomer in the nitrogen-containing polymer is too
little, the nitrogen-containing polymer cannot provide
adequate dye fixative properties and a recorded ink image on
the coated substrate can lack sufficient water and rub
fastness properties.
[0043] The nitrogen-containing monomers can be present in
the nitrogen-containing polymer in any range of values
inclusive of those stated above. The additional polymerizable
ethylenically unsaturated monomers can be present in an amount
such that the total percentage is 100 mol%.
00044] In alternate non-limiting embodiments of the present
invention, the aqueous solution of the nitrogen-containing

CA 02531021 2005-12-22
WO 2005/023543 PCT/US2004/026892
- 13 -
polymeric dye fixative includes at least 5 wt.%, or at least
wt. o, or at least 15 wt.% of the nitrogen-containing
polymer; and not more than 50 wt. o, or not more than 45 wt. o,
or not more than 40 wt.o of the nitrogen-containing polymer.
In general, when the concentration of the nitrogen-containing
polymer is too little, it may not economical for commercial
applications and can be too dilute to provide optimum ratios
with the polyurethane. In general, when the Concentration is
too much, the solution can be too viscous to easily handle in
a commercial environment. Non-limiting examples of cationic
nitrogen-containing polymers useful in the present invention
can include solutions of polyamide amines reacted with
epichlorohydrin, which are commercially available under the
trade name CinFix from Stockhausen GmbH & Co. KG, Krefeld,
Germany.
(0045] In alternate non-limiting embodiments, the ink jet
recordable substrate coating composition of the present
invention can include from 10 wt.% to 70 wt.%, or from 20 wt.%
to 60 wt. o, or from 30 wt.% to 50 wt.% of an aqueous
polyurethane dispersion; and from 30 wt.% to 90 wt.%, or from
40 wt.% to 80 wt. o, or from 50 wt.o to 70 wt.% of an aqueous
solution of the nitrogen-containing polymer. The weight
percentages are based on the total weight of the ink jet
recordable substrate coating composition.
[0046] In a non-limiting embodiment of the present
invention, the coating composition of the present invention 1
can include an acrylic polymer. The acrylic polymer can be
selected from a wide variety of anionic, cationic and nonionic
acrylic polymers known to a person skilled in the art.
i
[0047] Non-limiting examples of suitable cationic acrylic
polymers can include but are not limited to polyacrylates,
polymethacrylates, polyacrylonitriles and polymers having
monomer types selected from the group consisting of
acrylonitrile, acrylic acid, acrylamide and mixtures thereof.

CA 02531021 2005-12-22
WO 2005/023543 PCT/US2004/026892
- 14 -
[0048] The cationic acrylic polymer can be prepared by a
variety of methods known in the art. In a non-limiting
embodiment, a cationic acrylic polymer can be synthesized via
a free radical solution polymerization from monomer types
butyl acrylate, methyl methacrylate and 2-(tert-
butylamino)ethyl methoacrylate. The molar equivalent of butyl
acrylate can be from 0.10 to 0.95, or from 0.15 to 0.75; the
molar equivalent ,of methyl methacrylate can be from 0.10 to
0.85, or from 0.15 to 0.70; and the molar equivalent of 2-
(tert-butylamino)ethyl methyacrylate can be from 0.10 to 0.25,
or from 0.12 to 0.20. The reaction mixture can be treated with
acid such that the pH is within a range of from 4.0 to 7Ø
The mixture then can be diluted with water and solvent
stripped. Non-limiting examples of suitable acids for use in
the treatment step can include a wide variety of acids which
can function as a solubilizing or dispersing agent to produce
a stable dispersion of a cationic polymer. Non-limiting
examples of suitable solvents for use in the stripping process
can include but are not limited to isopropanol and
methyisobutyl ketone (MIBK).
[0049] In alternate non-limiting embodiments of the present
invention, the molar equivalent of butyl acrylate, methyl
methacrylate and 2-(tert-butylamino)ethyl methacrylate,, can be
from 0.200 to 0.250 . 0.600 to 0.630 . 0.150 to 0.17Q,
respectively ; or from 2.19 to 0.621 to 0.160, respectively.
[0050] In further alternate non-limiting embodiments, the
cationic acrylic polymer for use in the present invention can
have a number average molecular weight of at least 1500 or
less than 8000; or from 1500 to 8150, or from 2900 to 7125.
[0051] In alternate non-limiting embodiments of the present
invention, the ink jet recordable substrate coating
composition can include from 20 wt.o to 75 wt.%, or from 25
wt.o to 70 wt. a, or from 30 wt.o to 60 wt.% of aqueous
polyurethane dispersion; from 5 wt.o to 75 wt.%, or from 15
wt.% to 70 wt. o, or from 30 wt.% to 65 wt.% of aqueous

CA 02531021 2005-12-22
WO 2005/023543 PCT/US2004/026892
- 15 -
solution of the nitrogen-containing polymer; and from 1 wt.%
to 75 wt.o, or from 20 wt.o to 60 wt.o, or from 25 wt.% to 50
wt.o of acrylic polymer. The weight percentages are based on
the total weight of the ink jet recordable substrate coating
composition.
[0052] In another non-limiting embodiment of the present
invention, water can be present with the nitrogen-containing
polymer, polyurethane and acrylic polymer. When water is
present, the resulting ink jet recordable substrate coating
composition can have a total resin solids of from 5 wt.% to 35
wt.%, or from 5 wt.% to 20 wt.%, or from 5 wt.% to 15 wt.%
based on the total weight of the ink jet recordable substrate
coating composition. In general, a total resin solids that is
too high, can cause the viscosity of the coating composition
to increase such that the resulting penetration of the coating
composition to the substrate can be less than desired. In
general, a total resin solids that is too low, can cause the
viscosity of the coating composition to decrease such that the
resulting penetration of the coating to the substrate can be
less than desired. In alternate non-limiting embodiments, the
viscosity of the coating composition can be less than 500 cps,
or less than 400 cps and at least 10 cps, or at least 25 cps
when measured using a Brookfield viscometer at 25°C.
[0053] In a further non-limiting embodiment, the coating
composition of the present invention can include a co-solvent.
Suitable co-solvents can include a wide variety known to a
person skilled in the art. Non-limiting examples can include
but are not limited to lower alkyl alcohols, n-
methylpyrrolidone, Dowanol PM, toluene, and glycol ethers.
[0054] The coating composition of the present invention can
also include other additives typically known in the art. Such
additives can include but are not limited to surfactants, such
as nonionic, cationic, anionic, amphoteric and zwiterionic
surfactants; rheology modifiers, such as polyvinyl alcohols,
polyvinyl pyrrolidones, polyethylene oxides, polyacrylamides,.

CA 02531021 2005-12-22
WO 2005/023543 PCT/US2004/026892
- 16 -
natural and synthetic gums; biocides, such as a blend of 5-
chloro-2-methyl-4-isothiazoline-3-one and 2-methyl-4-
isothiazolin-3-one available commercially by the trade name
Kathon, from Rohm and Haas Co., 2-hydroxypropylmethane
thiosulfonate, and dithiocarbamates; and coupling agents, such
as titanium, silane-type, trisodium pyrophosphate.
[0055] The present invention is also directed to a method
of preparing the ink jet recordable substrate coating
composition. In a non-limiting embodiment, the aqueous
solution of a nitrogen-containing polymer can be added into an
aqueous polyurethane dispersion. In another non-limiting
embodiment, the acrylic polymer can be added. Sufficient
mixing can be maintained during the addition such that a
homogeneous mixture can result.
[0056] The present invention is further directed to a
method of coating an ink jet recordable substrate. The method
includes the steps of:
(a) providing an ink jet recordable substrate having
a top surface and a bottom surface;
(b) providing the coating composition described
above; and
(c) applying the coating composition to at least one
surface of the ink jet recordable substrate.
[0057] A variety of ink jet recordable substrate known in
the art can be used in the present invention. In a non-
limiting embodiment, the ink jet recordable substrate can
include a cellulosic-based paper. United States Patents
4,861,644 and 5,196,262 describe suitable microporous
substrates for use in the present invention.
[0058] In another non-limiting embodiment, the ink jet
recordable substrate can be a microporous substrate. A non-
limiting example of a suitable microporous substrate can
include an ink jet recordable substrate having a top surface
and a bottom and which includes:
(a) a matrix comprising a polyolefin;

CA 02531021 2005-12-22
WO 2005/023543 PCT/US2004/026892
- 17 -
(b) a particulate siliceous filler distributed throughout
the matrix; and
(c) a network of pores wherein the pores constitute at
least 35 percent by volume of the microporous substrate.
[0059] A wide variety of polyolefins known in the art such
as but not limited to polyethylene or polypropylene can be
used in the microporous substrate. In a non-limiting
embodiment, the polyethylene can be a linear high molecular
weight polyethylene having an intrinsic viscosity of at least
deciliters/gram and the polypropylene can be a linear high
molecular weight polypropylene having an intrinsic viscosity
of at least 5 deciliters/gram. As used herein and the claims,
"high molecular weight" refers to a weight average molecular
weight of from 20,000 to 2,000,000.
[0060] Intrinsic viscosity can be determined using a
variety of conventional techniques. As recorded herein and in
the claims, intrinsic viscosity is determined by extrapolating
to zero concentration the reduced viscosities or the inherent
viscosities of several dilute solutions of the polyolefin
wherein the solvent is distilled decahydronaphthalene to which
0.2 percent by weight, 3,5-di-tert-butyl-4-
hydroxyhydrocinnamic acid, neopentanetetrayl ester [CAS
Registry No. 6683-19-8] has been added. The reduced
viscosities or the inherent viscosities of the palyolefin are
ascertained from relative viscosities obtained at 135°C using
an Ubbelohde No. 1 viscometer.
[0061] On a coating-free, printing ink free, impregnant-
free, and pre-bonding basis, pores constitute at least 35
percent by volume of the microporous substrate. In alternate
non-limiting embodiments, the pores can constitute at least 60
percent by volume of the microporous substrate, or from 35
percent to about 80 percent, or from 60 percent to 75 percent
by volume of the microporous substrate.

CA 02531021 2005-12-22
WO 2005/023543 PCT/US2004/026892
- 18 -
[0062] In alternate non-limiting embodiments, the siliceous
particles can be in the form of ultimate particles, aggregates
of ultimate particles, or a combination of both. As used
herein and in the claims, the term "ultimate particles" refers
to small discrete particles of colloidal polymerized silicic
acid units which make up amorphous silica. The term
"aggregate" as used herein and in the claims, refers to a
structure wherein ultimate particles are condensed to produce
an open but essentially continuous structure of chains or a
solid structure of substantially interconnecting pores.
[0063] In an embodiment, the siliceous particles are
finely-divided. As used herein and in the claims, "finely-
divided" refers to a maximum retention of 0.01% by weight on a
40-mesh sieve screen.
L0064] In a further non-limiting embodiment, the siliceous
particles can be substantially insoluble. As used herein and
in the claims, the term "substantially insoluble" refers to
amorphous silica exhibiting a reproducible equilibrium
solubility in water which can range from 70 ppm to greater
than 150 ppm in water at a temperature of 25°C. It is believed
that variations in solubility can be due to differences in
particle size, state of internal hydration and the presence of
trace impurities in the silica or absorbed on its surface.
The solubility of the silica can also depend on the pH of the
water. As pH increases from neutrality (i.e., pH of 7) to
alkalinity (i.e., pH greater than 9), the solubility of silica
can also increase. (See "The Chemistry of Silica", R.K. Iler,
Wiley-Interscience, NY (1979), pp. 40-58.)
[0065] In a non-limiting embodiment of the present
invention, at least 90 percent by weight of the siliceous
particles used in preparing the microporous substrate can have
particle sizes in the range of from 5 to 40 micrometers. The
particle size can be determined by a variety of conventional
techniques. In present invention, a Model TaII Coulter
Multisizer Particle Size Analyzer (Coulter Electronics, Inc.)

