U.S. patent application number 10/324173 was filed with the patent office on 2004-06-24 for polymer blend compositions.
This patent application is currently assigned to Westvaco Corporation, a corporation of the State of Delaware. Invention is credited to St. Arnauld, Jean Caprice.
Application Number | 20040121173 10/324173 |
Document ID | / |
Family ID | 32507322 |
Filed Date | 2004-06-24 |
United States Patent
Application |
20040121173 |
Kind Code |
A1 |
St. Arnauld, Jean Caprice |
June 24, 2004 |
POLYMER BLEND COMPOSITIONS
Abstract
This invention relates to polymer blend compositions and the
process for preparing the same. In particular, the invention
relates to novel blends of cationic polymers and anionic polymers
which exhibit properties that make them useful as coatings for
various substrates.
Inventors: |
St. Arnauld, Jean Caprice;
(Charleston, SC) |
Correspondence
Address: |
MEADWESTVACO CORPORATION
5255 VIRGINIA AVENUE
P.O. BOX 118005
CHARLESTON
SC
29423-8005
US
|
Assignee: |
Westvaco Corporation, a corporation
of the State of Delaware
Stamford
CT
|
Family ID: |
32507322 |
Appl. No.: |
10/324173 |
Filed: |
December 20, 2002 |
Current U.S.
Class: |
428/500 |
Current CPC
Class: |
B41M 5/52 20130101; B41M
5/5236 20130101; Y10T 428/31895 20150401; B41M 5/5245 20130101;
B41M 5/5218 20130101; C08L 33/068 20130101; Y10T 428/31938
20150401; C08L 33/14 20130101; Y10T 428/31511 20150401; B41M 5/5227
20130101; B41M 5/5254 20130101; Y10T 428/3188 20150401; Y10T
428/31935 20150401; Y10T 428/31855 20150401; B41M 5/508
20130101 |
Class at
Publication: |
428/500 |
International
Class: |
B32B 027/38 |
Claims
What is claimed is:
1. A polymer blend composition comprising, in admixture: A) from
about 1.0 to about 99.0% by weight of the composition of at least
one cationic polymer composition produced by reacting in a free
radical polymerization reaction a mixture comprising: 1) about 6.0
to about 28.0% by total weight of the mixture of a member selected
from the group consisting of amine-containing ethylenically
unsaturated monomers, ethylenically unsaturated monomers containing
at least one quaternary ammonium group, N-hydroxymethyl acrylamide,
N-hydroxymethyl methacrylamide, N-hydroxymethyl-substituted
acrylamide, N-hydroxymethyl-substituted methacrylamide, and
combinations thereof; 2) about 0.1 to about 40.0% by total weight
of the mixture of a member selected from the group consisting of
acrylic esters of alcohols containing from 1 to 22 carbon atoms,
methacrylic esters of alcohols containing from 1 to 22 carbon
atoms, styrene, substituted styrenes, acrylonitrile,
methacrylonitrile, vinyl chloride, vinylidene chloride, vinyl
ethers, vinyl esters, N-vinyl amides, and combinations thereof; 3)
about 3.0 to about 5.0% by total weight of the mixture of a member
selected from the group consisting of cationic surfactants and
combinations thereof; 4) up to about 3.0% by total weight of the
mixture of a member selected from the group consisting of non-ionic
surfactants and combinations thereof; 5) up to about 9.0% by total
weight of the mixture of a member selected from the group
consisting of ethylenically unsaturated monomers containing at
least one hydroxyl group and combinations thereof; 6) up to about
4.0% by total weight of the mixture of at least one chain transfer
agent; 7) a catalytic amount of polymerization initiator; and 8)
the balance of the mixture being water; to produce the cationic
polymer composition having a solids content in the range of about
1.0% to about 50.0% and a pH in the range of about 3.5 to about
8.5; and B) from about 1.0 to about 99.0% by total weight of the
composition of at least one anionic polymer composition produced by
reacting in a free radical polymerization reaction a mixture
comprising: 1) about 20.0 to about 50.0% by total weight of the
mixture of a member selected from the group consisting of vinylic
monomers and combinations thereof; 2) up to about 20.0% by total
weight of the mixture of a member selected from the group
consisting of water-dispersible polymers having an acid number of
no greater than 250 and a weight average molecular weight in the
range of about 4,000 to about 20,000 and combinations thereof; 3)
up to about 5.0% by total weight of the mixture of a member
selected from the group consisting of epoxy monomers that contain
at least two ethylene oxide groups, epoxy monomers that contain at
least two epoxide groups, epoxy monomers that contain at least one
ethylene oxide group and at least one epoxide group, and
combinations thereof; 4) up to about 5.0% by total weight of the
mixture of a member selected from the group consisting of anionic
surfactants, non-ionic surfactants, and combinations thereof; 5) up
to about 4.0% by total weight of the mixture of a member selected
from the group consisting of chain transfer agents and combinations
thereof; 6) up to about 5.0% by total weight of the mixture of at
least one organic solvent; 7) a catalytic amount of polymerization
initiator; and 8) the balance of the mixture being water; to
produce an anionic polymer composition having a solids content in
the range of about 1.0% to about 50.0%, a pH in the range of about
3.5 to about 9.0, and an acid number of no greater than about 22;
and wherein said polymer blend composition has an acid number no
greater than about 22.
2. The polymer blend composition of claim 1 which comprises, in
admixture: A) from about 10.0 to about 90.0% by weight of the
composition of at least one cationic polymer composition produced
reacting in a free radical polymerization reaction a mixture
comprising: 1) about 10.0% to about 15.0% by total weight of the
mixture of a member selected from the group consisting of
amine-containing ethylenically unsaturated monomers, ethylenically
unsaturated monomers containing at least one quaternary ammonium
group, N-hydroxymethyl acrylamide, N-hydroxymethyl methacrylamide,
N-hydroxymethyl-substituted acrylamide, N-hydroxymethyl-substituted
methacrylamide, and combinations thereof; 2) about 5.0% to about
20.0% by total weight of the mixture of a member selected from the
group consisting of acrylic esters of alcohols containing from 1 to
22 carbon atoms, methacrylic esters of alcohols containing from 1
to 22 carbon atoms, styrene, substituted styrenes, acrylonitrile,
methacrylonitrile, vinyl chloride, vinylidene chloride, vinyl
ethers, vinyl esters, N-vinyl amides, and combinations thereof; 3)
about 4.0% to about 5.0% by total weight of the mixture of a member
selected from the group consisting of cationic surfactants and
combinations thereof; 4) up to about 3.0% by total weight of the
mixture of a member selected from the group consisting of non-ionic
surfactants and combinations thereof; 5) up to about 9.0% by total
weight of the mixture of a member selected from the group
consisting of ethylenically unsaturated monomers containing at
least one hydroxyl group and combinations thereof; 6) up to about
4.0% by total weight of the mixture of at least one chain transfer
agent; 7) a catalytic amount of polymerization initiator; and 8)
the balance of the mixture being water; to produce the cationic
polymer composition having a solids content in the range of about
1.0% to about 50.0% and a pH in the range of about 3.5 to about
8.5; and B) from about 10.0% to about 90.0% by total weight of the
composition of at least one anionic polymer composition produced by
reacting in a free radical polymerization reaction a mixture
comprising: 1) about 35.0% to about 50.0% by total weight of the
mixture of a member selected from the group consisting of vinylic
monomers and combinations thereof; 2) about 5.0% to about 10.0% by
total weight of the mixture of a member selected from the group
consisting of water-dispersible polymers having an acid number of
no greater than 250 and a weight average molecular weight in the
range of about 4,000 to about 20,000 and combinations thereof; 3)
up to about 4.0% by total weight of the mixture of a member
selected from the group consisting of epoxy monomers that contain
at least two ethylene oxide groups, epoxy monomers that contain at
least two epoxide groups, epoxy monomers that contain at least one
ethylene oxide group and at least one epoxide group, and
combinations thereof; 4) about 1.0% to about 3.0% by total weight
of the mixture of a member selected from the group consisting of
anionic surfactants, non-ionic surfactants, and combinations
thereof; 5) up to about 4.0% by total weight of the mixture of a
member selected from the group consisting of chain transfer agents
and combinations thereof; 6) up to about 5.0% by total weight of
the mixture of at least one organic solvent; 7) a catalytic amount
of polymerization initiator; and 8) the balance of the mixture
being water; to produce an anionic polymer composition having a
solids content in the range of about 1.0% to about 50.0%, a pH in
the range of about 3.5 to about 9.0, and an acid number of no
greater than about 22; and wherein said polymer blend composition
has an acid number no greater than about 22.
3. The polymer blend composition of claim 1 wherein the
amine-containing ethylenically unsaturated monomer is a member
selected from the group consisting of dimethylaminoethyl acrylate,
dimethylaminoethyl methacrylate, diethylaminoethyl methacrylate,
t-butylaminoethyl methacrylate, dimethylaminopropyl methacrylamide,
allylamine, 2-vinylpyridine, 4-vinylpyridine, and combinations
thereof.