CA 02531021 2005-12-22
WO 2005/023543 PCT/US2004/026892
- 19 -
was use, wherein prior to analysis by the Coulter Analyzer,
. the filler was stirred for 10 minutes in Isoton II electrolyte
solution (Cumin Matheson Scientific, Inc.) using a four-
blade, 4.445 centimeter diameter propeller stirrer. In a non-
limiting embodiment, at least 90 percent by weight of the
siliceous particles can have particle sizes in the range of
from 10 to 30 micrometers. It is believed that the sizes of
filler agglomerates can be reduced during processing of the
ingredients to prepare the microporous substrate.
[0066] Suitable siliceous particles can include a wide
variety known to a person skilled in the art. Non-limiting
i
examples can include but are not limited to particles of
silica, mica, montmorillonite, kaolinite, asbestos; talc,
diatomaceous earth, vermiculite, natural and synthetic
zeolites, cement, calcium silicate, aluminum silicate, sodium
aluminum silicate, aluminum polysilicate, alumina silica gels,
and glass particles. In a non-limiting embodiment, silica and
clay can be used as siliceous particles. In a further non-
limiting embodiment, precipitated silica, silica gel, or fumed
silica can be used.
[0067] In general, silica can be prepared by combining an
aqueous solution of a soluble metal silicate with an acid.
The soluble metal silicate can be an alkali metal silicate
such as sodium or potassium silicate. The acid can be
selected from the group consisting of mineral acids, organic
acids, and carbon dioxide. The silicate/acid slurry can then
be aged. An acid or base can be added to the silicate/acid
slurry. The resultant silica particles can be separated from
the liquid portion of the mixture; the separated silica can be
washed with water; the wet silica product can be dried; and
the dried silica can be separated from residues of other
reaction products; using conventional washing, drying and
separating methods.
[0068] In a non-limiting embodiment, the siliceous
particles can be coated using the above-described coating

CA 02531021 2005-12-22
WO 2005/023543 PCT/US2004/026892
- 20 -
compositions prior to incorporation into the microporous
substrate. A variety of methods known in the art can be used
to at least partially coat the particles. The selected
coating method is not critical. In a further non-limiting
embodiment, the coating ingredients can be added to an aqueous
slurry of pre-washed silica filter cake under sufficient
stirring to allow for substantially complete mixing of the
ingredients, followed by drying, using conventional techniques
known in the art.
(0069] United States Patent Applications having serial
numbers 09/636,711; 09/636,312; 09/636,310; 09/636,308;
09/636,311 and 10/041,114; disclose suitable coating
compositions and methods of coating silica particles which may
be used in the present invention.
[0070] In alternate non-limiting embodiments, the
particulate siliceous filler can constitute from 50% to 90%,
or from 55o to 85%, or from 60% to 80o by weight of the
microporous substrate.
[0071] In a non-limiting embodiment, in addition to the
siliceous particles, substantially water-insoluble non-
siliceous filler particles can also be used in the microporous
substrate. Non-limiting examples of such optional non-
siliceous filler particles can include but are not limited to
particles of titanium oxide, iron oxide, copper oxide, zinc
oxide, antimony oxide, zirconia, magnesia, alumina, molybdenum
disulfide, zinc sulfide, barium sulfate, strontium sulfate,
calcium-carbonate, magnesium carbonate, magnesium hydroxide,
and finely divided substantially water-insoluble flame
retardant filler particles such as but not limited to
particles of ethylenebis(tetra-bromophthalimide),
octabromodiphenyl oxide, decabromodiphenyl oxide, and
ethylenebisdibromonorbornane dicarboximide.
[0072] In a non-limiting embodiment of the invention, the
substrate can be highly porous. The term "highly porous"
refers to a substrate having a porosity of not more than

CA 02531021 2005-12-22
WO 2005/023543 PCT/US2004/026892
- 21 -
20,000, or not more than 10,000 or not more than 7,500
seconds/100cc air. In a further non-limiting embodiment, the
porosity can be at least 50 seconds/100cc air. These porosity
values are determined in accordance with the method described
in ASTM D726, with the following exceptions relative to
Section 8 of the ASTM method. In the present invention, the
sheet samples are tested without conditioning in accordance
with ASTM D685, and only three (3) specimens for a given
sample type are tested for a total of six (6) measurements
(three measurements per two surfaces) for a given specimen
type rather than a minimum of ten specimens for a given sample
as stated in ASTM D726. In general, the lower the value in
seconds/cc air, the more porous is the substrate. Highly
porous substrates can be produced by various methods known in
the art, such as thermally treating a substrate, orienting,
compositionally by~increasing the filler content, microvoiding
films, or etching. Non-limiting examples of highly porous
substrates can include but are not limited to thermally-
treated microporous substrates such as Teslin~ TS-1000 which
is commercially available from PPG Industries, Inc.,
Pittsburgh, PA.
[0073] In alternate non-limiting embodiments of the present
invention, the coated microporous substrate can have a
thickness of at least 0.1 mils, or from 0.5 to 100 mils, or
from 1 to 50 mils, or from 4 to 14 mils. In general, when the
coated microporous substrate has a thickness which exceeds the
aforementioned ranges, it may not feed properly through an ink
jet printer. In general, when the thickness of the coated
microporous substrate is less than the stated ranges, it may
not have sufficient strength for its intended use.
[0074] A wide variety of methods known in the art can be
used to at least partially apply the coating composition of
the present invention to the ink jet recordable substrate.
Non-limiting examples of suitable methods can include but are
not limited to flexography, spraying, air knife coating,

CA 02531021 2005-12-22
WO 2005/023543 PCT/US2004/026892
- 22 -
curtain coating, dipping, rod coating, blade coating, gravure,
reverse roll, roller application, imbibing, size press,
printing, brushing, drawing, slot-die coating, and extrusion.
[0075] In a non-limiting embodiment of the present
invention, the coating composition can be at least partially
applied to the substrate using an air knife coating technique
where at least a portion of the excess coating can be 'blown
off' by a powerful jet from the air knife. In another non-
limiting embodiment, a reverse roll coating method can be
used. In this procedure, the coating composition can be
measured onto an applicator roller by precision setting of the
gap between an upper metering roller and the application
roller below it. The coating can be at least partially wiped-
off the application roller by the substrate as it passes
around the support roller at the bottom.
[0076] In another non-limiting embodiment of the present
invention, gravure coating can be used to at least partially
apply the coating composition. In the gravure coating method,
an engraved roller runs in a coating bath, which at least
partially fills the engraved dots or lines of the roller with
the coating composition. At least a portion of the excess
coating on the roller can be at least partially wiped-off by a
doctor blade and the coating can be deposited onto the
substrate as it passes between the engraved roller and a
pressure roller. Reverse gravure coating methods also can be
used. In this method, the coating composition can metered by
the engraving on a roller before being at least partially
wiped-off as in a conventional reverse roll coating process.
[0077] In a further non-limiting embodiment, a metering rod
can be used to at least partially apply the coating
composition. When a metering rod is used, at least a portion
of the excess of the coating can be deposited onto the
substrate as it passes over a bath roller. The wire-wound
metering rod, sometimes known as a Meyer Bar, allows the
desired quantity of the coating to remain on the substrate.

CA 02531021 2005-12-22
WO 2005/023543 PCT/US2004/026892
- 23 -
The quantity is determined by the diameter of the wire used on
the rod.
[0078] The amount of the substantially dry coating applied
to the substrate, or "coat weight", can be measured as coating
weight per coated area. The coat weight can vary widely. In a
alternate non-limiting embodiments, the coat weight can be at
least 0.001 g/m2, or at least 0.01 g/m2, or at least 0.1 g/m2;
or not more than 50 g/m2, or not more than 40 g/m2, or not more
than 35 g/m2. The coat weight can vary between any of the
stated amounts.
[0079] Following application of the coating composition to
the substrate, solvent can be removed from the applied coating
by any conventional drying technique. In a non-limiting
embodiment, the coating can be dried by exposing the coated
substrate to a temperature ranging from ambient to 350°F.
[0080] The coating composition can be at least partially
applied at least one time to at least one surface of the
substrate. In a non-limiting embodiment, the coating
composition can be applied more than one time. In this
embodiment, the applied coating can be at least partially
dried between coating applications.
[0081] When the coating composition is applied to a
microporous substrate, the coating composition can at least
partially penetrate into the substrate. Penetration of the
coating into the microporous substrate can improve the ink jet
print quality on the coated substrate. In alternate non-
limiting embodiments, the coating can penetrate into at least
the first one (1) micron, or at least the first ten (10)
microns, or at least the first twenty (20) microns or at least
the first thirty (30) microns of the microporous substrate.
[0082] The present invention is also directed to a coated
microporous substrate. The coated microporous substrate can
include at least one coated surface. The surface can be
coated with the aforementioned coating compositions using the
above-described coating techniques.

CA 02531021 2005-12-22
WO 2005/023543 PCT/US2004/026892
- 24 -
[0083] In alternate non-limiting embodiments, the
substantially dried coating layer can include polyurethane in
an amount of from 10 to 70 percent, or from 20 to 60 percent,
or from 30 to 55 percent by weight of the coating layer; and
nitrogen-containing polymer in an amount of from 30 to 90
percent, or from 40 to 80 percent, or from 45 to 70 percent by
weight of the coating layer. The amount of each component in
the substantially dried coating layer can determined by the
amount of each used to prepare the coating composition.
[0084] As used herein and in the claims, "substantially
dry" is used to refer to the coating layer that feels dry to
touch.
[0085] The ink jet recordable substrate can be printed with
a wide variety of printing inks using a wide variety of
printing processes. Both the printing inks and the printing
processes are themselves conventional and known in the art.
In a non-limiting embodiment, the substrate of the present
invention can be used as an ink jet recordable substrate for
ink jet printing. In alternate non-limiting embodiments,
printing can be accomplished prior to assembly of the ink jet
recordable substrate into multilayer articles of the present
invention or following the assembly of such multilayer
articles.
[0086] In the present invention, the substantially water-
resistant, at least partially coated, ink jet recordable
substrate can be connected to at least one substantially
nonporous material. As used herein and the claims, the term
"connected to" means to link together or place in relationship
either directly, or indirectly by one or more intervening
materials. As used herein and the claims, the term
"substantially nonporous material" refers to a material which
is generally impervious to the passage of liquid, gas, and
bacteria. On a macroscopic scale, a substantially nonporous
material exhibits few if any pores. As used herein and the
claims, the term "pore(s)" refers to a minute openings)

CA 02531021 2005-12-22
WO 2005/023543 PCT/US2004/026892
- 25 -
through which matter can pass. Substantially nonporous
materials for use in the present invention can vary widely and
can comprise those materials customarily recognized and
employed for their known barrier properties. Non-limiting
examples of such suitable materials can include substantially
nonporous thermoplastic polymers, substantially nonporous
metalized thermoplastic polymers, substantially nonporous
thermoset polymers, substantially nonporous elastomerics, and
substantially nonporous metals. The substantially nonporous
material can be in the form of a sheet, film, or foil, or
other shapes can be used when desired, such as for example,
plates, bars, rods, tubes, and forms of more complex shape.
In further alternate non-limiting embodiments, the
substantially nonporous material for use in the present
invention can be in the form or a sheet, film or foil.
[0087) As used herein and the claims, the term
"thermoplastic polymer" refers to a polymer that can be
softened by heat and then regain its original properties upon
cooling. The term "thermoset polymer" as used herein and the
claims refers to a polymer that solidifies or sets on heating
and cannot be re-melted.
[0088] Non-limiting examples of suitable thermoplastic
polymeric materials can include but are not limited to
polyethylene, high density polyethylene, low density
polyethylene, polypropylene, polyvinyl chloride), saran,
polystyrene, high'impact polystyrene, nylons, polyesters such
as polyethylene terephthalate), copolymers of ethylene and
acrylic acid, copolymers of ethylene and methacrylic acid, and
mixtures thereof. In further alternate non-limiting
embodiments, all or a portion of the carboxyl groups of
carboxyl-containing copolymers can be neutralized with sodium,
zinc, or the like. A non-limiting example of a metalized
thermoplastic polymeric material can be aluminized
polyethylene terephthalate).

CA 02531021 2005-12-22
WO 2005/023543 PCT/US2004/026892
- 26 -
[0089] Non-limiting examples of suitable thermoset
polymeric materials can include but are not limited to
thermoset phenol-formaldehyde resin, thermoset melamine-
formaldehyde resin, and mixtures thereof.
[0090] Non-limiting examples of suitable elastomeric
materials can include but are not limited to natural rubber,
neoprene, styrene-butadiene rubber, acrylonitrile-butadiene-
styrene rubber, elastomeric polyurethanes, and elastomeric
copolymers of ethylene and propylene.
[0091] Non-limiting examples of suitable metals can include
but are not limited to iron, steel, copper, brass, bronze,
chromium, zinc, die metal, aluminum, and cadmium.
[0092] The multilayer article of the present invention can
be constructed using a wide variety of known methods for at
least partially connecting at least one layer of an ink jet
recordable substrate with at least one layer of a
substantially nonporous material. In a non-limiting
embodiment, at least one layer of a substantially water-
resistant, at least partially coated ink jet recordable
substrate can be fusion bonded to at least one layer of a
substantially nonporous material. The ink jet recordable
substrate generally comprises opposed major surfaces which are
characteristic of sheets, films, foils, and plates. The
resulting multilayer article can comprise one layer or more
than one layer of the ink jet recordable substrate, and one
layer or more than one layer of the substantially nonporous
material. In a non-limiting embodiment, at least one exterior
layer can be the ink jet recordable substrate. In an
alternate non-limiting embodiment, the ink jet recordable
substrate can be a microporous substrate.
[0093] In a non-limiting embodiment, the multilayer article
of the present invention can be produced by fusion bonding in
the absence of an adhesive. Fusion bonding can be
accomplished using conventional techniques such as sealing
through use of heated rollers, heated bars, heated plates,

CA 02531021 2005-12-22
WO 2005/023543 PCT/US2004/026892
- 27 -
heated bands, heated wires, flame bonding, radio frequency
(RF) sealing, and ultrasonic sealing. Solvent bonding can be
used where the substantially nonporous material can be at
least partially soluble in the applied solvent to the extent
that the surface becomes tacky. The ink jet recordable
substrate can be contacted with the tacky surface, and the
solvent then can be removed to form the fusion bond. In a
non-limiting embodiment, foamable compositions can be foamed
in at least partial contact with the ink jet recordable
substrate to form a fusion bond between the foam and the
substrate. Films or sheets of nonporous substrate can be
extruded and while still hot and tacky, can be contacted with
the ink jet recordable substrate to form a fusion bond. The
fusion bond can be permanent or peelable, depending upon the
known bonding technique and/or the nature of the substantially
nonporous material employed.
(0094] In a non-limiting embodiment, heat sealing can be
used to fusion bond the ink jet recordable substrate to the
substantially nonporous material. In general, heat sealing
can include inserting an ink jet recordable substrate into
standard heat sealing equipment which is known in the art. In
a non-limiting embodiment, the ink jet recordable substrate
can be inserted in conjunction with a substantially nonporous
material which can be a thermoplastic and/or thermoset
polymer. Heat and/or pressure can be applied to the
substrate/polymer construction for a period of time. The
amount of heat and/or pressure and length of time can vary
widely. In general, the temperature, pressure and time are
selected such that the substrate and polymer can be at least
partially connected together to form a multilayer article. In
a non-limiting embodiment, the temperature can be within the
range of from 100°F to 400°F. In another non-limiting
embodiment, the pressure can be within the range of from 5 psi
to 250 psi. In a further non-limiting embodiment, the time
period can range from one (1) second to thirty (30) minutes.

CA 02531021 2005-12-22
WO 2005/023543 PCT/US2004/026892
_ ~8 _
The multilayer article then can be cooled while under pressure
for a period of time, such as but not limited; to thirty (30)
minutes. Although the strength of the bond formed between the
substrate and polymer can vary, the strength is generally such
that it can exceed the tensile properties of the substrate
alone. ,
[0095] In a non-limiting embodiment, the substantially
nonporous material can be polyvinyl chloride.
[0096] In a non-limiting embodiment, the ink jet recordable
substrate employed in the present invention can be at least
partially connected to a nonporous substrate such as
polyethylene and polypropylene by heat sealing in the absence
of an extrinsic adhesive. The resultant fusion bond can be
sufficiently strong which is surprising inasmuch as the
lamination of materials to polyolefins is typically difficult
unless special adhesives are used.
[0097] In alternate non-limiting embodiments, the ink jet
recordable substrate can be substantially continuously at
least partially connected to the substantially nonporous
material, or it can be discontinuously at least partially
connected to the substantially nonporous material. Non-
limiting examples of discontinuous bonds can include bonding
areas in the form of one or more spots, patches, strips,
stripes, chevrons, undulating stripes, zigzag stripes, open-
curved stripes, closed-curved stripes, irregular areas, and
the like. In alternate non-limiting embodiments, when patterns
of bonds are present, they can be random, repetitive, or a
combination of both.
[0098] In another non-limiting embodiment, an ink jet
recordable substrate can be at least partially connected to a
substantially nonporous material in the presence of an
adhesive. The adhesive for use in the present invention can
be selected from a wide variety of adhesives known in the art.
Suitable adhesives can include those having a sufficient
molecular weight and viscosity such that the adhesive will not

CA 02531021 2005-12-22
WO 2005/023543 PCT/US2004/026892
- 29 -
substantially migrate into or substantially penetrate the ink
jet recordable substrate. Migration or penetration of the
adhesive into the substrate can reduce the tack and bond
strength of the adhesive. Non-limiting examples of suitable
adhesives for use in the present invention can include but are
not limited to polyvinyl acetate, starches, gums, polyvinyl
alcohol, animal glues, acrylics, epoxies, polyethylene-
containing adhesives, and rubber-containing adhesives. In
alternate non-limiting embodiments, the adhesive can be
applied to the substrate, or to the substantially nonporous
material, or to both the substrate and the substantially
nonporous material. In a further non-limiting embodiment, the
adhesive can be introduced via the use of a tie carrier
coating.
L0099] The process of bonding the substrate and
substantially nonporous material in the presence of an
adhesive can be. accomplished using a variety of conventional
techniques known in the art. In a non-limiting embodiment,
the substrate/adhesive/material construction can be inserted
into standard processing equipment. Heat and/or pressure can
be applied to the substrate/adhesive/material construction for
a period of time. The amount of heat and/or pressure and
length of time can vary widely. In general, the temperature,
pressure and time are selected such that the substrate and
substantially nonporous material can be at least partially
connected together to form a multi-layer article. In a non-
limiting embodiment, the temperature can be within the range
of from 100°F to 400°F. In another non-limiting embodiment,
the pressure can be within the range of from 5 psi to 250 psi.
In still another non-limiting embodiment, the period of time
can be in the range of from one (1) second to thirty (30)
minutes. The multilayer article then can be cooled under
pressure for a time period, such as thirty (30) minutes.
Although the strength of the bond formed between the ink jet
recordable substrate and the substantially nonporous material

CA 02531021 2005-12-22
WO 2005/023543 PCT/US2004/026892
- 30 -
can vary, the bond is generally such that it exceeds the
tensile properties of the substrate alone.
[00100 The ink jet recordable substrate of the present
invention can be molded using,conventional molding techniques
known in the art. In alternate non-limiting embodiments,~the
substrate can be molded in the presence of or in the absence
of a substantially nonporous material, such as but not limited
to a thermoplastic and/or thermoset polymer. In general, the
ink jet recordable substrate can be inserted into standard
molding equipment. In a non-limiting embodiment, a
thermoplastic and/or thermoset polymer can be introduced onto
the substrate and then the substrate/polymer construction can
be inserted into the mold cavity. In another non-limiting
embodiment, the substrate can be placed into the mold cavity
and then the thermoplastic and/or thermoset polymer can be
introduced onto the substrate. Heat and/or pressure can be
applied to the substrate/polymer construction for a period of
time. The amount of heat and/or pressure and length of time
can vary widely. In general, the temperature, pressure and
time can be selected such that the 'substrate and polymer can
be at least partially connected together to form a multi-layer
article. A typical temperature can be within the range of
from 100°F to 400°F. In a non-limiting embodiment, wherein the
polymer comprises a thermoplastic polymer, the
substrate/polymer construction can be heated to a temperature
that equals or exceeds the melt temperature of the
thermoplastic polymer. In another non-limiting embodiment,
wherein the thermoplastic polymer can be amorphous, the
substrate polymer construction can be heated to a temperature
that equals or exceeds the Vicat temperature. In still
another non-limiting embodiment, wherein the polymer comprises
a thermoset polymer, the temperature can be below the curing
or crosslinking temperature of the polymer. A typical
pressure can be within the range of from 5 psi to 250 psi, and
a typical period of time can be in the range of from one (1)

CA 02531021 2005-12-22
WO 2005/023543 PCT/US2004/026892
- 31 -
second to fifteen (15) minutes. A typical result of a molding
process can be a re-shaping of the original article. The re-
shaping is generally defined by the design of the mold cavity.
Thus, in a standard molding process, a two-dimensional flat
sheet can be re-shaped into a three-dimensional article.
[001017 In a non-limiting embodiment of the present
invention, the ink jet recordable substrate can comprise
Teslin~ which is commercially available from PPG Industries,
Incorporated in Pittsburgh, PA. The thickness of the ink jet
recordable substrate of the present invention can vary widely
I
depending on the application or use. In a non-limiting
embodiment, the ink jet recordable substrate can be from 5 to
20 mils thick.
[00102] In general, the multilayer article of the present
invention can be produced employing a variety of molding and
laminating procedures known in the art, which include but are
not limited to compression molding, rotational molding,
injection molding, calendering, roll/nip laminating,
thermoforming, vacuum forming, extrusion coating, continuous
belt laminating, and extrusion laminating.
[00103] In a non-limiting embodiment, other tie coatings
known in the art can be used in conjunction with the substrate
and the substantially nonporous material.
[00104] In another non-limiting embodiment, a friction-
reducing coating composition can be at least partially applied
to at least one of the ink jet recordable substrate and the
substantially nonporous material. In a further non-limiting
embodiment, the friction-reducing coating composition can
comprise at least one lubricant and at least one resin. There
are a wide variety of lubricants and resins known to the
skilled artisan that can be used.
[00105] Non-limiting examples of such suitable lubricants
can include but are not limited to natural and synthetic
waxes, natural and synthetic oils, polypropylene waxes,
polyethylene waxes, silicone oils and waxes, polyesters,

CA 02531021 2005-12-22
WO 2005/023543 PCT/US2004/026892
- 32 -
polysiloxanes, hydrocarbon waxes, carnauba waxes,
microcrystalline waxes and fatty acids, and mixtures thereof.
In a non-limiting embodiment, the lubricant for use in the
present invention can include polysiloxanes, such as but not
limited to silicone.
[00106] Non-limiting examples of suitable resins can include
but are not limited to polyurethanes, polyesters, polyvinyl
acetates, polyvinyl alcohols, epoxies, polyamides, polyamines,
polyalkylenes, polypropylenes, polyethylenes, polyacrylics,
polyacrylates, polyalkylene oxides, polyvinyl pyrrolidones,
polyethers, polyketones, and co-polymers and mixtures thereof.
In a non-limiting embodiment, the resin for use in the present
invention can include styrene acrylic polymers such as but not
limited to styrene acrylic-comprising polyurethanes,
polyepoxies, polyvinyl alcohols, polyesters, polyethers, and
co-polymers and mixtures thereof.
[00107] In a further non-limiting embodiment, the friction-
reducing coating composition for use in the present invention
can include Wikoff SCW 4890 and 2295 which are commercially
available from Wikoff Industries, Incorporated, as poly board
aqua coat products.
[00108] Not intending to be bound by any particular theory,
it is believed that the molecules of the resin component of
the friction-reducing coating can be at least partially
interconnected or interlinked with the ink jet recordable
substrate and/or the substantially nonporous material, such
that the silicone can be essentially fixed to the surface of
said substrate and/or said material. In a non-limiting
embodiment, the molecules of a thermoplastic resin component
can be at least partially interconnected by fusion to the ink
jet recordable substrate and/or the substantially nonporous
material. Tn another non-limiting embodiment, the molecules
of a thermoset resin component can be at least partially
interlinked by crosslinking to the ink jet recordable
substrate and/or the substantially nonporous material.

CA 02531021 2005-12-22
WO 2005/023543 PCT/US2004/026892
- 33 -
[00109] In a further non-limiting embodiment, the friction-
reducing coating composition can comprise water and/or an
organic solvent. A wide variety of organic solvents known to
the skilled artisan can be used. Non-limiting examples of
such suitable organic solvents can include but are not limited
to N-methyl pyrrolidone (NMP), methyl ethyl ketone (MEK),
acetone, diethyl ether, toluene, Dowanol PM, Butyl Cellosolve,
and mixtures thereof. In a non-limiting embodiment, the
friction-reducing coating composition can comprise water and
an organic solvent, wherein said organic solvent is at least
partially miscible with water.
[00110] In a non-limiting embodiment, the friction-reducing
coating composition can be at least partially applied to at
least one of the ink jet recordable substrate and the
substantially nonporous material of the present invention.
Application of said friction-reducing coating composition to
said substrate and/or said material can employ a wide variety
of known techniques. In alternate non-limiting embodiments,
the techniques described previously herein for applying the
substantially water-resistant coating to the ink jet
recordable substrate can be used for application of the
friction-reducing coating composition to the ink jet
recordable substrate and/or the substantially nonporous
material.
[00111] The amount of the substantially dry friction-
reducing coating applied to the substrate/material, or "coat
weight", is typically measured as coating weight per coated
area. The coat weight can vary widely. In alternate non-
limiting embodiments, the coat weight of the substantially dry
friction-reducing coating can be at least 0.1 gram per square
meter, or from greater than 0 to 50 grams per square meter, or
from 1 gram per square meter to 15 grams per square meter.
[00112] In a non-limiting embodiment, the multilayer article
of the present invention can include a 10 mil thick sheet of
Teslin~ comprising a essentially water-resistant coating

CA 02531021 2005-12-22
WO 2005/023543 PCT/US2004/026892
- 34 -
composition, a 10 mil sheet of polyvinylchloride, a 10 mil
thick sheet of polyvinylchloride, and a 2 mil thick sheet of
polyvinylchloride comprising a friction-reducing coating
composition. In a further non-limiting embodiment, the
friction-reducing coating composition can comprise a
polysiloxane and a styrene acrylic polymer.
[00113] In a non-limiting embodiment, the multilayer article
of the present invention can include a magnetizable material.
As used herein and the claims, the term "magnetizable
material" means a material to which magnetic properties can be
communicated. A wide variety of magnetizable materials are
known to one skilled in the art. Known magnetizable materials
are available in various forms such as but not limited to
sheet, film, tape or stripe.
[00114] Magnetizable materials for use in the present
invention can be selected from a variety of materials capable
of being magnetized by a magnetic field. Suitable
magnetizable materials can include but are not limited to
oxide materials. Non-limiting examples of suitable oxide
materials can include ferrous oxide,~,iron oxide, and mixtures
thereof. In a non-limiting embodiment, the oxide particles
can be present in a slurry formulation.
[00115] Suitable magnetizable materials for use in the
present invention can include those known in the art which
demonstrate performance characteristics such as but not
limited to the ability to be encoded with sufficient ease,
ability to encode a sufficient amount of information, and
ability to be erased with sufficient resistance. In a non-
limiting embodiment, the amount of information encoded onto
the magnetizable material can be referred to as the number of
stages or tracks. The number of stages or tracks can vary.
In alternate non-limiting embodiments, the magnetizable
material for use in the present invention can have at least
one (1) track, or not more than six (6) tracks, or from three
(3) to four (4) tracks.