4. The polymer blend composition of claim 1 wherein the
ethylenically unsaturated monomer containing at least one
quaternary ammonium group is a member selected from the group
consisting of hydroxyethyl acrylate, hydroxypropyl acrylate,
hydroxybutyl acrylate, hydroxyethyl methacrylate, hydroxypropyl
methacrylate, butanediol monovinyl ether, allyl alcohol, and
combinations thereof.
5. The polymer blend composition of claim 1 wherein the cationic
surfactant is a member selected from the group consisting of
alkyltrimethylammonium salts wherein the alkyl group contains from
8 to 22 carbon atoms and the counterion of the salt is a member
selected from the group consisting of chloride, bromide,
methylsulfate, and ethylsulfate; alkylbenzyldimethylammonium salts
wherein the alkyl group contains from 8 to 22 carbon atoms and the
counterion of the salt is a member selected from the group
consisting of chloride, bromide, methylsulfate, and ethylsulfate;
alkylpyridinium salts wherein the alkyl group contains from 8 to 22
carbon atoms and the counterion of the salt is a member selected
from the group consisting of chloride, bromide, methylsulfate, and
ethylsulfate; and combinations thereof.
6. The polymer blend composition of claim 1 wherein the nonionic
surfactant in the mixture reacted to produce the cationic polymer
composition is a member selected from the group consisting of
ethoxylated alkylphenols, ethoxylated fatty alcohols, ethylene
oxide/propylene oxide block copolymers, and combinations
thereof.
7. The polymer blend composition of claim 1 wherein the
ethylenically unsaturated monomer containing at least one hydroxyl
group is a member selected from the group consisting of
hydroxyethyl acrylate, hydroxypropyl acrylate, hydroxybutyl
acrylate, hydroxyethyl methacrylate, hydroxypropyl methacrylate,
butanediol monovinyl ether, allyl alcohol, and combinations
thereof
8. The polymer blend composition of claim 1 wherein the chain
transfer agent in the mixture reacted to produce the cationic
polymer composition is a member selected from the group consisting
of dodecyl mercaptan, 2-mercaptoethanol, alkyl mercaptopropionates,
mercaptoacetic acid, mercaptopropionic acid, octyl mercaptan, and
combinations thereof.
9. The polymer blend composition of claim 1 wherein the
polymerization initiator in the mixture reacted to produce the
cationic polymer composition comprises from about 0.1% to about
3.0% by total weight of the mixture reacted to produce the cationic
polymer composition and is a member selected from the group
consisting of thermal initiators, redox initiators, and
combinations thereof.
10. The polymer blend composition of claim 9 wherein the thermal
initiator is a member selected from the group consisting of
hydrogen peroxide, t-butyl hydroperoxide, di-t-butyl peroxide,
benzoyl peroxide, benzoyl hydroperoxide, 2,4-dichlorobenzoyl
peroxide, t-butyl peracetate, azobisisobutyronitrile, isopropyl
peroxycarbonate, and combinations thereof.
11. The polymer blend composition of claim 9 wherein the redox
initiator is a member selected from the group consisting of cumene
hydroperoxide-sodium metabisulfite, cumene hydroperoxide-iron (II)
sulfate, and combinations thereof.
12. The polymer blend composition of claim 1 wherein the cationic
polymer composition has a solids content in the range of about
35.0% to about 45.0%.
13. The polymer blend composition of claim 1 wherein the cationic
polymer composition has a pH in the range of about 4.5 to about
8.0.
14. The polymer blend composition of claim 1 wherein the vinylic
monomer is a member selected from the group consisting of styrenic
monomers, acrylic monomers, methacrylic monomers, ethylenic
monomers, and combinations thereof.
15. The polymer blend composition of claim 14 wherein the vinylic
monomer is a member selected from the group consisting of acrylic
acid, methacrylic acid, methyl methacrylate, ethyl methacrylate,
n-propyl methacrylate, n-butyl methacrylate, isopropyl
methacrylate, isobutyl methacrylate, n-amyl methacrylate, n-hexyl
methacrylate, isoamyl methacrylate, 2-hydroxyethyl methacrylate,
2-hydroxypropyl methacrylate, N,N-dimethylaminoethyl methacrylate,
N,N-diethylaminoethyl methacrylate, t-butylaminoethyl methacrylate,
2-sulfoethyl methacrylate, trifluoroethyl methacrylate, glycidyl
methacrylate, benzyl methacrylate, allyl methacrylate,
2-n-butoxyethyl methacrylate, 2-chloroethyl methacrylate,
sec-butyl-methacrylate, tert-butyl methacrylate, 2-ethybutyl
methacrylate, cinnamyl methacrylate, crotyl methacrylate,
cyclohexyl methacrylate, cyclopentyl methacrylate, 2-ethoxyethyl
methacrylate, furfuryl methacrylate, hexafluoroisopropyl
methacrylate, methallyl methacrylate, 3-methoxybutyl methacrylate,
2-methoxybutyl methacrylate, 2-nitro-2 methylpropyl methacrylate,
n-octylmethacrylate, 2-ethylhexyl methacrylate, 2-phenoxyethyl
methacrylate, 2-phenylethyl methacrylate, phenyl methacrylate,
propargyl methacrylate, tetrahydrofurfuryl methacrylate,
tetrahydropyranyl methacrylate, methyl acrylate, ethyl acrylate,
n-propyl acrylate, isopropyl acrylate, n-butyl acrylate, n-decyl
acrylate, 2-ethylhexal acrylate, salts of methacrylic acid,
methacrylonitrile, methacrylamide, N-methylmethacrylamide,
N-ethylmethacrylamide, N,N-diethymethacrylamide,
N,N-dimethylmethacrylami- de, N-phenyl-methacrylamide,
methacrolein, salts of acrylic acid, acrylonitrile, acrylamide,
methyl alpha-chloroacrylate, methyl 2-cyanoacrylate,
N-ethylacrylamide, N,N-diethylacrylamide acrolein, vinyl acetate,
vinyl chloride, vinyl pyridine, vinyl pyrollidone, sodium
crotonate, methyl crotonate, crotonic acid, maleic anhydride, and
combinations thereof
16. The polymer blend composition of claim 1 wherein the
water-dispersible polymer is a member selected from the group
consisting of acrylic acid, methacrylic acid, fumaric acid, maleic
anhydride and combinations thereof.
17. The polymer blend composition of claim 1 wherein the
water-dispersible polymer has a weight average molecular weight in
the range of about 5,000 to about 12,000.
18. The polymer blend composition of claim 1 wherein the
water-dispersible polymer has an acid number in the range of about
180 to 250.
19. The polymer blend composition of claim 1 wherein the epoxy
monomer is a member selected from the group consisting of aliphatic
epoxidized urethanes, aromatic epoxidized urethanes, glycidyl
acrylate esters, esters, siloxanes, aliphatic hydrocarbons, cyclic
hydrocarbons, and combinations thereof.
20. The polymer blend composition of claim 1 wherein the anionic
surfactant is a member selected from the group consisting of alkyl
sulfates, ether sulfates, phosphate esters, sulfonates, and
combinations thereof.
21. The polymer blend composition of claim 1 wherein the nonionic
surfactant in the mixture reacted to produce the anionic polymer
composition is a member selected from the group consisting of
ethoxylated alkylphenols, ethoxylated fatty alcohols, ethylene
oxide/propylene oxide block copolymers, and combinations
thereof.
22. The polymer blend composition of claim 1 wherein the chain
transfer agent in the mixture reacted to produce the anionic
polymer composition is a member selected from the group consisting
of dodecyl mercaptan, 2-mercaptoethanol, alkyl mercaptopropionates,
mercaptoacetic acid, mercaptopropionic acid, octyl mercaptan, and
combinations thereof.
23. The polymer blend composition of claim 1 wherein the
polymerization initiator in the mixture reacted to produce the
anionic polymer composition comprises from about 0.1% to about 3.0%
by total weight of the mixture reacted to produce the anionic
polymer composition and is a member selected from the group
consisting of thermal initiators, redox initiators, and
combinations thereof.
24. The polymer blend composition of claim 23 wherein the thermal
initiator is a member selected from the group consisting of
hydrogen peroxide, t-butyl hydroperoxide, di-t-butyl peroxide,
benzoyl peroxide, benzoyl hydroperoxide, 2,4-dichlorobenzoyl
peroxide, t-butyl peracetate, azobisisobutyronitrile, isopropyl
peroxycarbonate, and combinations thereof.
25. The polymer blend composition of claim 23 wherein the redox
initiator is a member selected from the group consisting of cumene
hydroperoxide-sodium metabisulfite, cumene hydroperoxide-iron (II)
sulfate, and combinations thereof.
26. The polymer blend composition of claim 1 wherein the anionic
polymer composition has a solids content in the range of about
35.0% to about 50.0%.
27. The polymer blend composition of claim 1 wherein the anionic
polymer composition has a pH in the range of about 8.0 to about
9.0.
28. The polymer blend composition of claim 1 wherein the anionic
polymer composition has an acid number no greater than about
10.
29. The polymer blend composition of claim 1 wherein the anionic
polymer composition has an acid number no greater than about 5.
30. The polymer blend composition of claim 1 wherein said
composition has an acid number no greater than about 10.
31. The polymer blend composition of claim 1 wherein said
composition has an acid number no greater than about 5.
32. An ink jet receptive coating comprising the polymer blend
composition of claim 1.
33. The ink jet receptive coating of claim 32 wherein the coating
further comprises a pigment.
34. The ink jet receptive coating of claim 33 wherein the pigment
is a member selected from the group consisting of silica, alumina,
plastic pigments, calcium carbonate, kaolin clay, and combinations
thereof.
35. An ink jet printable product comprising a substrate coated on
at least one side with the coating of claim 32.
36. The ink jet printable product of claim 35 where the substrate
is a member selected from the group consisting of paper,
paperboard, wood, plastics, metal foil, textiles, and combinations
thereof.
37. A coating comprising the polymer blend composition of claim
1.
38. The coating of claim 37 wherein the coating further comprises a
pigment.
39. The coating of claim 38 wherein the pigment is a member
selected from the group consisting of silica, alumina, plastic
pigments, calcium carbonate, kaolin clay, organic based pigments,
inorganic based pigments, and combinations thereof.
Description
FIELD OF INVENTION
[0001] This invention relates to polymer blend compositions and the
process for preparing the same. In particular, the invention
relates to novel blends of cationic polymers and anionic polymers
which exhibit properties that make them useful as coatings for
various substrates.
BACKGROUND OF THE INVENTION
[0002] Ink jet printing is widely used to print on a variety of
substrates (including paper, textiles, and plastics). These
substrates are often coated with a material that enhances their
receptivity for the ink jet ink. In the case of aqueous dye-based
inks, which comprise the majority of inks currently used in ink jet
printing, the property of dye fixation is particularly important.
Most aqueous ink jet inks are based on dyes rather than pigments.
To obtain sharp prints with high color density, the dye molecules
must be immobilized almost immediately upon contact of the ink with
the substrate. Penetration of the dyes into the substrate will
result in reduced color density, while lateral migration of the dye
molecules will cause indistinctness in the image formed.
[0003] The dyes that are commonly employed in aqueous ink jet inks
are anionic in nature, containing sulfonic acid groups.
Accordingly, dye fixation is generally accomplished by
incorporating cationic polymers into the ink jet receptive
coatings. These cationic polymers employ salt formation mechanisms
to fix the dyes. The most widely used cationic dye fixative in ink
jet receptive coatings is poly(diallyldimethylammonium chloride),
although other water-soluble cationic polymers are known in the
art. For example, U.S. Pat. No. 6,010,790 teaches the use of
poly(vinylbenzylquaternary ammonium salts). Other examples of
water-soluble cationic polymers are cationic starch, cationic
polyvinyl alcohol, guanidine-formaldehyde resins,
epichlorohydrin-polyamine condensates, and water-soluble cationic
acrylic resins.
[0004] However, problems exist with the use of soluble or
water-borne cationic polymers. For example, unless these polymers
are cross-linked in some way, their presence often has a
detrimental effect on the water resistance and chemical resistance
of ink jet prints and other coatings. Also, as these cationic
polymers are relatively expensive, their use in traditional
packaging applications is limited. Furthermore, in many
applications it is desirable to match the gloss of the coating to
the appearance of the substrate. However, due to the glossy nature
of most cationic polymers, it is often necessary to use
gloss-modifying pigments to adjust the appearance of the finished
coating. Also, the chemical nature of cationic polymers limits the
materials available to modify the physical properties of the
cationic-based coatings, in that many of the additives commonly
used with anionic-based coatings would form precipitants or gels if
employed with cationic-based coatings. Furthermore, as coatings
produced with cationic polymers are normally transparent in nature,
the color development of inks may be adversely effected by the
color of the underlying substrate. Finally, cationic-based coatings
are usually much slower to dry than anionic coatings. As most
machinery used in coatings (e.g., flexographic printing presses,
gravure printing presses, rod-coater, etc.) are designed for use
with faster-drying anionic systems, the applicability of
cationic-based coatings systems are limited.
[0005] Anionic polymers are normally added to a coating formulation
in order to improve the chemical resistance, water resistance,
and/or rub resistance of the coating. However, anionic polymers are
not commonly employed in ink jet receptive coatings because, as
most ink jet inks are composed of anionic dyes, an anionic ink jet
receptive coating would not adequately fixate the dyes to the
coated substrate.
[0006] It would be desirable to be able to produce a stable blend
of cationic polymers and anionic polymers for use in various
coating applications.
[0007] Therefore, an object of this invention is to disclose stable
polymer blend compositions comprising mixtures of cationic polymer
compositions and anionic polymer compositions.
[0008] Another object of this invention is to disclose polymer
blend compositions which exhibit properties that allow them to be
useful as coating formulations.
[0009] A further object of this invention is to disclose polymer
blend compositions which exhibit properties that allow them to be
useful in producing ink jet ink printing coating formulations.
SUMMARY OF THE INVENTION
[0010] The present invention achieves these objects and others via
the production of polymer blend compositions that are stable
mixtures of cationic polymer compositions and anionic polymer
compositions. These novel blends minimize many of the problems
involved in using either a cationic polymer composition or an
anionic polymer composition in various coatings.
[0011] Skilled artisans would anticipate that the blending of
cationic polymer compositions with anionic polymer compositions
would not produce a stable polymer blend, as the negatively-charged
particles and the positively-charged particles would tend to
aggregate together to form a gel or to produce coagulum in the
polymer solution. It was, therefore, unexpected that stable polymer
blend compositions which exhibited no precipitate formation or
gelling could be produced via the present method.
[0012] By way of explanation, but without limitation, this result
may be caused by the employment of the particular cationic polymer
compositions and anionic polymer compositions of the present
invention. The free radical polymerization reaction utilized herein
results in the production of cationic polymer compositions that
contain at least one cationic functionality in the backbone of the
polymer. The chemical characteristics of these cationic polymer
compositions, coupled with the chemical characteristics and
relatively low acid numbers of the anionic polymer compositions,
may serve to retard the susceptibility of the respective polymers
to react chemically.
[0013] Irrespective of the exact chemical mechanism, the ability to
create stable water-borne polymer blend compositions which comprise
a mixture of cationic polymers and anionic polymers allows the
practitioner to produce compositions having chemical
characteristics not easily obtained through the use of either
cationic polymers or anionic polymers alone. For example, the
employment of polymer blend compositions allows one to match the
gloss of coatings to substrates, thereby improving the appearance
of the printed finished product. Also, a stable polymer blend
composition permits the utilization of a cationic polymer to modify
an anionic coating system to produce desired coating viscosities
without the loss of chemical resistance or other advantageous
properties. Moreover, the ability to blend cationic polymer
compositions with anionic polymer compositions allows one to
produce a polymer blend coating compositions with desired drying
rates. Finally, the broader versatility exhibited by the polymer
blend ink jet receptive coating compositions of the present
invention allows their employment in a variety of applications not
commercially viable for traditional cationic ink jet receptive
coatings.
DESCRIPTION OF THE PREFERRED EMBODIMENT
[0014] The polymer blend compositions of the present invention
comprise, in admixture:
[0015] A) from about 1.0% to about 99.0% by weight of the
composition of at least one cationic polymer composition produced
by reacting in a free radical polymerization reaction a mixture
comprising:
[0016] 1) about 6.0% to about 28.0% by total weight of the mixture
of a member selected from the group consisting of amine-containing
ethylenically unsaturated monomers, ethylenically unsaturated
monomers containing at least one quaternary ammonium group,
N-hydroxymethyl acrylamide, N-hydroxymethyl methacrylamide,
N-hydroxymethyl-substituted acrylamide, N-hydroxymethyl-substituted
methacrylamide, and combinations thereof;
[0017] 2) about 0.1% to about 40.0% by total weight of the mixture
of a member selected from the group consisting of acrylic esters of
alcohols containing from 1 to 22 carbon atoms, methacrylic esters
of alcohols containing from 1 to 22 carbon atoms, styrene,
substituted styrenes, acrylonitrile, methacrylonitrile, vinyl
chloride, vinylidene chloride, vinyl ethers, vinyl esters, N-vinyl
amides, and combinations thereof;
[0018] 3) about 3.0% to about 5.0% by total weight of the mixture
of a member selected from the group consisting of cationic
surfactants and combinations thereof;
[0019] 4) up to about 3.0% by total weight of the mixture of a
member selected from the group consisting of non-ionic surfactants
and combinations thereof;
[0020] 5) up to about 9.0% by total weight of the mixture of a
member selected from the group consisting of ethylenically
unsaturated monomers containing at least one hydroxyl group and
combinations thereof;
[0021] 6) up to about 4.0% by total weight of the mixture of at
least one chain transfer agent;
[0022] 7) a catalytic amount of polymerization initiator; and
[0023] 8) the balance of the mixture being water; to produce the
cationic polymer composition having a solids content in the range
of about 1.0% to about 50.0% and a pH in the range of about 3.5 to
about 8.5; and
[0024] B) from about 1.0 to about 99.0% by total weight of the
composition of at least one anionic polymer composition produced by
reacting in a free radical polymerization reaction a mixture
comprising:
[0025] 1) about 20.0 to about 50.0% by total weight of the mixture
of a member selected from the group consisting of vinylic monomers
and combinations thereof;
[0026] 2) up to about 20.0% by total weight of the mixture of a
member selected from the group consisting of water-dispersible
polymers having an acid number of no greater than 250 and a weight
average molecular weight in the range of about 4,000 to about
20,000 and combinations thereof;
[0027] 3) up to about 5.0% by total weight of the mixture of a
member selected from the group consisting of epoxy monomers that
contain at least two ethylene oxide groups, epoxy monomers that
contain at least two epoxide groups, epoxy monomers that contain at
least one ethylene oxide group and at least one epoxide group, and
combinations thereof;
[0028] 4) up to about 5.0% by total weight of the mixture of a
member selected from the group consisting of anionic surfactants,
non-ionic surfactants, and combinations thereof;
[0029] 5) up to about 4.0% by total weight of the mixture of a
member selected from the group consisting of chain transfer agents
and combinations thereof;
[0030] 6) up to about 5.0% by total weight of the mixture of at
least one organic solvent;
[0031] 7) a catalytic amount of polymerization initiator; and
[0032] 8) the balance of the mixture being water; to produce an
anionic polymer composition having a solids content in the range of
about 1.0% to about 50.0%, a pH in the range of about 3.5 to about
9.0, and an acid number of no greater than about 22; and
[0033] wherein said polymer blend composition has an acid number no
greater than about 22.