CA 02531021 2005-12-22
WO 2005/023543 PCT/US2004/026892
- 35 -
[00116] In a non-limiting embodiment, the resistance to
erasure can be referred to as "coercivity°. In general, the
higher the coercivity value, the greater the resistance to
erasure. The coercivity value can vary. In alternate non-
limiting embodiments, the magnetizable material for use in the
present invention can have a coercivity of at least 200, or
not more than 5000, or from 500 to 2500, or from 100 to 1500.
[00117] Non-limiting examples of suitable magnetizable
materials for use in the present invention can include but are
not limited to magnetic foils which are commercially available
from JCP, Kurz, EMTEC and DuPont.
[00118] In a non-limiting embodiment, the magnetizable
material can be at least partially connected to at least one
or more materials selected from a protective material, a
carrier material or an adhesive material. The protective
material, carrier material and adhesive material can be
selected from a wide variety of materials known in the art as
useful for each function. Non-limiting examples of suitable
protective materials can include but are not limited to PET
(polyethylene terapthalate), polyester and combinations
thereof. Non-limiting examples of carrier materials can
include but are not limited to PET, polyester and combinations
thereof. Non-limiting examples of suitable adhesive materials
can include but are not limited to those recited herein.
[00119] In another non-limiting embodiment, the protective
material can be at least partially connected to the
magnetizable material, the magnetizable material can be at
least partially connected to the carrier material, and the
carrier material can be at least partially connected to the
adhesive material.
[00120] In alternate non-limiting embodiments, the
magnetizable material can be at least partially connected to
an ink jet recordable substrate and/or at least one
substantially nonporous material. Non-limiting examples of
ink jet recordable substrates can include but are not limited

CA 02531021 2005-12-22
WO 2005/023543 PCT/US2004/026892
- 36 -
to those previously recited herein. In a non-limiting
embodiment, the ink jet recordable substrate can be a
microporous substrate such as those previously recited herein.
In a further non-limiting embodiment, the microporous
substrate can be Teslin° printing sheet which is commercially
available from PPG Industries, Incorporated. Non-limiting
examples of suitable substantially nonporous materials can
include but are not limited to those previously recited
herein. In a non-limiting embodiment, the substantially
nonporous material can be polyvinyl chloride.
[00121] The magnetizable material-containing multilayer
article of the present invention can be prepared by various
methods known in the art. In a non-limiting embodiment, the
magnetizable material can be at least partially connected to
at least one substantially nonporous material. Various
application techniques suitable for at least partially
connecting the magnetizable material to the substantially
I
nonporous material are known to a skilled artisan. In a non-
limiting embodiment, the magnetizable material can be at least
partially connected using an adhesive material. Non-limiting
examples of suitable adhesive materials can include but are
not limited to a wide variety of adhesives known to the
skilled artisan, such as but not limited to those previously
recited herein. In a non-limiting embodiment, the adhesive
material can be selected from thermal- or pressure-sensitive
adhesives.
[00122] In a further non-limiting embodiment, the
magnetizable material can be at least partially connected to
the adhesive material, and the adhesive material can be at
least partially connected to a surface of the microporous
substrate and/or at least one substantially nonporous
material.
[00123] In alternate non-limiting embodiments, the
magnetizable material can be at least partially connected to a
microporous substrate and/or at least one substantially

CA 02531021 2005-12-22
WO 2005/023543 PCT/US2004/026892
- 3~ _.
nonporous material prior to, during, or following a
conventional lamination process such as but not limited to the
lamination process previously described herein.
[00124] In another non-limiting embodiment, the magnetizable
material can be essentially flush with the surface of the
microporous substrate and/or substantially nonporous material
to which it can be connected.
[00125] In a non-limiting embodiment, a substantially water-
resistant coating composition can be at least partially
applied to the magnetizable material. In alternate non-
limiting embodiments, the coating can be at least partially
applied to the magnetizable material either prior to or
following at least partially connecting the magnetizable
material to a microporous substrate or a substantially
nonporous material. In a further non-limiting embodiment, an
adhesive material can be at least partially applied to the
uncoated surface of the magnetizable material, and the
adhesive-containing surface can be at least partially
connected to the microporous substrate or substantially
nonporous material. In alternate non-limiting embodiments,
the substantially~water-resistant coating composition can be
at least partially applied to at least one of the magnetizable
material, the microporous substrate and the substantially
nonporous material. In still a further non-limiting
embodiment, the substantially water-resistant coating
composition can include that which is recited herein.
[00126] In a non-limiting embodiment, a friction reducing
coating composition can be at least partially applied to the
magnetizable material. In alternate non-limiting embodiments,
the coating can be at least partially applied to the
magnetizable material either prior to or following at least
partially connecting the magnetizable material to a
micorporous substrate or a substantially nonporous material.
In a further non-limiting embodiment, an adhesive material can
be at least partially applied to the uncoated surface of the

CA 02531021 2005-12-22
WO 2005/023543 PCT/US2004/026892
- 38 -
magnetizable material, and the adhesive-containing surface can
be at least partially connected to the microporous substrate
or substantially nonporous material. In alternate non-
limiting embodiments, the friction reducing coating
composition can be at least partially applied to at least one
of the magnetizable material, the microporous substrate, and
substantially nonporous material. In still a further non-
limiting embodiment, the substantially friction reducing
coating composition can include that which is recited herein.
[00127] The coating compositions can be applied by a variety
of methods known in the art. In alternate non-limiting
embodiments, the coating compositions can be applied by the
methods previously described herein.
[00128] In a further non-limiting embodiment, a multilayer
article of the present invention can include a microporous
substrate at least partially connected to a first
substantially nonporous material; the first substantially
nonporous material can be at least partially connected to a
second substantially nonporous material; the second
substantially nonporous material can be at least partially
connected to a third substantially nonporous material; said
third substantially nonporous material can include a
magnetizable material. In a further non-limiting embodiment,
the microporous substrate and/or substantially nonporous
materials can be at least partially connected using an
adhesive material which can be at least partially applied to
at least one surface of the substrate and/or materials.
[00129] In another non-limiting embodiment, a release liner
can be at least partially connected to at least one surface of
the multilayer article of the present invention. The release
liner can function as a barrier to essentially prevent or
minimize damage of the article during the manufacture process.
In a non-limiting embodiment, a coating residue can be
deposited on the stainless steel equipment during the
lamination process as a result of print-off. Deposition of

CA 02531021 2005-12-22
WO 2005/023543 PCT/US2004/026892
- 39 -
the coating on the equipment can result in at least partial
damage to the coated surface of the multilayer article. In
alternate non-limiting embodiments, a release liner can be at
least partially connected to a coated or uncoated magnetizable
material, a coated or uncoated substantially nonporous
material, and/or a coated or uncoated microporous substrate.
[00130] The release liner can be selected from a wide
variety of materials known in the art to perform the above-
stated function. In general, a material suitable for use as,a
release liner in the present invention can have at least one
of the following characteristics: a melt temperature in
excess of the lamination temperature, the ability to
essentially not migrate into the material and an acceptable
tear strength such that it, can be pulled away with sufficient
ease.
[00131] In a further non-limiting embodiment, the
microporous substrate, the substantially non-porous material,
and magnetizable-containing substantially non-porous material
can be aligned in an essentially parallel configuration to
form a stacked article.
[00132] In another non-limiting embodiment, the microporous
substrate can be at least partially connected to the
substantially nonporous material in the absence of an adhesive
material. In another non-limiting embodiment, the
substantially nonporous material can be at least partially
connected to another substantially nonporous material in the
absence of an adhesive material.
[00133] In another non-limiting embodiment, the multilayer
article of the present invention can include a data
transmittance/storage device. Such devices can vary widely.
Suitable devices for use in the present invention can include
those known in the art. In a non-limiting embodiment, the
device can include an antenna, electronic chip and/or other
related circuitry. In a further embodiment, the device can
include a carrier material. The carrier material can be

CA 02531021 2005-12-22
WO 2005/023543 PCT/US2004/026892
- 40 -
selected from a wide variety of materials known in the art.
In a non-limiting embodiment, the carrier material can be a
substantially nonporous material. Suitable substantially
nonporous materials can include those previously recited
herein. In a non-limiting embodiment, the carrier material
can be polyvinylchloride.
[00134] In still a further embodiment, the device can
include a barrier material on at least one side of the
circuitry. A function of the barrier material can be to
encompass the circuitry and provide a substantially flat
surface on the outside of the device. The barrier material
can be selected from a wide variety of materials known in the
art. In a non-limiting embodiment, the barrier material can
be a substantially nonporous material. Suitable substantially
nonporous materials can include those previously recited
herein. In a non-limiting embodiment, the barrier material
can be polyvinylchloride.
[00135] In a non-limiting embodiment, the multilayer article
of the present invention can include an ink jet recordable
substrate, a data transmittance/storage device, and at least
one substantially nonporous material. The ink jet recordable
substrate can be selected from a wide variety~of such
materials known in the art. Suitable non-limiting examples
can include those previously described herein. In a non-
limiting embodiment, the ink jet recordable substrate can be a
microporous substrate such as those previously recited herein.
In a further non-limiting embodiment, the ink jet recordable
substrate can be Teslin~ printing sheet which is commercially
available from PPG Industries, Incorporated. As previously
described herein, the ink jet recordable substrate can be at
least partially coated on at least one surface or uncoated.
Suitable coating Compositions can include those previously
described herein. In a non-limiting embodiment, a
substantially water-resistant coating composition can be at
least partially applied to the ink jet recordable substrate.

CA 02531021 2005-12-22
WO 2005/023543 PCT/US2004/026892
- 41 -
[00136] The substantially nonporous material can be selected
from a wide variety of such materials known in the art.
Suitable non-limiting examples of substantially nonporous
materials can include those previously described herein. In a
non-limiting embodiment, the substantially nonporous material
can be polyvinylchloride. As previously described herein, the
substantially nonporous material can be at least partially
coated on at least one surface or uncoated. Suitable coating
compositions can include those previously described herein.
In a non-limiting embodiment, a friction-reducing coating
composition can be at least partially applied to the
substantially nonporous material.
[00137] In a further non-limiting embodiment, the data
transmittance/storage device can be at least partially
connected to the barrier material using an adhesive material.
A wide variety of suitable adhesive materials and methods of
application are known in the art. Non-limiting examples
include those adhesive materials and methods of application
previously described herein.
[00138] In another non-limiting embodiment, the barrier
material can have at least one surface at least partially
coated with a coating composition. Suitable coating
compositions can include those previously described herein.
In a non-limiting embodiment, a friction-reducing coating
composition can be at least partially applied to the barrier
material.
[00139] In a non-limiting embodiment, the multilayer article
with magnetizable material or with a transmittance/storage
device, can have a thickness that varies widely. In alternate
non-limiting embodiments, the thickness of the article can be
at least 10 mils, or less than 60 mils, or from 30 to 50 mils.
[00140] The multilayer article with magnetizable material or
with a data transmittance/storage device can be useful in a
wide variety of applications. In alternate non-limiting
embodiments, it can be used in applications related to

CA 02531021 2005-12-22
WO 2005/023543 PCT/US2004/026892
- 42 -
security access, access-control, data storage and data
transmittance.
[00141] The multilayer article of the present invention has
many and varied uses including but not limited to gaskets,
cushion assemblies, signs, cards, printing substrates,
substrates for pen and ink drawings, maps (particularly
maritime maps), book covers, book pages, wall coverings, and
seams, joints, and seals of breathable packages.
[00142] The multilayer article of the present invention can
be useful for the purpose of decorating or identifying the
substantially nonporous material, or imparting to the
substantially nonporous material unique properties of the
substrate surface. The ink jet recordable substrate can be
decorated with a variety of methods including but not limited
to: offset/lithographic printing, flexographic printing;
painting, gravure printing, inkjet printing,
electrophotographic printing, sublimation printing, thermal
transfer printing, and screen printing. Decorating can also
include at least partially applying a single or multilayer
coating to the ink jet recordable substrate via normal coating
methods known in the art. In general, the unique properties)
that an ink jet recordable substrate can impart on a
substantially nonporous material include, but are not limited
to one or more of: improved surface energy, increased
porosity, decreased porosity, increased bond strength of post
coat layer, and modification of the polymer's surface texture
or pattern.
[00143] Polymer processing techniques are disclosed in U.S.
Patent No. 4,892,779.
[00144] The present invention is more particularly described
in the following examples, which are intended to be
illustrative only, since numerous modifications and variations
therein will be apparent to those skilled in the art. Unless
otherwise specified, all parts and percentages are by weight
and all references to water are meant to be deionized water.