[0034] Preferred polymer blend compositions of the present
invention comprise, in admixture:
[0035] A) from about 10.0% to about 90.0% by weight of the
composition of at least one cationic polymer composition produced
reacting in a free radical polymerization reaction a mixture
comprising:
[0036] 1) about 10.0% to about 15.0% by total weight of the mixture
of a member selected from the group consisting of amine-containing
ethylenically unsaturated monomers, ethylenically unsaturated
monomers containing at least one quaternary ammonium group,
N-hydroxymethyl acrylamide, N-hydroxymethyl methacrylamide,
N-hydroxymethyl-substituted acrylamide, N-hydroxymethyl-substituted
methacrylamide, and combinations thereof;
[0037] 2) about 5.0% to about 20.0% by total weight of the mixture
of a member selected from the group consisting of acrylic esters of
alcohols containing from 1 to 22 carbon atoms, methacrylic esters
of alcohols containing from 1 to 22 carbon atoms, styrene,
substituted styrenes, acrylonitrile, methacrylonitrile, vinyl
chloride, vinylidene chloride, vinyl ethers, vinyl esters, N-vinyl
amides, and combinations thereof;
[0038] 3) about 4.0% to about 5.0% by total weight of the mixture
of a member selected from the group consisting of cationic
surfactants and combinations thereof;
[0039] 4) up to about 3.0% by total weight of the mixture of a
member selected from the group consisting of non-ionic surfactants
and combinations thereof;
[0040] 5) up to about 9.0% by total weight of the mixture of a
member selected from the group consisting of ethylenically
unsaturated monomers containing at least one hydroxyl group and
combinations thereof;
[0041] 6) up to about 4.0% by total weight of the mixture of at
least one chain transfer agent;
[0042] 7) a catalytic amount of polymerization initiator; and
[0043] 8) the balance of the mixture being water; to produce the
cationic polymer composition having a solids content in the range
of about 1.0% to about 50.0% and a pH in the range of about 3.5 to
about 8.5; and
[0044] B) from about 10.0% to about 90.0% by total weight of the
composition of at least one anionic polymer composition produced by
reacting in a free radical polymerization reaction a mixture
comprising:
[0045] 1) about 35.0% to about 50.0% by total weight of the mixture
of a member selected from the group consisting of vinylic monomers
and combinations thereof;
[0046] 2) about 5.0% to about 10.0% by total weight of the mixture
of a member selected from the group consisting of water-dispersible
polymers having an acid number of no greater than 250 and a weight
average molecular weight in the range of about 4,000 to about
20,000 and combinations thereof;
[0047] 3) up to about 4.0% by total weight of the mixture of a
member selected from the group consisting of epoxy monomers that
contain at least two ethylene oxide groups, epoxy monomers that
contain at least two epoxide groups, epoxy monomers that contain at
least one ethylene oxide group and at least one epoxide group, and
combinations thereof;
[0048] 4) about 1.0% to about 3.0% by total weight of the mixture
of a member selected from the group consisting of anionic
surfactants, non-ionic surfactants, and combinations thereof;
[0049] 5) up to about 4.0% by total weight of the mixture of a
member selected from the group consisting of chain transfer agents
and combinations thereof;
[0050] 6) up to about 5.0% by total weight of the mixture of at
least one organic solvent;
[0051] 7) a catalytic amount of polymerization initiator; and
[0052] 8) the balance of the mixture being water; to produce an
anionic polymer composition having a solids content in the range of
about 1.0% to about 50.0%, a pH in the range of about 3.5 to about
9.0, and an acid number of no greater than about 22; and
[0053] wherein said polymer blend composition has an acid number no
greater than about 22.
[0054] From about 1.0% to about 99.0% (preferably from about 10.0%
to about 90.0%) by weight of the polymer blend composition of the
present invention is composed of a cationic polymer composition or
combination of cationic polymer compositions. Cationic polymer
compositions which are suitable for use in the present invention
are produced by reacting in a free radical polymerization reaction
a mixture comprising:
[0055] 1) about 6.0% to about 28.0% (preferably from about 10.0% to
about 15.0%) by total weight of the mixture of a member selected
from the group consisting of amine-containing ethylenically
unsaturated monomers, ethylenically unsaturated monomers containing
at least one quaternary ammonium group, N-hydroxymethyl acrylamide,
N-hydroxymethyl methacrylamide, N-hydroxymethyl-substituted
acrylamide, N-hydroxymethyl-substituted methacrylamide, and
combinations thereof;
[0056] 2) about 0.1% to about 40.0% (preferably from about 5.0% to
about 20.0%) by total weight of the mixture of a member selected
from the group consisting of acrylic esters of alcohols containing
from 1 to 22 carbon atoms, methacrylic esters of alcohols
containing from 1 to 22 carbon atoms, styrene, substituted
styrenes, acrylonitrile, methacrylonitrile, vinyl chloride,
vinylidene chloride, vinyl ethers, vinyl esters, N-vinyl amides,
and combinations thereof;
[0057] 3) about 3.0 to about 5.0% (preferably from about 4.0% to
about 5.0%) by total weight of the mixture of a member selected
from the group consisting of cationic surfactants and combinations
thereof;
[0058] 4) up to about 3.0% by total weight of the mixture of a
member selected from the group consisting of non-ionic surfactants
and combinations thereof;
[0059] 5) up to about 9.0% by total weight of the mixture of a
member selected from the group consisting of ethylenically
unsaturated monomers containing at least one hydroxyl group and
combinations thereof,
[0060] 6) up to about 4.0% by total weight of the mixture of at
least one chain transfer agent;
[0061] 7) a catalytic amount of polymerization initiator; and
[0062] 8) the balance of the mixture being water; to produce a the
cationic polymer composition having a solids content in the range
of about 1.0% to about 50.0% (preferably from about 35.0% to about
45.0%) and a pH in the range of about 3.5 to about 8.5 (preferably
from about 4.5 to about 8.0).
[0063] Preferred amine-containing ethylenically unsaturated
monomers suitable for use in the present invention, include, but
are not limited to, the following: dimethylaminoethyl acrylate,
dimethylaminoethyl methacrylate, diethylaminoethyl methacrylate,
t-butylaminoethyl methacrylate, dimethylaminopropyl methacrylamide,
allylamine, 2-vinylpyridine, 4-vinylpyridine, and combinations
thereof.
[0064] Preferred ethylenically unsaturated monomers containing at
least one quaternary ammonium group suitable for use in the present
invention, include, but are not limited to, the following:
hydroxyethyl acrylate, hydroxypropyl acrylate, hydroxybutyl
acrylate, hydroxyethyl methacrylate, hydroxypropyl methacrylate,
butanediol monovinyl ether, allyl alcohol, and combinations
thereof.
[0065] Preferred cationic surfactants suitable for use in the
present invention, include, but are not limited to, the following:
alkyltrimethylammonium salts wherein the alkyl group contains from
8 to 22 carbon atoms and the counterion of the salt is a member
selected from the group consisting of chloride, bromide,
methylsulfate, and ethylsulfate; alkylbenzyldimethylammonium salts
wherein the alkyl group contains from 8 to 22 carbon atoms and the
counterion of the salt is a member selected from the group
consisting of chloride, bromide, methylsulfate, and ethylsulfate;
alkylpyridinium salts wherein the alkyl group contains from 8 to 22
carbon atoms and the counterion of the salt is a member selected
from the group consisting of chloride, bromide, methylsulfate, and
ethylsulfate; and combinations thereof.
[0066] Where desired, at least one nonionic surfactant may be added
to the mixture undergoing free radical polymerization to produce
the cationic polymer composition. Preferred nonionic surfactants
suitable for use in the present invention, include, but are not
limited to, the following: ethoxylated alkylphenols, ethoxylated
fatty alcohols, ethylene oxide/propylene oxide block copolymers,
and combinations thereof.