CA 02531021 2005-12-22
WO 2005/023543 PCT/US2004/026892
_ 43 _ .
EXAMPLES
Example 1
[007.45] A coating composition of the present invention was
prepared by diluting in a stainless steel mix tank under high
speed mixing with an overhead mixer, a 61.5% solids by weight
anionic polyurethane dispersion sold under the trade name
WitcoBond~ 234 available from Crompton Corporation, Greenwich,
Connecticut, to 9.22% solids by weight. In a separate feed
tank a 55o solids by weight solution of a polyamide amine
reacted with epichlorohydrin sold under the trade name CinFix
NF by Stockhausen GmbH & Co. KG, Krefeld, Germany, was diluted
to 5.78% solids by weight, and subsequently added to the
diluted anionic polyurethane dispersion, and the mixture was
mixed for 15 minutes. The pH was adjusted with glacial acetic
acid to 5.0 ~ 0.5. The total resin solids of the mixture was
7.5% and the viscosity of the mixture was 46 cps as measured
using a Brookfield viscometer, RVT, spindle no. 1, at 50 rpm
and 25°C.
Examples 2-5
[00146] A coating composition was prepared as described in
Example 1 and applied to Teslin~ microporous substrates. Two
substrates (Examples 2 and 4) were coated using a metering
bar. A metering bar was placed 1 - 2 inches above the Teslin°
sheet, parallel to the top edge. A 10 - 20 ml quantity of
coating was drawn into a disposable plastic syringe. The
coating was deposited as a bead strip (approximately 1/8
inches wide) directly next to and touching the metering bar.
The bar was drawn completely across the sheet of Teslin~,
attempting a continuousjconstant rate. The resultant wet sheet
was placed in a forced air oven, secured and dried at 95°C for
2 minutes. The dried sheet was removed from the oven and the
same coating procedure was repeated on the opposite side of
the sheet. The sheet was then printed and tested. For coating

CA 02531021 2005-12-22
WO 2005/023543 PCT/US2004/026892
- 44 -
compositions having a total resin solids of 7.5a, the
viscosity was 46 cps; and for 10.0% solids, the viscosity was
63 cps. The viscosity values were measured using a Brookfield
viscometer, RVT, spindle no. 1, at 50 rpm and 25°C.
[00147] Two substrates (Examples 3 and 5) were coated using
a flexographic or gravure coating method to apply the coating.
In this coating method, a line consisting of two coating
stations, each with a forced air drying oven was used. Each
coating station consists of a coating feed chamber, anilox
roll and rubber application roll. The coating feed chamber was
supplied from a coating holding tank and pump. Both sides of
the Teslin° sheet were coated. The apparatus was fitted with a
7 BCM (billion cubic microns) anilox roll, line speed was 180
fpm, oven temperature was 105°C (220°F) and 8 passes per roll
were made, which translates into four passes per surface.
[00148] The coating compositions were applied with an
approximate coat weight of 0.73 g/m2 (total front and back).
The coat weight was determined as follows: the coat weight of
"X" grams of coating (as dry solids) consumed in coating "Y"
square meters of Teslin~, is "X divided by Y" grams per square
meter.
[00149] Table 1 shows the characteristics of the sheets
produced.
TABLE 1
Total
Substrate Polyurethane Coating Resin
Method Solids
Example Teslin~ WitcoBond 234 Meyer #9 Rod 7.5
2 TS1000
7 BCM Anilox
Example Teslin~ WitcoBond 234 (5 BPS*) 7.5
3 TS1000
Example Teslin~ WitcoBond 234 Meyer #9 Rod 10.0

CA 02531021 2005-12-22
WO 2005/023543 PCT/US2004/026892
- 45 -
4 TS1000
7 BCM Anilox
Example Teslin WitcoBond 234 (4 BPS*) 10.0
TS1000
F~rS = rsumps Yer Sur~ace
(00150] The resultant coated sheets were printed with a test
print pattern on a Model HP970 (Hewlett Packard Company) ink
jet printer. Color bars from the test print pattern were
measured for optical density by submerging in deionized water
at ambient temperature for a period of 15 minutes, removing
from the water and allowing to air dry for one hour and
measuring each color for optical density. The optical density
of cyan (C) , magenta (M)'~, yellow, black (K) and composite black
(CMY) were measured using a Model RD922, MacBeth ANSWER II
densitometer, manufactured by Kolimorgen Instrument
Corporation, before and after water soak. The results are
shown in Table 2.
TABLE 2
Initial Optical
Optical Density
Densityl @
15
Minute
Water
Soak
CMY C M Y K CMY C M Y K
Example 1.3 1.0 1.0 0.7 1.3 1.3 1.0 1.0 0.8 1.4
2 4 4 8 6 7 3 7 4 1 2
Example 1.3Ø9 1.0 0.7 1.3 1.3 1.0 1.0 0.7 1.3
3 3 9 3 3 3 4 7 6 8 7
Example 1.3 1.0 1.0 0.7 1.3 1.3 1.0 1.0 0.7 1.3
4 6 4 9 7 8 3 5 2 9 7
Example 1.2 1.1 1.1 0.8 1.2 1.2 1.1 1.1 0.9 1.2
5 1 1 9 7 0 3 8 9 2 2
Example 6

CA 02531021 2005-12-22
WO 2005/023543 PCT/US2004/026892
- 46 -
[00151] A 9.22% solids by weight solution of WitcoBond 234
was applied to a Teslin~ TS1000 substrate using a metering bar
as described in Examples 2-5. Immediately thereafter, a 5.78a
solids by weight solution of CinFix NF was similarly applied
to the substrate. The coated Teslin° TS1000 was then dried at
95°C for 2 minutes. The dried sheet was removed from the oven
and the same coating procedure was repeated on the opposite
side of the sheet. A test print pattern was printed on the
coated Teslin~ using an HP970 Inkjet Printer as described in
Examples 2-5. Based on visual inspection, the printed image
demonstrated excessive ink bleeding and poor drying
properties.
Example 7
[00152] A coating composition was prepared by diluting in a
stainless steel mix tank under high speed mixing with an
overhead mixer, a 61.50 solids by weight anionic polyurethane
dispersion sold under the trade name WitcoBond° 234 available
from Crompton Corporation, Greenwich, Connecticut, to 9.22%
solids by weight. In a separate feed tank a 55% solids by
weight solution of a polyamide amine reacted with
epichlorohydrin sold under the trade name CinFix NF by
Stockhausen GmbH & Co. KG, Krefeld, Germany, was diluted to
5.78% solids by weight. The WitcoBond 234 dispersion was
added to the diluted CinFix NF solution. The resulting
suspension demonstrated an unacceptably heavy precipitate
which was a polysalt of the CinFix NF and WitcoBond 234.
Examples 8-10
[00153] Coating compositions were prepared as in Example 1
and were applied to silk fabric (O.lOlb/sq yd, 5mi1 gauge),
cotton fabric (0.341b/sq yd, 13.6mi1 gauge) and a
polypropylene/cellulose nonwoven substrate (0.141b/sq yd,
9.5mi1 gauge). For each material coated, a sheet (8.5" x 11")
was fixed to a 15" x 20" x 20 mil backing sheet. A metering

CA 02531021 2005-12-22
WO 2005/023543 PCT/US2004/026892
- 47 -
bar was placed 1 - 2 inches above the top of the sheet,
parallel to the top edge. A 10 - 20 ml quantity of coating was
drawn into a disposable plastic syringe. The coating was
deposited as a bead strip (approximately 1/8 inches wide)
directly next to and touching the metering bar. The bar was
drawn completely across the sheet at a continuous/constant
rate. The resultant wet sheet was placed in a forced air oven,
secured and dried at 95°C for 2 minutes. The dried sheet was
removed from the oven and the same coating procedure was
repeated on the opposite side of the sheet. The sheet was then
taped to a transparency sheet to provide rigidity and was then
ready to be printed and tested. The coating compositions were
applied with an approximate coat weight of 0.73 g/m2 (total
front and back). Coat weight was determined as previously
described in Examples 2-5.
[00154] Examples 8 - 10 were printed with an ink jet
printer, Model HP970 by Hewlett Packard Company, Palo Alto,
California and compared to the same substrates without
coating. After printing, each sheet was removed from the
rigid transparency sheet. Coated and uncoated printed sheet
types were soaked in water at ambient temperature for 5 days.
Optical density was measured after 5 days of soaking. The
optical density of cyan (C), magenta (M), yellow (Y), black
(K) and composite black (CMY), were measured using a Model
RD922, MacBeth ANSWER II Densitometer, manufactured by
Kolimorgen Instrument Corporation, before and after water
soak.
[00155] The recorded images for the coated substrates
remained intact after 15 minutes, i.e., the ink did not bleed
or the optical density of the image was not significantly
decreased for each sample. The uncoated sheets bled
immediately, completely washing away the printed image within
the 15 minute soak time. The printed image on each of the
coated substrate did experience ink bleed after 5-day water
soak exposure, as seen by the optical density values. The

CA 02531021 2005-12-22
WO 2005/023543 PCT/US2004/026892
- 48 -
resultant printed images were faded but had good line
sharpness and legible text.
Initial Optical
Optical Density
~
5day
Density Water
Soak
CMY C M Y K CMY C M Y K
Example 8 1.2 1.0 1.2 1.0 1.2 0.8 0.7 0.6 0.5 0.8
3 4 4 8 4 7 1 2 5 0
Silk 0.9 0.8 0.8 0.7 0.9 Color
bars
washed
(uncoated) 7 4 8 2 5 out/not
measurable
Example 9 1.2 1.1 1.3 1.1 1.2 0.8 0.6 0.7 0.5 0.9
6 3 1 1 7 1 9 6 4 2
Cotton 0.9 0.8 0.9 0.8 0.9 Color
bars
washed
(uncoated) 4 1 1 1 5 out/not
measurable
Example 10 1.4 1.1 1.4 1.1 1.4 1.1 0.8 0.6 0.5 1.2
2 9 6 1 6 4 9 7 8 1
Polypropylen/1.2 1.1 1.4 1.0 1.2 Color
bars
washed
Cellulose 6 5 3 6 9 out/not
measurable
(uncoated)
Example 11
[00156 A coating composition designated herein as "01" was
prepared as follows. In a mixing vessel under high speed
mixing with an overhead mixer, a 61.5% solids by weight
anionic polyurethane dispersion sold under the trade name
Witcobond W-234 available from Crompton Corporation,
Greenwich, Connecticut, was diluted with deionized water to a
10.0% solids by weight dispersion. In a separate vessel, a
55o solids by weight solution of a polyamide amine reacted
with epichlorohydrin sold under the trade name CinFix NF
available from Stockhausen GmbH & Co. KG, Krefeld, Germany,
was diluted with deionized water to a 10.00 solids by weight
solution, and was subsequently added to the diluted anionic
polyurethane dispersion. The mixture was mixed for fifteen
minutes following completion of the addition. The resulting

CA 02531021 2005-12-22
WO 2005/023543 PCT/US2004/026892
- 49 -
mixture contained 40 parts by weight of solids of CinFix NF
and 60 parts by weight of solids of Witcobond W-234.
[00157] A second coating was prepared as above-described
with the exception that CinFix NF was replaced on an
equivalent dry solids basis with CinFix RDF. This second
coating composition is referred to herein as Ol/RDF. CinFix
RDF is a water solution of poly(diallyl dimethyl ammonium
chloride) at 31% solids commercially available from
Stockhausen GmbH & Co. KG, Krefeld, Germany. The CinFix RDF
was diluted to 10.00 solids by weight prior to addition to the
Witcobond W-234.
[00158] A third coating was prepared as above-described for
the "O1" composition with the exception that CinFix NF was
replaced on an equivalent dry solids basis with
diallyldimethylammonium chloride. This third coating
composition is referred~to herein as "01/DADMAC".
Diallyldimethyl ammonium chloride is commercially available
from Aldrich Chemical Company of Milwaukee, WI, as a 650
solution in water. It was diluted to 10.00 solids by weight
prior to addition to the Witcobond W-234.
[00159] A fourth coating was prepared as above-described for
the "01" composition with the exception that CinFix NF was
replaced on an equivalent dry solids basis with the reaction
product of equimolar amounts of diethyl amine and
epichlorohydrin at 30% solids in water. This fourth coating
composition is referred to herein as "O1/DEA-EPI'°. The
reaction product was not completely miscible with water in the
30/70 parts by weight mix necessary for 30% solids and
therefore, was acidified to a pH of 5 with acetic acid to
render it soluble in water for use in the coating. It was
diluted to 10.0% solids prior to addition to the Witcobond W-
234.
[00160] Sheets of Teslin° TS1000 and SP1000 were coated on
both sides with each of the above-mentioned coatings using a
#9 rod. The coating was applied to the front surface, dried

CA 02531021 2005-12-22
WO 2005/023543 PCT/US2004/026892
- 50 -
for a period of two minutes at a temperature of 95°C, and then
applied to the back surface and dried for two minutes at 95°C.
The finished sheets were then printed with a pattern on a
Hewlett-Packard 960C printer at "HP Premium Photo Paper -
Glossy" setting. The color density of the printed color bar
section of the pattern was measured using an X-Rite Model 418
Densitometer, calibrated on a white tile standard. The
printed color bar section was cut out of each sheet and
immersed in a beaker of de-ionized water overnight (i.e., 14
hours). The sections were then removed from the water baths
and allowed to air dry for a period of four hours. The color
density after soak was then measured.
(00161) The results are shown in the following table:
Coating SubstrateSoak CMY C-100 M-100 Y-100 K-100
"01" TS1000 No 1.31 1.23 1.24 0.93 1.31
"01" Yes 1.33 1.16 1.20 0.92 1.33
"01" SP1000 No 1.32 1.23 1.25 0.93 1.32
"01" Yes 1.32 1.16 1.19 0.90 1.33
"01/RDF" TS1000 No 1.52 1.10 1.20 0.88 1.55
'
"01/RDF" Yes 1.54 1.04 1.10 0.84 1.55
"01/RDF" SP1000 No 1.16 0.97 1.28 0.99 1.20
"01/RDF" Yes 1.13 0.91 1.21 1.00 1.15
"01/DADMAC"TS1000 No 1.73 1.13 1.01 0.82 1.80
"01/DADMAC" Yes 1.53 0.11 0.17 0.13 1.55
"01/DADMAC"SP1000 No 1.37 0.91 1.44 1.06 1.58
"01/DADMAC" Yes 0.26 0.14 0.20 0.15 0.16
"01/DEA-EPI"TS1000 No 0.81 0.98 0.85 0.57 0.81
"01/DEA-EPI" Yes 0.60 0.66 0.36 0.24 0.59
"01/DEA-EPI"SP1000 No 0.75 0.92 0.82 0.55 0.76
"01iDEA-EPl" Yes 0.54 0.62 0.35 0.23 0.55
(001627 The "01" coating on either substrate exhibited
acceptable color density and water resistance and there was no
visual evidence of color bleed. Based on visual inspection,
the printed images were crisp and clear. The "01/RDF" coating
also demonstrated acceptable color density and water
resistance, showing no visual bleed. However, based on visual
inspection there was a slight "feathering" or blurring of the
image on the SP1000 substrate. The "01/DADMAC" coating had
high color density before the soak, but based on visual
inspection, the inks did not completely dry on the surface and

CA 02531021 2005-12-22
WO 2005/023543 PCT/US2004/026892
- 51 -
were almost completely removed from both of the substrates
during the soak. Further, based on visual inspection, the
images were not distinct, there was significant color bleed
and the images were not clear. The "01/DEA-EPI" coating had
low color density on both substrates and the water resistance
was poor. Based on visual inspection, there was no color
bleed and the images were clear but appeared faded.
Example 12
[00163] One coated Teslin° sheet was placed on top of one
20-inch x 25-inch sheet of 0.10-inch polyvinylchloride (PVC),
supplied by Empire Plastics. The PVC sheet was cut in the
grain long direction. Below the PVC ply was a second ply of
20-inch x 25-inch x l0mil PVC, cut grain short. Below the
l0mil PVC grain short ply was a 20-inch x 25-inch x 2mi1 PVC
sheet of Itlockner ZE84 cut grain long. A sheet 21-inch x 26-
inch of 2-mil clear polyester was placed over the Teslin~
sheet to act as a release liner. This construction was placed
between two 21" x 26" x 30rriil polished stainless steel metal
plate. An identical polyester/treated Teslin~
sheet/PVC/PVC/PVC lay-up was placed on top of a stainless
plate from the existing construction. A polished metal plate
was placed over the exposed polyester release liner. The
pattern was repeated ten more times so that twelve pre-pressed
mufti-layer plys existed in the-stack. The resultant stack
was placed between buffer pads. The buffer pads are a
combination polyamide fiber and mechanical rubber,
manufactured and supplied by Yamauchi Corporation, designed to
more uniformally distribute temperature and press during
thermal lamination. The resultant stack plus buffer pads was
then placed between two slightly larger 125mi1 un-polished
non-corrosive metal plates. This entire construction,
referred to as a book, was placed in a TMP laminating press,
preheated to 300°F. The composite construction was compression
laminated at a pressure of 203psi. The entire book was held

CA 02531021 2005-12-22
WO 2005/023543 PCT/US2004/026892
- 52 -
under this condition until the middle ply's of the book
reached a temperature of 261°F. Then while still under press,
the platens were cooled long enough to allow the same center
plys to reach 100°F. After being removed from the press, all
twelve composite sheets were removed from the book. All
twelve composite sheets were topically treated with static
guard on the pvc surface. All twelve finished composite
sheets had good integrity; any attempt to delaminate destroyed
the Teslin° layer, which demonstrated a good adhesive and
seamless bond between the Teslin~ and the PVC. IS07910 ID-1
cards were die cut using PMC high die equipment with the
Teslin~ surface facing the cutting blade of the die. The
finished cards from each composite sheet had good integrity
and good lat flat. The resultant cards blocked slightly and
did not demonstrate required slip performance.
Example 13
,,
[00164] Coating composition Wikoff SCW 4890, manufactured
and supplied by Wikoff Industries was applied to 300ft of 2mi1
Klockner ZE84 pvc sheet using a flexographic or gravure
coating method. A single coating station was fixtured with a
6bcm anilox roll and non-textured rubber application roll.
The coating feed chamber was supplied from a coating holding
tank and pump. Continuous roll stock was threaded through the
equipment so that the coated sheet passed through a drying
oven, with the coated surface facing the hot air source. The
line speed was 200fpm, oven temperature was 105°C (220°F) and a
single coating pass was applied. The coating composition was
applied with an approximate coat weight of 6.lmg/sqin. The
resultant coated roll was converted into 20" x 25" sheets,
grain long.
Example 14

CA 02531021 2005-12-22
WO 2005/023543 PCT/US2004/026892
- 53 -
[00165] The 2mil coated pvc sheet prepared as described in
Example 13 was fabricated into cards using the following
procedure. One coated Teslin° sheet was placed on top of one
20-inch x 25-inch sheet of 0.10-inch polyvinylchloride (PVC),
supplied by Empire Plastics. The PVC sheet was cut in the
grain long direction. Below the PVC ply was a second ply of
20-inch x 25-inch x lOmil PVC, cut grain short. Below the
l0mil PVC grain short ply was the coated 20-inch x 25-inch x
2mil PVC sheet cut grain long, positioned with the coated
surface facing away from the adjacent 10mi1 pvc ply. A sheet
21-inch x 26-inch of 2-mil clear polyester was placed over the
Teslin~ sheet to act as a release liner. This construction
was placed between two 21" x 26" x 30mi1 polished stainless
steel metal plate. An identical polyester/treated Teslin°
sheet/PVC/PVC/PVC lay-up was placed on top of a stainless
plate from the existing construction. A polished metal plate
was placed over the exposed polyester release liner. The
pattern was repeated ten more times so that twelve pre-pressed
multi-layer plys existed in the stack. The resultant stack
was placed between buffer pads. The buffer pads are a
combination polyamide fiber and mechanical rubber,
manufactured and supplied by Yamauchi Corporation, designed to
more uniformally distribute temperature and press during
thermal lamination. The resultant stack plus buffer pads was
then placed between two slightly larger 125mi1 un-polished
non-corrosive metal plates. This entire construction,
referred to as a book, was placed in a TMP laminating press,
preheated to 300°F. The composite construction was compression
laminated at a pressure of 203psi. The entire book was held
under this condition until the middle ply's of the book
reached a temperature of 261°F. Then while still under press,
the platens were cooled long enough to allow the same center
plys to reach 100°F. After being removed from the press, all
twelve composite sheets were removed from the book. All

CA 02531021 2005-12-22
WO 2005/023543 PCT/US2004/026892
- 54 -
twelve finished composite sheets had good integrity; any
attempt to delaminate destroyed the Teslin° layer, which
demonstrated a good adhesive and seamless bond between the
Teslin~ and the PVC. IS07910 ID-1 cards were die cut from the
each of the 20-inch x 25-inch x 30.5mi1 composite sheets. The
finished cards from each composite sheet had good integrity
and good lat flat. The resultant cards demonstrated non-
blocking behavior and required slip performance.
[00166] Friction Force Test Method
A card was fixed to a smooth flat base.
A second card was placed on top of the base card, with an
offset of ~-inch over the long edge.
The second card was attached to a force gauge through a
cable and pulley system. The force gauge was fixed to the
travel arm of an instron.
A symmetrical weight was placed on the second card with
the back edge of the weight centered and flush with the
trailing edge of the second card.
The card pair was staged one (1) minute prior to pulling.
The top card was slid over the bottom card approximately
1.5-inch and the maximum pull force measured on the force
gauge was recorded.
The procedure was repeated five (5) times, each time with
a different card pair.
The average, standard deviation and % coefficient of
variation of all six measurements were calculated and
reported.
Card Slip Performance
Friction Uncoated 4890/lpass 4890/2passes
Force
Measurements
1kg load 1.33 1.105 0.984
results

CA 02531021 2005-12-22
WO 2005/023543 PCT/US2004/026892
- 55 -
(1b. )
Std dev. 0.073 0.192 0.068
%COV 5.5 17.4 6.9
200g load 0.284 0.179 0.144
results
(1b. )
Std. Dev. 0.036 0.027 0.014
aCOV 12.6 15.1 9.79
Example 15
[00167] One coated Teslin° sheet was placed on top of one
' 20-inch x.25-inch sheet of 0.10-inch polyvinylchloride (PVC),
supplied by Empire Plastics. The PVC sheet was cut in the
grain long direction. Below the PVC ply was a second ply of
20-inch x 25-inch x lOmil PVC, cut grain short. Below the
lOmil PVC grain short ply was a 20-inch x 25-inch x 2mi1 PVC
sheet of Klockner ZE84 cut grain long. A sheet 21-inch x 26-
inch of 2-mil clear polyester was placed over the Teslin°
sheet to act as a release liner. This construction was placed
between two 21" x 26" x 30mi1 polished stainless steel metal
plate. An identical polyester/treated Teslin~
sheet/PVC/PVC/PVC lay-up was placed on top of a stainless
plate from the existing construction. A polished metal plate
was placed over the exposed polyester release liner. The
pattern was repeated ten more times so that twelve pre-pressed
multi-layer plys existed in the stack. The resultant stack
was placed between buffer pads. The buffer pads are a
combination polyamide fiber and mechanical rubber,
manufactured and supplied by Yamauchi Corporation, designed'to
more uniformally distribute temperature and press during

CA 02531021 2005-12-22
WO 2005/023543 PCT/US2004/026892
- 56 -
thermal lamination. The resultant stack plus buffer pads was
then placed between two slightly larger 125mi1 un-polished
non-corrosive metal plates. This entire construction,
referred to as a book, was placed in a TMP laminating press,
preheated to 300°F. The composite construction was compression
laminated at a pressure of 203psi. The entire book was held
under this condition until the middle ply's of the book
reached a temperature of 261F. Then while still under press,
the platens were cooled long enough to allow the same center
plys to reach 100°F. After being removed from the press, all
twelve composite sheets were removed from the book. All
twelve composite sheets were topically treated with static
guard on the pvc surface. All twelve finished composite
sheets had good integrity; any attempt to delaminate destroyed
the Teslin~ layer, which demonstrated a good adhesive and
seamless bond between the Teslin~ and the PVC. IS07910 ID-1
cards were die cut from the each of the 20-inch x 25-inch x
30.5mi1 composite sheets. The finished cards from each
composite sheet had good integrity and good lat flat. The
resultant cards demonstrated non-blocking behavior and
required slip performance. These cards did, however, block
when placed in a 100card stack following exposure to 24hours,
85% RH, 55C, under a 1 kg. load. Any attempt to delaminate
destroyed the Teslin~ layer, which demonstrated a good
adhesive and seamless bond between the Teslin~ and the~PVC.
Lamination Plate Build-up & Friction Force vs.
PVC Surface Treatment
Sample 2mi1 PVC surface Initial Friction Build-
ID
treatment 1kg Force up/Lamination
(Anilox Friction following Cycles
Roll/Chemistry) Force 85%RH/55C/lkg
(1b.) /24hrs
(1b.)
Uncoated Not Applicable >2.0 Cards BlockedNo
residue/build
-up
8181-92- 6bcm/solid 0.728 0.851 Heavy /

CA 02531021 2005-12-22
WO 2005/023543 PCT/US2004/026892
- 57 -
O1 roll/4890/lpass 2cycles
8181-92- 5bcm/solid 0.669 0.859 Slight /
02 roll/4890/lpass 3cycles
8181-92- 5bcm/solid 0.888 0.938 Very Slight
/
04 roll/75/25- 3cycles
1124/4890b1end/lpa
ss
Lot #24 Laminates 0.721 Cards blockedNo
topically treated residue/build
with DMDTAC -up
[00168] Teslin~ Coating Method (25 Gallon Mix)
Ingredients Amounts
CinFix RDF 13.46kg
Deionized Water 24.98kg
PPG WC-71-2134 12.24kg
Deionized Water 16.74kg
Witcobond W240 12.17kg
Deionized Water 16.65kg
Mix Procedure
- Added specified amount of CinFix RFD to the main mix
container and stirred.
- Added specified amount of DI water to the CinFix RFD
and stirred for 10 minutes prior to the next premix
addition. Continued to stir throughout the entire mix
procedure.
- Added specified amount of PPG WC-71-2134 to a premix
container and stirred.
Added specified amount of DI water to the PPG WC-71-
2134 and stirred for 10 minutes.
- Added PPG WC-71-2134 premix to the main mix container.
- Added specified amount of Witcobond W240 to a premix
container and stirred.