[0067] Where desired, at least one ethylenically unsaturated
monomer containing at least one hydroxyl group may be added to the
mixture undergoing free radical polymerization to produce the
cationic polymer composition. Preferred ethylenically unsaturated
monomers containing at least one hydroxyl group suitable for use in
the present invention, include, but are not limited to, the
following: hydroxyethyl acrylate, hydroxypropyl acrylate,
hydroxybutyl acrylate, hydroxyethyl methacrylate, hydroxypropyl
methacrylate, butanediol monovinyl ether, allyl alcohol, and
combinations thereof.
[0068] Where desired, at least one chain transfer agent may be
added to the mixture undergoing free radical polymerization to
produce the cationic polymer composition. Preferred chain transfer
agents suitable for use in the present invention, include, but are
not limited to, the following: dodecyl mercaptan,
2-mercaptoethanol, alkyl mercaptopropionates, mercaptoacetic acid,
mercaptopropionic acid, octyl mercaptan, and combinations
thereof.
[0069] A catalytic amount of at least one polymerization initiator
is used in the free radical polymerization reaction to produce the
cationic polymer composition. The amount of initiator employed
commonly comprises from about 0.1% to about 3.0% (preferably from
about 0.2% to about 2.0%) by weight of the total mixture used to
produce the cationic polymer composition. Traditional emulsion
polymerization initiators (such as thermal initiators, redox
initiators, and the like) are suitable for use in the free radical
emulsion polymerization reaction. Examples of suitable thermal
initiators include, but are not limited to, the following: hydrogen
peroxide, t-butyl hydroperoxide, di-t-butyl peroxide, benzoyl
peroxide, benzoyl hydroperoxide, 2,4-dichlorobenzoyl peroxide,
t-butyl peracetate, azobisisobutyronitrile, isopropyl
peroxycarbonate, and combinations thereof. Examples of suitable
redox initiators include, but are not limited to, the following:
cumene hydroperoxide-sodium metabisulfite, cumene
hydroperoxide-iron (II) sulfate, and combinations thereof.
Preferred initiators include water-soluble azo compounds (such as
V-50 or VA-086 manufactured by Wako Chemicals).
[0070] Sufficient water is added to the mixture to produce a
cationic polymer composition having a solids content in the range
of about 1.0% to about 50.0%. The preferred solids content for the
cationic polymer composition is in the range of about 35.0% to
about 45.0%.
[0071] Cationic polymer compositions suitable for use in the
present invention have a pH in the range of about 3.5 to about 8.5,
preferably in the range from about 4.5 to about 8.0. Where desired,
the pH of the cationic polymer composition may be adjusted via the
addition of a member selected from the group consisting of mineral
acids, water-soluble carboxylic acids, water-soluble sulfonic
acids, and combinations thereof. Where employed, it is preferred to
use at least one low molecular weight carboxylic acid such as
acetic acid, propionic acid, glycolic acid, lactic acid, and the
like.
[0072] From about 1.0% to about 99.0% (preferably from about 10.0%
to about 90.0%) by weight of the polymer blend composition of the
present invention is composed of an anionic polymer composition or
combination of anionic polymer compositions. Anionic polymer
compositions which are suitable for use in the present invention
are produced by reacting in a free radical polymerization reaction
a mixture comprising:
[0073] 1) about 20.0% to about 50.0% (preferably from about 35.0%
to about 50.0%) by total weight of the mixture of a member selected
from the group consisting of vinylic monomers and combinations
thereof;
[0074] 2) up to about 20.0% (preferably from about 5.0% to about
10.0%) by total weight of the mixture of a member selected from the
group consisting of water-dispersible polymers having an acid
number of no greater than 250 (preferably in the range of about 180
to 250) and a weight average molecular weight in the range of about
4,000 to about 20,000 (preferably from about 5,000 to about 12,000)
and combinations thereof;
[0075] 3) up to about 5.0% (preferably up to about 4.0%) by total
weight of the mixture of a member selected from the group
consisting of epoxy monomers that contain at least two ethylene
oxide groups, epoxy monomers that contain at least two epoxide
groups, epoxy monomers that contain at least one ethylene oxide
group and at least one epoxide group, and combinations thereof;
[0076] 4) up to about 5.0% (preferably from about 1.0% to about
3.0%) by total weight of the mixture of a member selected from the
group consisting of anionic surfactants, non-ionic surfactants, and
combinations thereof;
[0077] 5) up to about 4.0% by total weight of the mixture of a
member selected from the group consisting of chain transfer agents
and combinations thereof;
[0078] 6) up to about 5.0% by total weight of the mixture of at
least one organic solvent;
[0079] 7) a catalytic amount of polymerization initiator; and
[0080] 8) the balance of the mixture being water; to produce an
anionic polymer composition having a solids content in the range of
about 1.0% to about 50.0% (preferably in the range of about 35.0%
to about 50.0%), a pH in the range of about 3.5 to about 9.0
(preferably in the range of about 8.0 to about 9.0), and an acid
number of no greater than about 22 (preferably no greater than 10
and more preferably no greater than 5).
[0081] It is preferred that the vinylic monomer used in the free
radical polymerization reaction to produce the anionic polymer
composition be a member selected from the group consisting of
styrenic monomers, acrylic monomers, methacrylic monomers,
ethylenic monomers, and combinations thereof. It is further
preferred that the vinylic monomer is a member selected from the
group consisting of acrylic acid, methacrylic acid, methyl
methacrylate, ethyl methacrylate, n-propyl methacrylate, n-butyl
methacrylate, isopropyl methacrylate, isobutyl methacrylate, n-amyl
methacrylate, n-hexyl methacrylate, isoamyl methacrylate,
2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate,
N,N-dimethylaminoethyl methacrylate, N,N-diethylaminoethyl
methacrylate, t-butylaminoethyl methacrylate, 2-sulfoethyl
methacrylate, trifluoroethyl methacrylate, glycidyl methacrylate,
benzyl methacrylate, allyl methacrylate, 2-n-butoxyethyl
methacrylate, 2-chloroethyl methacrylate, sec-butyl-methacrylate,
tert-butyl methacrylate, 2-ethybutyl methacrylate, cinnamyl
methacrylate, crotyl methacrylate, cyclohexyl methacrylate,
cyclopentyl methacrylate, 2-ethoxyethyl methacrylate, furfuryl
methacrylate, hexafluoroisopropyl methacrylate, methallyl
methacrylate, 3-methoxybutyl methacrylate, 2-methoxybutyl
methacrylate, 2-nitro-2 methylpropyl methacrylate,
n-octylmethacrylate, 2-ethylhexyl methacrylate, 2-phenoxyethyl
methacrylate, 2-phenylethyl methacrylate, phenyl methacrylate,
propargyl methacrylate, tetrahydrofurfuryl methacrylate,
tetrahydropyranyl methacrylate, methyl acrylate, ethyl acrylate,
n-propyl acrylate, isopropyl acrylate, n-butyl acrylate, n-decyl
acrylate, 2-ethylhexal acrylate, salts of methacrylic acid,
methacrylonitrile, methacrylamide, N-methylmethacrylamide,
N-ethylmethacrylamide, N,N-diethymethacrylamide,
N,N-dimethylmethacrylami- de, N-phenyl-methacrylamide,
methacrolein, salts of acrylic acid, acrylonitrile, acrylamide,
methyl alpha-chloroacrylate, methyl 2-cyanoacrylate,
N-ethylacrylamide, N,N-diethylacrylamide acrolein, vinyl acetate,
vinyl chloride, vinyl pyridine, vinyl pyrollidone, sodium
crotonate, methyl crotonate, crotonic acid, malcic anhydride, and
combinations thereof.
[0082] Where desired, a water-dispersible polymer or combination of
water-dispersible polymers may be added to the mixture undergoing
free radical polymerization to produce the anionic polymer
composition. Water-dispersible polymers which are suitable for use
in the present invention include those water-dispersible polymers
having an acid number of no greater than 250 and a weight average
molecular weight in the range of about 4,000 to about 20,000. It is
preferred that the water-dispersible polymers have an acid number
in the range of about 180 to 250. It is also preferred that the
water-dispersible polymers have a weight average molecular weight
in the range of about 4,000 to about 12,000. Water-dispersible
polymers having an acid number of 100 or less can be utilized in
the present invention without neutralization. However, polymers
having an acid number of greater than 100 must be neutralized prior
to dispersion in an aqueous medium. Aqueous bases suitable for use
in neutralizing these polymers to produce water-dispersible
polymers include organic and inorganic compounds (such as sodium
hydroxide, potassium hydroxide, ammonium hydroxide, amines,
sulfates, and the like). The term "water-dispersible polymers" as
used herein includes polymers having an acid number of greater than
100 that have been neutralized for dispersion in an aqueous medium.
Preferred water-dispersible stabilizing polymers include members
selected from the group consisting of acrylic acid, methacrylic
acid, fumaric acid, maleic anhydride, and combinations thereof.
Polar, non-ionic water-dispersible polymers can also be employed in
the present invention.