CA 02531021 2005-12-22
WO 2005/023543 PCT/US2004/026892
- 58 -
- Added specified amount of DI water to the PPG WC-71-
2134 and stirred for 10 minutes.
- Added Witcobond W240 premix to the main mix container.
- Stirred the final mix for 15 minutes.
- Measured/Monitored solids, pH and viscosity and made
any necessary adjustments.
Coating composition given in a descriptive format:
Coating Description: 40 active parts CinFix RDF
30 active parts PPG WC-71-2134
30 active parts Witcobond W240
12.5% Total Mix Solids
Example 16
[001697 A coating of Wikoff SCW 4890, manufactured and
supplied from Wikoff Industries was applied to 3,660 feet of 2
mil gauge Magnetic Stripe Master Roll, manufactured and
supplied from JCP, using a flexographic/gravure coating
method. A single coating station was fitted with a 5bcm
anilox roll and non-textured rubber application roll. The
coating feed chamber was supplied from a coating holding tank
and pump. Continuous roll stock was threaded through the
equipment such that the surface containing the magnetic stripe
tape would receive the coating. Also the coated sheet passed
through a drying oven, with the coated surface facing the hot
air source. The line speed was 300fpm; oven temperature was
105°C (220°F); and a single coating pass was applied. A gentle
curtain of air was directed towards the continuous coated
sheet just prior to the wind-up station to eliminate folds
and wrinkles. The coating was applied with an approximate
coat weight of 5mg/sqin. The resultant coated roll was
converted into 25" x 20" sheets, grain short.

CA 02531021 2005-12-22
WO 2005/023543 PCT/US2004/026892
- 59 -
Example 17
[00170] The 2 mil coated Magnetic Stripe Master Sheet
prepared as described in Example 16 was fabricated into cards
using the following procedure. One coated Teslin~ sheet was
placed on top of one 20-inch x 25-inch sheet of 0.10-inch
polyvinylchloride (PVC), supplied by Empire Plastics. The PVC
sheet was cut in the grain long direction. Below the PVC ply
was a second ply of 20-inch x 25-inch x 10 mil PVC, cut grain
long. Below the 10 mil PVC grain long ply was the coated 20-
inch x 25-inch x 2mil Magnetic Stripe Master Sheet cut grain
short, positioned with the coated surface facing away from the
adjacent 10 mil pvc ply. A sheet 21-inch x 26-inch of 2-mil
clear polyester was placed over the Teslin~ sheet to act as
release liner. This construction was placed between two 21" x
26" x 30 mil polished stainless steel metal plate. An
identical polyester/treated Teslin~ sheet/PVC/PVC/Magnetic
Stripe Master Sheet lay-up was placed on top of a stainless
plate from the existing construction. A polished metal plate
was placed over the exposed polyester release liner. The
pattern was repeated ten more times so that twelve pre-pressed
multi-layer plys existed in the stack. The resultant stack
was placed between buffer pads. The buffer pads are a
combination polyamide fiber and mechanical rubber,
manufactured and supplied by Yamauchi Corporation, designed to
more uniformly distribute temperature and press during thermal
lamination. The resultant stack plus buffer pads was then
placed between two slightly larger 125mi1 un-polished non-
corrosive metal plates. This entire construction, referred to
as a book, was placed in a TMP laminating press, preheated to
a temperature of 300°F. The composite construction was
compression laminated at a pressure of 203 psi. The entire
book was held under this condition until the middle plies of
the book reached a temperature of 261°F. While still hot, the
press was released from all books for one minute then the

CA 02531021 2005-12-22
WO 2005/023543 PCT/US2004/026892
- 60 -
pressure was re-introduced. The platens were cooled long
enough to allow the same center plies to reach a temperature
of 100°F. After being removed from the press, all twelve
composite sheets were removed from the book. The mylar
release liner was removed from the Teslin~ sheet. The
magnetic stripe surface showed defects resulting from print-
off of the Wikoff coating onto the lamination plate. All
twelve finished composite sheets had good integrity; any
attempt to delaminate the article resulted in destroying the
Teslin~ layer, which demonstrated a good adhesive and
essentially seamless bond between the Teslin° and the PVC.
IS07910 ID-1 cards were die cut frotri~the each of the 20-inch x
25-inch x 30.5 mil composite sheets. The finished cards from
each composite sheet had good integrity and good lat flat.
The resultant cards demonstrated non-blocking behavior and
good slip performance.
Example 18 - Thermal Lamination
[00171] A sheet of TS 1000 (which was available from PPG
Industries, Incorporated, under the trade name Teslin)
measuring 8.5 x 11 inches was cut from a master roll. The
Teslin sheet was coated using four (4) passes on each side.
The coating composition used to coat the Teslin was prepared
by first diluting a 31% solids anionic polyurethane sold under
the trade name WitcoBond 234 (available from Crompton
Corporation, Greenwich, Connecticut), to 12.3% solids in a
stainless steel mix tank under high speed mixing with an
overhead mixer. In a separate feed tank a 55% solids solution
of a polyamide amine reacted with dimethylamine and
epichlorohydrin (available under the trade name CinFix NF by
Stockhausen GmbH & Co. KG, Drefeld, Germany), was diluted to
7.7% solids and then subsequently added to the diluted anionic
polyurethane dispersion, at a 50/50 volume ratio, and the
mixture was mixed for 15 minutes. The pH was adjusted to 5.0
+/- 0.5. The total resin solids of the mixture was 10%.

CA 02531021 2005-12-22
WO 2005/023543 PCT/US2004/026892
- 61 -
[00172] The coating composition was applied to the sheet of
Teslin (10 mil thick) using flexographic coating technology
which included two coating stations containing forced air
drying ovens. Each coating station consisted of a coating
feed chamber, anilox roll and rubber roll. The coating feed
chamber was supplied from a coating holding tank and pump.
Only one coating station was used in the preparation of this
material. The apparatus was fitted with a 7 bcm (billion
cubic microns) anilox roll, the line speed was 180 fpm (feet
per minute), and the oven temperature was 105°C (220°F). Eight
(8) passes per roll were made, which corresponds to four (4)
passes per surface.
[00173] A test print was then printed onto the sheet using
an HP1220C color inkjet printer. The printed sheet was
laminated using the following lamination peel strength test
method. The 8.5 x 11 inch sheet of Teslin was covered with an
8.5 x 11 inch Sealtran 3/2 laminating film. A 2 x 11 inch
strip of 20 1b. bond paper was placed along the center line
(in the 11 inch direction) on the Teslin. The film to be
tested was cut to 8.5 inch by 11 inch and placed directly on.
top of the aforementioned structure. The laminated sheet was
cut into a piece 4.25 inches by 11 inches. Strips were then
cut (1 inch by 4.25 inches) using a JDC Precision Sample
Cutter (Thwing Albert Tnstruments). Each strip was placed in
a silicone-coated "laminating pocket". The pocket was fed
through a pocket laminator large enough to accommodate the
pocket. The laminating roll temperature varied within a range
of from 275 to 300°F (120-135°C). The laminated samples were
then stored at room temperature for at least 24 hours prior to
peel testing. The laminating film was peeled back from the
Teslin and placed into the top jaw of a tensile tester. The
bottom portion was placed into the bottom jaw of the tensile
tester. A 180° peel was performed at 0.5 inches/minute with a
sample rate of 4.0 pt./second. The test results showed the

CA 02531021 2005-12-22
WO 2005/023543 PCT/US2004/026892
- 62 -
initial peel strength was 9.6 lbs./inch and demonstrated that
the resulting substrate retained its integrity following a 24
hour water soak.
Example 19
[00174] In preparing a coating composition of the present
invention, a 31o polydimethyldiallylammonium chloride sold
under the trade name CinFix RDF available from Stockhausen
GmbH & Co. KG, Krefeld, Germany was diluted to loo with
deionized water in a stainless steel or polyethylene mix
vessel under mild agitation. Mild agitation defined by a
medium pitch three lobed mixing head, the system at a mix-head
to mix vessel diameter ratio of 1 to 3 and the mix-head
spinning at 600 - 1000 rpm and appropriately positioned. In a
separate mix container, a 29% aqueous cationic acrylic
solution sold under the name WC-71-2143 available from PPG
Industries, Inc. is diluted with deionized water to 10% and
added to the main mix vessel containing pre diluted CinFix
RDF. In a separate mix Container, a 30°s aqueous cationic
polyurethane dispersion sold under the trade name Witcobond
W240 available from Crompton Corporation is diluted with
deionized water to 10% and added to the main mix vessel
containing the CinFix RDF and PPG WC-71-2143 mixture. The
resultant coating composition is stirred for 15 minutes. The
resultant pH was 5.5 +/- 0.5. The total solids of the
composition was 10% and a viscosity of 56cps measured using a
Brookfield viscometer, RVT, spindle no. 1, at 50 rpm and 25°C.
[00175] For comparison, other coating compositions were
produced using alternate CinFix additives and polyurethane
dispersions with or without WC-71-2143.

CA 02531021 2005-12-22
WO 2005/023543 PCT/US2004/026892
- 63 -
Ingredients% solids 8181-67-01 02 -03 -04 -05 O6 -07 -08
.09
CinFix 51 18.5 - - - _ _ _ _ -
NF
CinFix 10 - 100 100 100 100 - - - _
167
CinFix 10 - - - - - 100 100 100 100
RDF
WitcoBond31 49.6 - - _ _ _ _ _ _
W-234
WitcoBond10 - 150 75 - - 150 75 -
X-051
WitcoBond10 - - - 150 75 - - 150 75
W-240
WC-71-214310 - - 75 - 75 - 75 - 75
[00176] All values are in parts by weight (pbw).
Ingredients:
CinFix NF - a 50-60% active aqueous solution of
poly(quaternary amine) polymer (CAS No. 68583-79-9) from
Stockhausen GmbH & Co. KG, Krefeld, Germany.
CinFix 167 - a 50-60% active aqueous solution of
poly(quaternary amine) (Composition -Trade Secret) from
Stockhausen GmbH & Co. KG, Krefeld, Germany.
CinFix RDF - a 30-35o active aqueous solution of
poly(quaternary amine) polymer (CAS No. 26062-79-3) from
Stockhausen GmbH & Co. KG, Kre'feld, Germany.
WitcoBond W-234 - a 30-35% solids water-based dispersion of an
anionic aliphatic urethane from Uniroyal Chemical of
Middlebury, CT.
WitcoBond X-051 - a 30-35% solids water-based dispersion of a
cationic urethane from Uniroyal Chemical of Middlebury, CT.
WitcoBond W-240 - a 30-35% solids water-based self-cross
linking anionic polyurethane dispersion from Uniroyal Chemical
of Middlebury, CT.
WC-71-2143 - a 25-30% solids aqueous dispersion of a cationic
acrylic polymer from PPG Industries of Pittsburgh, PA.
PPG formulation no. WC-71-2143 is as an aqueous secondary
amine and hydroxyl functional acrylic polymer prepared via

CA 02531021 2005-12-22
WO 2005/023543 PCT/US2004/026892
- 64 -
solution polymerization. Also described as a cationic acrylic
polymer aqueous dispersion. WC-71-2143 was prepared as
follows.
Ingredients Weight, grams
Initial Charge '
Isopropanol 130.0
Feed 1
Isopropanol 113.0
n-Butyl acrylate 69.2
Methyl methacrylate 153.0
2-(tert-Butylamino)ethyl methyacrylate
(CAS 3775-90-4) 73.0
Styrene 69.2
VAZO~ 67 Initiator) 18.2
Feed 2
Glacial Acetic Acid 17.7
Feed 3
Deionized Water 1,085.0
1 2, 2'-Azobis(2-methylbutanenitrile) initiator commercially
available from E. I. du Pont de Nemours and Company,
Wilmington, Delaware
(00177] The initial charge was heated in a reactor with
agitation to reflux temperature (80°C.). The Feed 1 was added
in a continuous manner over a period of 3 hours. At the
completion of Feed 1 addition, the reaction mixture was held

CA 02531021 2005-12-22
WO 2005/023543 PCT/US2004/026892
- 65 -
at reflux for 3 hours. The resultant acrylic polymer solution
had a total solids content of 61.7 percent (determined by
weight difference of a sample before and after heating at
110°C. for one hour) and number average molecular weight of
4792 as determined by gel permeation chromatography using
polystyrene as the standard. Thereafter, Feed 2 was added
over five minutes at room temperature with agitation. After
the completion of the addition of Feed 2, Feed 3 was added
over 30 minutes while the reaction mixture was heated for
azeotropic distillation of isopropanol. When the distillation
temperature reached 99°C, the distillation was continued about
one more hour and then the reaction mixture was cooled to room
temperature. The total distillation collected was 550.6
grams. The product, which was a cationic acrylic polymer
aqueous solution, had a solids content of 32.6 percent by
weight (determined by weight difference of a sample before and
after heating at 110°C. for one hour), and a pH of 5.25.
All % solids values are % by weight.
[00178] Coatings were applied to blank 8~" x 11" Teslin° TS
1000 sheet. Coating weight is measured by difference using an
electronic balance.
~ The blank sheet is weighed.
~ Coating is applied to the front side using a #9 wire-
wrapped rod.
The sheet is baked at 95° C in a textile oven (Model LTF
from Werner Mathis AG, Zurich, Switzerland) for 2
minutes.
~ The sheet is removed from the oven and coating is applied
to the backside using a #9 wire-wrapped rod.
~ The sheet is re-baked at 95° C in the textile oven for 2
minutes.
~ The sheet is removed, allowed to cool to the touch and
reweighed.

CA 02531021 2005-12-22
WO 2005/023543 PCT/US2004/026892
- 66 -
~ Coating weight in milligrams/square-inch is determined by
dividing weight difference in milligrams by coated area.
(00179] The dynamic viscosity of the mixed coatings was
measured using a #2 Zahn cup and the static viscosity was
measured using a Brookfield Model DV-1-~- viscometer using a #2
spindle at 100 rpm.
Coating Coating Weight #2ZahncupBrookfieldViscosity
mg./square inch(seconds)(Centipoise C~ 22°C)
-01 2.5 16.5 51.6
-02 0.4 23.6 236.4
-03 0.9 17.7 65.6
-04 1.5 15.5 40
-05 0.3 21.1 85.6
-06 0.4 21.7 125.2
-07 0.9 16.1 40.8
-08 0.6 16.3 48.8
-09 1.1 15.4 41.2
(00180] Test prints from the coated Teslin sheets were
generated off of an HP960C printer, set to normal default
print mode. Optical density values were measured using an X-
Rite° densitometer, model type 418, normalized against a
Macbeth° black/white standard plate. Test prints were also
generated using uncoated Teslin TS1000 for comparison. Optical
density values are listed in the following table.
Coating CMY C M Y K
No 0.76 1.02 0.81 0.55 0.76
coating
-Ol 1.30 1.05 1.32 1.04 1.13

CA 02531021 2005-12-22
WO 2005/023543 PCT/US2004/026892
- 67 -
-02 1.01 0.84 1.05 0.84 1.03
-03 1.08 0.83 1.03 0.83 1.08
-04 1.05 0.95 1.23 0.96 1.04
-05 1.15 0.87 1.07 0.87 1.15
-06 1.25 1.11 1.26 0.97 1.28
-07 , 1.23 1.27 '1.21 1.01 1.39
-08 1.27 1.07 1.28 1.00 1.16
-09 1.30 1.24 1.41 1.13 1.29
1.6
1.4
1.2
1
~ CMY
N
G ~C
N
° 0.8 ~ M
.Q D Y
o ~K
0.6
0.4
0.2
[00181 The 09 coating was applied to 8i~" x 11" sheets of
Teslin~ TS1000 and SP1000 and cured as described above. Test
prints from the coated Teslin sheets were generated off of an
HP960C printer, set to normal default print mode. Optical
density values were measured using an X-Rite densitometer,
model type 418, normalized against a Macbeth° black/white
standard plate. Optical density values are listed in the
following table.
0
No coating 8181-67-01 -02 -03 -04 -05 -06 -07 -08 -09
Coating

CA 02531021 2005-12-22
WO 2005/023543 PCT/US2004/026892
- 68 -
Teslin CMY C M y R
TS1000 1.08 1.20 1.23 0.99 1.16
SP1000 1.09 1.22 1.22 1.02 1.16
Example 20
[00182] Several 6,600ft rolls of 10.5mi1 Teslin TS1000 were
sized with coating composition described in Example 19 in
accordance the technique described in Example 19. The
resultant rolls was converted into 8.5" x 11"sheets, grain
long. Test prints were generated off of an HP960C printer,
set to best ink jet photo grade matte finish. Both sides of
the substrate were printed. The optical density of color bars
representing the five primary color/ink types: composite
black, cyan, magenta, yellow and pigment black were measured.
The printed color bars were submerged in tap water for
l5minutes and the resultant optical densities measured. The
procedure was then repeated after a total of 24hours of
continuous soaking. The optical density values are given in
the following tables.
Optical Density Retention - Side A
24hrs, Tap Water
Water CMY Cyan Magenta Yellow Pigment
Soak Time Black
Initial 1.31 1.13 1.26 0.88 1.30
15 1.31 1.14 1.25 0.90 1.30
minutes
24 hours 1.32 1.12 1.24 0.89 1.29
Optical Density Retention - Side B

CA 02531021 2005-12-22
WO 2005/023543 PCT/US2004/026892
- 69 -
24hrs, Tap Water
Water CMY Cyan Magenta Yellow Pigment
Soak Time Black
Initial 1.31 1.14 1.27 0.89 1.30
15 1.33 1.14 1.23 0.91 1.30
minutes
24 hours 1.29 7..10 1.23 0.90 1.29
[00183] All color bars remained solid after 24hours of
soaking time in tap water. No bleed was visible off of any of
the colors. Bold l0point font that was part of the test print
samples, printed in composite black maintained good optical
clarity.
Example 21
[00184] Sheets 26-inch x 38-inch of treated Teslin TS1000
substrate, 10.5mils thick, were cut from a master roll in the
grain long direction. The Teslin had been coated with 3
passes on each side (3x3) using the same coating composition
as described in Example 19 and the same Flexographic coating
technology described in Example 19. One coated Teslin sheet
was placed on top of one 26-inch x 38-inch sheet of 0.21-inch
polyvinylchloride (PVC), supplied by Empire Plastics. The PVC
sheet was cut in the grain long direction. A sheet 27-inch x
39-inch of 2-mil clear polyester was placed over the Teslin
sheet to act as a release liner. This release liner was
removed from the composite sheet following lamination and is
not an integral part of the final composite sheets. This
construction was placed between two 27" x 39" x 30mi1 polished
stainless steel metal plate. The resultant stack was then
placed between two 27" x 39" x 125mi1 un-polished non-
corrosive metal plates. This entire construction was placed

CA 02531021 2005-12-22
WO 2005/023543 PCT/US2004/026892
- 70 -
in a 200-Ton Wabash laminating press, preheated to 220F. The
composite construction was compression laminated at a pressure
of 200psi for 8minutes at a temperature of 220F. While under
press, the platens were cooled to less than 100°F, which took
approximately 22minutes. After being removed from the press,
the resultant composite sheet was removed from the stack '
construction. The finished composite sheet had good
integrity; any attempt to delaminate destroyed the Tesliiz
layer, which demonstrated a good adhesive and seamless bond
between the Teslin and the PVC. IS07910 TD-1 cards were die
cut from the resultant 26-inch x 38-inch x 30.5mi1 composite
sheet. The finished cards had good integrity and good lat
flat. Any attempt to delaminate destroyed the Teslin layer,
which demonstrated a good adhesive and seamless bond between
the Teslin and the PVC.
Example 22
[00185] Sheets 20-inch x 25-inch of treated Teslin
substrate, 10.5mils thick, were cut from a master roll in the
grain long direction. The Teslin had been coated with 3
passes on each side (3x3) using the same coating composition
as described in example 1 and the same Flexographic coating
technology described in example 2. One coated Teslin sheet
was placed on top of one 20-inch x 25-inch sheet of 0.10-inch
polyvinylchloride (PVC), supplied by Empire Plastics. The PVC
sheet was cut in the grain long direction. Below the PVC ply
was a second ply of 20-inch x 25-inch x 10mi1 PVC, cut grain
short. Below the l0mil PVC grain. short ply was a 20-inch x
25-inch x 2mi1 PVC sheet cut grain long. A sheet 21-inch x
26-inch of 2-mil clear polyester was placed over the Teslin
sheet to act as a release liner. This construction was placed
between two 21" x 26" x 30mi1 polished stainless steel metal
plate. An identical polyester/treated Teslin
sheet/PVC/PVC/PVC lay-up was placed on top of a stainless
plate from the existing construction. A polished metal plate

CA 02531021 2005-12-22
WO 2005/023543 PCT/US2004/026892
- 71 -
was placed over the exposed polyester release liner. The
pattern was repeated ten more times so that twelve pre-pressed
multi-layer plys existed in the stack. The resultant stack
was placed between buffer pads. The buffer pads are a
combination polyamide fiber and mechanical rubber,
manufactured and supplied by Yamauchi Corporation, designed to
more uniformally distribute temperature and press during
thermal lamination. The resultant stack plus buffer pads was
then placed between two slightly larger 125mi1 un-polished
non-corrosive metal plates. This entire construction,
referred to as a book, was placed in a TMP laminating press,
preheated to 300°F. The composite construction was compression
laminated at a pressure of 203psi for l8minutes at a
temperature of 300°F. While under press, the platens were
cooled to less than 100°F, which took approximately l9minutes.
After being removed from the press, all twelve composite
sheets were removed from the book. All twelve finished
composite sheets had good integrity; any attempt to delaminate
destroyed the Teslin layer, which demonstrated a good adhesive
and seamless bond between the Teslin and the PVC. IS07910 ID-
1 cards were die cut from the each of the 20-inch x 25-inch x
30.5mi1 composite sheets. The finished cards from each
composite sheet had good integrity and good lat flat. Ai~.y
attempt to delaminate destroyed the Teslin layer, which
demonstrated a good adhesive and seamless bond between the
Teslin and the PVC.
[00186] This foregoing example was also conducted using
Teslin SP1000 which produced the same results as the Teslin
TS1000.
Example 23
[00187] Composite sheets fabricated according to Example 19,
were individually soaked in deionized water for l5minutes then
allowed air dry for 24 hours. IS07910 ID-1 cards were die cut

CA 02531021 2005-12-22
WO 2005/023543 PCT/US2004/026892
- 72 -
from the each of the 20-inch x 25-inch x 30.5mi1 composite
sheets. The finished cards from each composite sheet had good
integrity and good lat flat. Any attempt to delaminate
destroyed the Teslin layer,~'which demonstrated a good adhesive
and seamless bond between the Teslin and the PVC. Resultant
conditioned cards demonstrated easier separation from a stack
and slip characteristics compared to the unconditioned
version.
[00188] The following table compares the optical density
retention performance of the new offering (8181-67-09 recipe)
to standard IJ1000WP (2 component recipe). Test print
patterns used in this study were produced off of an HP970
color inkjet printer, set on best quality and photo grade ink
jet glossy paper.
Optical Density following De-Ionized Water Soak
Soak Composite Cyan Magenta Yellow Pigmented
Time Black Black
(hrs)
Std. Teslin0 1.26 1.2 1.18 0.86 1.25
IJ1000WP
24 1.21 1.13 1.03 0.74 1.19
96 1.18 1.08 1.03 0.71 1.17
New Teslin 0 1.39 1.33 1.22 0.91 1.37
IJ1000WP
(8181-67-09)
24 1.39 1.35 1.29 0.92 1.37
96 1.39 1.32 1.31 0.92 1.36
[00189] The invention has been described with reference to
specific embodiments. Obvious modifications and alterations
will occur to others upon reading and understanding the

CA 02531021 2005-12-22
WO 2005/023543 PCT/US2004/026892
- 73 -
detailed description. It is intended that the invention be
construed as including all such modifications and alterations
insofar as they come within the scope of the invention or the
equivalents thereof.