[0083] Where desired, an epoxy monomer or combination of epoxy
monomers may be added to the mixture undergoing free radical
polymerization to produce the anionic polymer composition. Epoxy
monomers which are suitable for use in the present invention
include epoxy monomers that contain at least two ethylene oxide
groups, epoxy monomers that contain at least two epoxide groups,
epoxy monomers that contain at least one ethylene oxide group and
at least one epoxide group, and combinations thereof. Both
water-soluble and water-insoluble epoxy monomers can be utilized in
the present invention. Epoxy monomers which are preferred for use
in the present invention include, but are not limited to, the
following: aliphatic epoxidized urethanes, aromatic epoxidized
urethanes, glycidyl acrylate esters, esters, siloxanes, aliphatic
hydrocarbons, cyclic hydrocarbons, and combinations thereof.
[0084] Where desired, at least one anionic surfactant may be added
to the mixture undergoing free radical polymerization to produce
the anionic polymer composition. Preferred anionic surfactants
suitable for use in the present invention, include, but are not
limited to, the following: alkyl sulfates, ether sulfates,
phosphate esters, sulfonates, and combinations thereof.
[0085] Where desired, at least one nonionic surfactant may be added
to the mixture undergoing free radical polymerization to produce
the anionic polymer composition. Preferred nonionic surfactants
suitable for use in the present invention, include, but are not
limited to, the following: ethoxylated alkylphenols, ethoxylated
fatty alcohols, ethylene oxide/propylene oxide block copolymers,
and combinations thereof.
[0086] Where desired, at least one chain transfer agent may be
added to the mixture undergoing free radical polymerization to
produce the anionic polymer composition. Preferred chain transfer
agents suitable for use in the present invention, include, but are
not limited to, the following: dodecyl mercaptan,
2-mercaptoethanol, alkyl mercaptopropionates, mercaptoacetic acid,
mercaptopropionic acid, octyl mercaptan, and combinations
thereof.
[0087] Where desired, at least one organic solvent may be added to
the mixture undergoing free radical polymerization to produce the
anionic polymer composition. Organic solvents that are suitable for
use in the present invention include polar organic solvents,
non-polar organic solvents, and combinations thereof. Examples of
suitable organic solvents include aliphatic hydrocarbons,
napththenic hydrocarbons, aromatic hydrocarbons, aliphatic
monohydric alcohols, alicyclic monohydric alcohols, glycols; glycol
ethers; ketones, esters, aldehydes, ethers, saturated fatty acids,
unsaturated fatty acids, soya oils, tall oils, vegetable oils,
spirits, amines, polyols, and the like.
[0088] A catalytic amount of at least one polymerization initiator
is used in the free radical polymerization reaction to produce the
anionic polymer composition. The amount of initiator employed
commonly comprises from about 0.1% to about 3.0% (preferably from
about 0.2% to about 2.0%) by weight of the total mixture used to
produce the anionic polymer composition. Traditional emulsion
polymerization initiators (such as thermal initiators, redox
initiators, and the like) are suitable for use in the emulsion
polymerization reaction. Examples of suitable thermal initiators
include, but are not limited to, the following: hydrogen peroxide,
t-butyl hydroperoxide, di-t-butyl peroxide, benzoyl peroxide,
benzoyl hydroperoxide, 2,4-dichlorobenzoyl peroxide, t-butyl
peracetate, azobisisobutyronitrile, isopropyl peroxycarbonate, and
combinations thereof. Examples of suitable redox initiators
include, but are not limited to, the following: cumene
hydroperoxide-sodium metabisulfite, cumene hydroperoxide-iron (II)
sulfate, and combinations thereof. Preferred initiators include
water-soluble azo compounds (such as V-50 or VA-086 manufactured by
Wako Chemicals).
[0089] Sufficient water is added to the mixture to produce an
anionic polymer composition having a solids content in the range of
about 1.0% to about 50.0%. The preferred solids content for the
cationic emulsion polymerization product is in the range of about
35.0% to about 50.0%.
[0090] Anionic polymer compositions which are suitable for use in
the present invention have a pH in the range of about 3.5 to about
9.0. It is preferred that the anionic polymer compositions have a
pH in the range of about 8.0 to about 9.0.
[0091] Anionic polymer compositions which are suitable for use in
the present invention have an acid number of no greater than about
22. It is preferred that the anionic polymer compositions have an
acid number of no greater than about 10, and it is more preferred
that the acid number be no greater than about 5.
[0092] The cationic polymer compositions and the anionic polymer
compositions are mixed together to form the polymer blend
compositions of the present invention. These polymer blend
compositions have an acid number of no greater than about 22. It is
preferred that the anionic polymer compositions have an acid number
of no greater than about 10, and it is more preferred that the acid
number be no greater than about 5.
[0093] The polymer blend compositions of the present invention are
superior ink jet receptive coatings. Such ink jet receptive
coatings can be employed to produce ink jet printable products via
the process of coating a chosen substrate on at least one side with
the ink jet receptive coating. Substrates which are suitable for
use in producing such ink jet printable products include paper,
paperboard, wood, plastics, metal foil, textiles, and the like.
Where desired, any of the pigments traditionally used in ink jet
receptive coatings can be employed in the coating. Such pigments
include, but are not limited to, the following: silica, alumina,
plastic pigments, calcium carbonate, kaolin clay, and combinations
thereof.
[0094] The polymer blend compositions of the present invention also
exhibit properties that make them useful as water-borne vehicles
for various coatings, such as inks, varnishes, paints, functional
coatings, and the like. Where desired, any of the pigments
traditionally used in the formulation of such coatings can be
employed in the coating provided that the pigments are compatible
with the polymer blend compositions. Such pigments include, but are
not limited to, the following: silica, alumina, plastic pigments,
calcium carbonate, kaolin clay, organic based pigments, inorganic
based pigments, and combinations thereof.
[0095] As appreciated in the art, the exact components and
properties of components desired for any coating application can
vary and, therefore, routine experimentation may be required to
determine the optional components and proportions of components for
a given application and desired properties.
[0096] The following examples are provided to further illustrate
the present invention and are not to be construed as limiting the
invention in any manner.
EXAMPLE 1
[0097] A cationic polymer composition suitable for use in producing
a polymer blend composition was prepared as follows. A round bottom
flask was equipped with a stirrer, thermometer, nitrogen inlet and
reflux condenser. To the flask was added 427 g of deionized water
(DIW), 32 g of ARQUAD C-50 (a 50% solution of
dodecyltrimethylammonium chloride in isopropyl alcohol commercially
available from Akzo Nobel), and 7.1 g of 3-methacyloylaminopropyl
trimeammonium chloride (METAC), and the mixture was heated to a
temperature of 140.degree. F. A first monomer mixture (composed of
15 g of butyl acrylate, 2.4 g of dimethylaminoethylmethacryl- ate,
and 23.4 g of styrene) was added to the flask. An initiator
solution composed of 6.4 g of V-50 (an azo free radical initiator
commercially available from Wako Chemicals) and 35 g of DIW was
added to the flask and the temperature was maintained at
140.degree. F. After 30 minutes, a second monomer mixture (composed
of 25 g DIW and 41 g of METAC) and a third monomer mixture
(composed of 84 g of butyl acrylate, 13.5 g of
dimethylaminoethylmethacrylate, and 132 g of styrene) were added to
the flask over a three-hour period. Upon completion of the feed,
the reaction was heated to 160.degree. F. and maintained at that
temperature for 60 minutes. Upon cooling, the resulting cationic
emulsion (hereafter "Cationic Polymer No. 1") contained a solids
level of 37% and had a pH of 7.5.
EXAMPLE 2
[0098] A cationic polymer composition suitable for use in producing
a polymer blend composition was prepared as follows. A round bottom
flask was equipped with a stirrer, thermometer, nitrogen inlet and
reflux condenser. To the flask was added 529 g of deionized water
(DIW), 32 g of ARQUAD C-50 (a 50% solution of
dodecyltrimethylammonium chloride in isopropyl alcohol commercially
available from Akzo Nobel), and 5 g of 3-methacyloylaminopropyl
trimeammonium chloride (METAC), and the mixture was heated to a
temperature of 140.degree. F. A first monomer mixture composed of
2.4 g of butyl acrylate, 14.6 g of dimethylaminoethylmethacry-
late, 24.3 g of styrene, and 2.4 g of hydroxymethylmethacrylate)
was added to the flask. Thereafter, an initiator solution composed
of 6.6 g of V-50 (an azo free radical initiator commercially
available from Wako Chemicals) and 16 g of DIW was added to the
flask and the temperature was maintained at 140.degree. F. After 30
minutes, 27 g of METAC and a second monomer mixture (composed of 14
g of butyl acrylate, 83 g of dimethylaminoethylmethacrylate, 138 g
of styrene, and 14 g of hydroxymethylmethacrylate) were charged
into the reaction over a three-hour period. Upon completion of the
feed, the reaction was heated to 160.degree. F. and maintained at
that temperature for 60 minutes. Upon cooling, the resulting
cationic emulsion (hereafter "Cationic Polymer No. 2") contained
40% solids and had a pH of 8.5.
EXAMPLE 3
[0099] A cationic polymer composition suitable for use in producing
a polymer blend composition was prepared as follows. A round bottom
flask was equipped with a stirrer, thermometer, nitrogen inlet and
reflux condenser. To the flask was added 348 g of deionized water
(DIW), 20 g of ARQUAD C-50 (a 50% solution of
dodecyltrimethylammonium chloride in isopropyl alcohol commercially
available from Akzo Nobel), and 3.4 g of TERGITOL NP-10 (a nonionic
surfactant commercially available from Dow Chemical Co.), and the
mixture was heated to a temperature of 140.degree. F. Thereafter, a
monomer mixture composed of 43 g of styrene and 27.8 g of
3-methacyloylaminopropyl trimeammonium chloride (METAC) was added
to the flask. An initiator solution composed of 6.6 g of V-50 (an
azo free radical initiator commercially available from Wako
Chemicals) and 14 g of DIW was then added to the flask and the
temperature was maintained at 140.degree. F. After 30 minutes, a
second monomer mixture (composed of 110 g of DIW, 2 g of ARQUAD
C-50, and 243 g of styrene) and 43 g of METAC were added to the
flask over a period of 180 minutes. Upon completion of the feed,
the reaction was heated to 160.degree. F. and maintained at that
temperature for 60 minutes. Upon cooling, the resulting cationic
emulsion (hereafter "Cationic Polymer No. 3") contained a solids
level of 40% and had a pH of 4.0.
EXAMPLE 4
[0100] An anionic polymer composition suitable for use in producing
a polymer blend composition was prepared as follows. A round bottom
flask was equipped with a stirrer, thermometer, nitrogen inlet and
reflux condenser. To the flask was added 296 g of deionized water
(DIW), 0.5 g of sodium lauryl sulfate, and 0.7 g of itaconic acid,
and the mixture was heated to 185.degree. F. Thereafter, 13.6 g of
styrene was added to the flask. An initiator solution composed of
0.2 g of ammonium persulfate and 8.2 g of DIW was then added to the
flask and the temperature was maintained at 185.degree. F. After 30
minutes, 355 g of styrene and an initiator mixture composed of 81 g
of DIW, 3 g of ammonium persulfate, and 7.7 g of sodium lauryl
sulfate were charged into the flask over a period of 200 minutes.
Upon completion of the feed, the reaction was cooled to 160.degree.
F. and maintained at that temperature for 60 minutes. Upon cooling
to 90.degree. F., 26 g of IGEPAL CA-897 (a modified alkylphenol
ethoxylate surfactant commercially available from Rhodia Chimie
Corp.) was added to the flask. Upon cooling to room temperature,
the resulting anionic emulsion (hereafter "Anionic Polymer No. 1")
had a solids level of 48%, a pH of 8.4, and an acid number of less
than 5.
EXAMPLE 5
[0101] An anionic polymer composition suitable for use in producing
a polymer blend composition was prepared as follows. A round bottom
flask was equipped with a stirrer, thermometer, nitrogen inlet and
reflux condenser. To the flask was added 385 g of deionized water
(DIW), 1 g of ammonium carbonate, and 1 g of RHODACAL DS-10 (sodium
dodecylebenzene sulfonate commercially available from Rhodia Chimie
Corp.), and the mixture was heated to 157.degree. F. Thereafter, a
monomer mixture composed of 2.7 g of EPON 828 (poly(bisphenol
A-co-epicholorhydrin commercially available from Shell Oil Co.
Corp.), 7.1 g of styrene, 2.1 g of ethyl acrylate, 1 g of CARBOWAX
350 (polyethylene glycol monomethylether commercially available
from Dow Chemical Co.), and 1 g of methacrylic acid) was added to
the flask. An initiator solution composed of 1 g of ammonium
persulfate and 8.5 g of DIW was charged to the flask and the
temperature was increased to 180.degree. F. After 30 minutes, a
monomer mixture composed of 16.4 g of EPON 828, 46.3 g of styrene,
13.2 g of ethyl acrylate, 6.6 g of CARBOWAX 350, and 6.6 g of
methacrylic acid was charged into the flask over a period of 45
minutes. Upon completion of the feed, the reaction was heated to
180.degree. F. After 60 minutes, a monomer mixture (composed of
34.5 g of butyl acrylate, 51 g of butyl methacrylate, 120 g of
methyl methacrylate, and 80 g of 2-ethylhexyl acrylate) and an
initiator mixture composed of 47.5 g DIW, 5.4 g Aerosol NPES 930P
(a sulfated ethoxylated nonyl phenol ammonium salt commercially
available from Cytec), 5.4 g of RHODAPEX CO-436 (a modified
alkylphenol ethoxylate surfactant commercially available from
Rhodia Chimie Corp.), and 4.6 g of ammonium persulfate were added
to the flask over a two-hour period. Upon cooling, the resulting
anionic emulsion (hereafter "Anionic Polymer No. 2") had a solids
content of 42%, a pH of 4.5, and an acid number in the range of 5
to 10.
EXAMPLE 6
[0102] An anionic polymer composition suitable for use in producing
a polymer blend composition was prepared as follows. A round bottom
flask was equipped with a stirrer, thermometer, nitrogen inlet and
reflux condenser. To the flask was added 775 g of deionized water
(DIW), 34 g of PLURONIC L-61 (polyoxyethylene-polyoxpropylene
glycol commercially available from BASF Corp.), 1.7 g of RHODAPEX
CO-436 (a modified alkylphenol ethoxylate surfactant commercially
available from Rhodia Chimie Corp.), 132 g of a styrene acrylate
methacrylic acid co-polymer ammonium salt water-dispersible
polymer, 21.5 g of methacrylic acid, and 25 g of ammonium
hydroxide, and the mixture was heated to 172.degree. F. Thereafter,
a monomer mixture composed of 5.5 g of butyl acrylate and 103 g of
styrene was charged into the flask. An initiator solution composed
of 6.8 g of ammonium persulfate and 26 g of DIW was then added to
the flask and the temperature was increased to 180.degree. F. After
30 minutes, a second monomer mixture composed of 37 g of butyl
acrylate, and 694 g of styrene was charged into the flask over a
period of 180 minutes. An initiator mixture composed of 35 g DIW
and 2.2 g of ammonium persulfate was also added to the reaction 90
minutes after the start of the charging of the second monomer
mixture into the flask. Upon completion of the feed, the reaction
was heated to 180.degree. F. After a period of 60 minutes, the
reaction was cooled to 90.degree. F. and a surfactant mixture
composed of 61 g of IGEPAL CA-897 (a modified alkylphenol
ethoxylate surfactant commercially available from Rhodia Chimie
Corp.) and 24 g of DIW was charged into the reaction. Upon cooling
to room temperature, the resulting anionic emulsion (hereafter
"Anionic Polymer No. 3") had a solids level of 49%, a pH of 8.8,
and an acid number of less than 22.
EXAMPLE 7
[0103] A cationic polymer composition suitable for use in producing
a polymer blend composition was prepared as follows. A round bottom
flask was equipped with a stirrer, thermometer, nitrogen inlet and
reflux condenser. To the flask was added 314 g of deionized water
(DIW), 27 g of ARQUAD C-50 (a 50% solution of
dodecyltrimethylammonium chloride in isopropyl alcohol commercially
available from Akzo Nobel), and 4 g of 3-methacyloylaminopropyl
trimeammonium chloride (METAC), and the mixture was heated to a
temperature of 140.degree. F. A monomer mixture composed of 2 g of
butyl acrylate, 12 g of dimethylaminoethylmethacrylate, and 22 g of
styrene was added to the flask. Thereafter, an initiator solution
composed of 5.5 g of V-50 (an azo free radical initiator
commercially available from Wako Chemicals) and 32 g of DIW was
added to the flask and the temperature was maintained at
140.degree. F. After 30 minutes, a first mixture (comprised of 23 g
of METAC and 29 g of DIW) and a second monomer mixture (composed of
11 g of butyl acrylate, 67 g of dimethylaminoethylmethacrylate, and
126 g of styrene) were charged into the reaction over a period of
180 minutes. Upon completion of the feed, the reaction was heated
to 160.degree. F. and maintained at that temperature for 60
minutes. Upon cooling, the resulting cationic emulsion (hereafter
"Cationic Polymer No. 4") contained 40% solids and had a pH of
8.5.
EXAMPLE 8
[0104] A polymer blend composition was prepared as follows. To a 4
oz jar was added 25 g of Cationic Polymer No. 1. Thereafter, 75 g
of Anionic Polymer No. 1 was added to the jar with stirring, and
the blend was mixed for an additional two minutes using a standard
lab mixer. The resulting polymer blend composition, which had a
viscosity of 20 seconds as measured via a Zahn 2 cup, was stable
and exhibited no precipitate formation or gelling.
EXAMPLE 9
[0105] A polymer blend composition was prepared as follows. To a 4
oz jar was added 50 g of Anionic Polymer No. 1. Thereafter, 50 g of
Cationic Polymer No. 1 was added to the jar with stirring, and the
blend was mixed for an additional two minutes using a standard lab
mixer. The resulting polymer blend composition, which had a
viscosity of 20 seconds as measured via a Zahn 2 cup, was stable
and exhibited no precipitate formation or gelling.
EXAMPLE 10
[0106] A polymer blend composition was prepared as follows. To a 4
oz jar was added 75 g of Cationic Polymer No. 1. Thereafter, 25 g
of Anionic Polymer No. 1 was added to the jar with stirring, and
the blend was mixed for an additional two minutes using a standard
lab mixer. The resulting polymer blend composition, which had a
viscosity of 20.8 seconds as measured via a Zahn 2 cup, was stable
and exhibited no precipitate formation or gelling.
EXAMPLE 11
[0107] A polymer blend composition was prepared as follows. To a 4
oz jar was added 80 g of Cationic Polymer No. 1. Thereafter, 20 g
of Anionic Polymer No. 5 was added to the jar with stirring, and
the blend was mixed for an additional two minutes using a standard
lab mixer. The resulting polymer blend composition, which had a
viscosity of 22.2 seconds as measured via a Zahn 2 cup and a pH of
7.5, was stable and exhibited no precipitate formation or
gelling.
EXAMPLE 12
[0108] A polymer blend composition was prepared as follows. To a 4
oz jar was added 10 g of Anionic Polymer No. 1. Thereafter, 90 g of
Cationic Polymer No. 5 was added to the jar with stirring, and the
blend was mixed for an additional two minutes using a standard lab
mixer. The resulting polymer blend composition, which had a
viscosity of 60 seconds as measured via a Zahn 2 cup and a pH of
8.0, was stable and exhibited no precipitate formation or
gelling.
EXAMPLE 13
[0109] A polymer blend composition was prepared as follows. To a 4
oz jar was added 90 g of Cationic Polymer No. 3. Thereafter, 10 g
of Anionic Polymer No. 5 was added to the jar with stirring, and
the blend was mixed for an additional two minutes using a standard
lab mixer. The resulting polymer blend composition, which had a
viscosity of 20 seconds as measured via a Zahn 2 cup and a pH of
5.08, was stable and exhibited no precipitate formation or
gelling.
EXAMPLE 14
[0110] A polymer blend composition was prepared as follows. To a 4
oz jar was added 81.0 g of Cationic Polymer No. 2. Thereafter, 9.0
g of Anionic Polymer No. 2 was added to the jar with stirring, and
the blend was mixed for an additional two minutes using a standard
lab mixer. The resulting polymer blend composition was stable and
exhibited no precipitate formation or gelling.
[0111] A non-pigmented coating was prepared by mixing together for
two minutes the polymer blend composition, 5.0 g of deionized
water, 0.1 g of Dow 62 (a silicon defoamer emulsion commercially
available from Dow Corning), 4.0 g of 392N35 (a 35% solids
polyethylene was commercially available from Chemcor) and 0.9 g of
BYK 302 (a polyether-modified dimethyl polysiloxane copolymer
commercially available from BYK Chemie GMBH Corp.). The resulting
polymer blend coating had a viscosity of 45 seconds as measured via
a Zahn 2 cup and a pH of 7.5.
[0112] For comparison purposes, a non-pigmented coating was made
using the above-noted procedure except that the polymer blend
composition was replaced with 90 g of Anionic Polymer No. 2.
[0113] The polymer blend coating and the coatings of the
comparative examples were each applied to CIS paperboard using a
No. 12 wire-wound rod. The coated sheets were then oven dried for
30 seconds at 60.degree. C. and allowed to dry overnight at room
temperature. The sheets were subsequently tested via a standard
spot test for periods of 2, 10, 30, and 60 minutes using the
following chemical reagents: FORMULA 409 PRO (a commercial cleaner
from Clorox Co.), 0.3% ammonium hydroxide, 70% isopropyl alcohol,
50% ethanol, and 0.5 molar potassium hydroxide. The sheets coated
with the polymer blend coating exhibited superior chemical
resistances when compared to the comparative example coating.
EXAMPLE 15
[0114] A polymer blend composition was prepared as follows. To a 4
oz jar was added 58.5 g of Cationic Polymer No. 2. Thereafter, 6.5
g of Anionic Polymer No. 2 was added to the jar with stirring, and
the blend was mixed for an additional two minutes using a standard
lab mixer. The resulting polymer blend composition was stable and
exhibited no precipitate formation or gelling.
[0115] A pigmented coating was prepared by mixing together for two
minutes the polymer blend composition, 5.0 g of deionized water,
and 30.0 g of BHD-6000 (a blue pigment resinless dispersion
commercially available from Sun Chemical). The resulting polymer
blend coating had a viscosity of 25 seconds as measured via a Zahn
2 cup and a pH of 7.5.
[0116] For comparison purposes, a pigmented coating was made using
the above-noted procedure except that the polymer blend composition
was replaced with either 65 g of Anionic Polymer No. 2.
[0117] The polymer blend coating and the coatings of the
comparative examples were each applied to CIS paperboard using a
No. 12 wire-wound rod. The coated sheets were then oven dried for
30 seconds at 60.degree. C. and allowed to dry overnight at room
temperature. The sheets were subsequently tested via a standard
spot test for periods of 2, 10, 30, and 60 minutes using the
following chemical reagents: FORMULA 409 PRO (a commercial cleaner
from Clorox Co.), 0.3% ammonium hydroxide, 70% isopropyl alcohol,
50% ethanol, and 0.5 molar potassium hydroxide. The sheets coated
with the polymer blend coating exhibited superior chemical
resistances when compared to the comparative example coating.
EXAMPLE 16
[0118] A polymer blend composition was prepared as follows. To a 4
oz jar was added 76.9 g of Cationic Polymer No. 1. Thereafter, 20.0
g of Anionic Polymer No. 1 was added to the jar with stirring, and
the blend was mixed for an additional two minutes using a standard
lab mixer. The resulting polymer blend composition was stable and
exhibited no precipitate formation or gelling.
[0119] An ink jet receptive coating was prepared by mixing together
for two minutes the polymer blend composition, 0.1 g of Dow 62 (a
silicone antifoam emulsion commercially available from Dow Corning)
and 3.0 g of 392N35 (a 35% solids polyethylene was commercially
available from Chemcor). The resulting polymer blend ink jet
receptive coating had a viscosity of 100 cps as measured by a #4
spindle at 100 rpms and a pH of 8.39.
[0120] A traditional polyvinyl alcohol-based ink jet receptive
coating was also produced as a comparative example. The above
procedure was repeated except that the polymer blend composition
was replaced with a 30 g of AIRVOL 205 (a polyvinyl alcohol
manufactured by Air Products, Inc.) mixed in 70 g of DIW.
[0121] The polymer blend ink jet receptive coating and the coating
of the comparative example were each applied to Hammermill
Multipurpose paper using a No. 12 wire-wound rod. The coated sheets
were then dried for 5 minutes at 110.degree. C., and test prints
were made on the dried sheets with black ink using an Epson 900
printer. The print made on the coating produced with the blend
polymer of the present invention showed much sharper definition,
increased edge acuity, greater water-resistance, and a higher color
density when compared with the print produced using the traditional
polyvinyl alcohol-based ink jet receptive coating.
EXAMPLE 17
[0122] A polymer blend composition was prepared as follows. To a 4
oz jar was added 25 g of Cationic Polymer No. 1. Thereafter, 75 g
of Anionic Polymer No. 6 was added to the jar with stirring, and
the blend was mixed for an additional two minutes using a standard
lab mixer. The resulting polymer blend composition, which had a
viscosity of 23 seconds as measured via a Zahn 2 cup, was stable
and exhibited no precipitate formation or gelling.
EXAMPLE 18
[0123] A polymer blend composition was prepared as follows. To a 4
oz jar was added 75 g of Cationic Polymer No. 1. Thereafter, 25 g
of Anionic Polymer No. 6 was added to the jar with stirring, and
the blend was mixed for an additional two minutes using a standard
lab mixer. The resulting polymer blend composition, which had a
viscosity of 27 seconds as measured via a Zahn 2 cup, was stable
and exhibited no precipitate formation or gelling.
EXAMPLE 19
[0124] A polymer blend composition was prepared as follows. To a 4
oz jar was added 50 g of Anionic Polymer No. 6. Thereafter, 50 g of
Cationic Polymer No. 2 was added to the jar with stirring, and the
blend was mixed for an additional two minutes using a standard lab
mixer. The resulting polymer blend composition, which had a
viscosity of 23 seconds as measured via a Zahn 2 cup, was stable
and exhibited no precipitate formation or gelling.
EXAMPLE 20
[0125] A polymer blend composition was prepared as follows. To a 4
oz jar was added 25 g of Anionic Polymer No. 6. Thereafter, 75 g of
Cationic Polymer No. 2 was added to the jar with stirring, and the
blend was mixed for an additional two minutes using a standard lab
mixer. The resulting polymer blend composition, which had a
viscosity of 27 seconds as measured via a Zahn 2 cup, was stable
and exhibited no precipitate formation or gelling.
[0126] Many modifications and variations of the present invention
will be apparent to one of ordinary skill in the art in light of
the above teachings. It is therefore understood that the scope of
the invention is not to be limited by the foregoing description,
but rather is to be defined by the claims appended hereto.
* * * * *