U.S. patent application number 11/564463 was filed with the patent office on 2008-05-29 for polymerizable composition comprising perfluoropolyether urethane having ethylene oxide repeat units.
This patent application is currently assigned to 3M Innovative Properties Company. Invention is credited to THOMAS P. KLUN, Joan M. Noyola, Richard J. Pokorny.
Application Number | 20080124555 11/564463 |
Document ID | / |
Family ID | 39464059 |
Filed Date | 2008-05-29 |
United States Patent
Application |
20080124555 |
Kind Code |
A1 |
KLUN; THOMAS P. ; et
al. |
May 29, 2008 |
POLYMERIZABLE COMPOSITION COMPRISING PERFLUOROPOLYETHER URETHANE
HAVING ETHYLENE OXIDE REPEAT UNITS
Abstract
Presently described are optical substrates having a surface
layer and optical displays comprising such optical substrates. The
surface layer comprises the reaction product of a polymerizable
mixture comprising at least one perfluoropolyether urethane
polymeric material comprising at least two free-radically
polymerizable groups and greater than 6 ethylene oxide repeat units
and at least one non-fluorinated crosslinker comprising at least
two free-radically polymerizable groups.
Inventors: |
KLUN; THOMAS P.; (Lakeland,
MN) ; Pokorny; Richard J.; (Maplewood, MN) ;
Noyola; Joan M.; (Maplewood, MN) |
Correspondence
Address: |
3M INNOVATIVE PROPERTIES COMPANY
PO BOX 33427
ST. PAUL
MN
55133-3427
US
|
Assignee: |
3M Innovative Properties
Company
|
Family ID: |
39464059 |
Appl. No.: |
11/564463 |
Filed: |
November 29, 2006 |
Current U.S.
Class: |
428/421 ;
528/70 |
Current CPC
Class: |
G02B 1/14 20150115; Y10T
428/31551 20150401; C08G 18/283 20130101; G02B 1/105 20130101; Y10T
428/31547 20150401; Y10T 428/31786 20150401; Y10T 428/3154
20150401; Y10T 428/31544 20150401; Y10T 428/31511 20150401; C08G
18/2885 20130101; Y10T 428/31507 20150401; C08G 18/672 20130101;
C08G 18/73 20130101; C09D 175/16 20130101 |
Class at
Publication: |
428/421 ;
528/70 |
International
Class: |
B32B 27/08 20060101
B32B027/08; C08G 18/72 20060101 C08G018/72 |
Claims
1. An optical display comprising: an optical substrate having a
surface layer comprising the reaction product of a polymerizable
mixture comprising at least one perfluoropolyether urethane
polymeric material comprising at least two free-radically
polymerizable groups and greater than 6 ethylene oxide repeat
units; at least one non-fluorinated crosslinker comprising at least
two free-radially polymerizable groups.
2. The optical display of claim 1 wherein the perfluoropolyether
urethane polymer comprises at least two (meth)acrylate groups.
3. The optical display of claim 2 wherein the perfluoropolyether
urethane comprises a terminal group having at least two
(meth)acrylate groups.
4. The optical display of claim 1 wherein the perfluoropolyether
urethane comprises a monovalent perfluoropolyether moiety.
5. The optical display of claim 1 wherein the perfluoropolyether
moiety is F(CF(CF.sub.3)CF.sub.2O)aCF(CF.sub.3)-- and a ranges from
4 to 15.
6. The optical display of claim 1 wherein the non-fluorinated
crosslinker comprise at least three free-radically polymerizable
groups.
7. The optical display of claim 1 wherein the substrate is selected
from polycarbonate, acrylic, cellulose acetate, and cellulose
triacetate.
8. The optical display of claim 1 wherein the surface layer further
comprises inorganic oxide particles.
9. The optical display of claim 1 wherein a hardcoat layer
comprising inorganic oxide particles is disposed between the
substrate and the surface layer.
10. An optical substrate having a surface layer comprising the
reaction product of a polymerizable mixture comprising at least one
perfluoropolyether urethane polymeric material comprising at least
two free-radically polymerizable groups and greater than 6 ethylene
oxide repeat units; at least one non-fluorinated crosslinker
comprising at least two free-radially polymerizable groups.
11. A multifunctional perfluoropolyether urethane composition
having the general formula Ri-(NHC(O)XQRf), --(NHC(O)OQ(A)p),
--(NHC(O)X.sup.j(C.sub.2H.sub.4O).sub.jR.sup.j wherein Ri is a
residue of a multi-isocyanate; X and X.sup.j are each independently
O, S or NR, where R is H or lower alkyl of 1 to 4 carbon atoms; Q
is independently a straight chain, branched chain, or
cyclic-containing connecting group having a valency at least 2; Rf
is a monovalent perfluoropolyether moiety composed of groups
comprising the formula F(RfcO)xCdF2d-, wherein each Rfc
independently represents a fluorinated alkylene group having from 1
to 6 carbon atoms, each x independently represents an integer
greater than or equal to 2, and wherein d is an integer from 1 to
6; A is a (meth)acryl functional group --XC(O)C(R2)=CH2, where R2
is a lower alkyl of 1 to 4 carbon atoms or H or F; p is 2 to 6; j
ranges from 7 to 40; and R.sup.j is H,
--C(O)C(R.sub.2).dbd.CH.sub.2, where R.sub.2 is a lower alkyl of 1
to 4 carbon atoms or H or F, or a group selected from alkyl, aryl,
alkaryl, aralkyl, optionally substituted with a heteroatom,
heteoratom functional group, or a (meth)acryl functional group.
12. The composition of claim 11 with the proviso that when X is O,
Q is not methylene.
13. The composition of claim 11 wherein Q is selected from an
alkylene having at least two carbon atoms, arylene, aralkylene, and
alkarylene.
14. The composition of claim 13 wherein Q comprises a heteroatom
selected from O, N, and S.
15. The composition of claim 14 wherein Q comprise a nitrogen
containing group.
16. The composition of claim 15 wherein Q contains an amide
group.
17. The composition of claim 16 wherein Q is selected from
--C(O)NHCH.sub.2CH.sub.2--, --C(O)NH(CH.sub.2).sub.6--, and
--C(O)NH(CH.sub.2CH.sub.2O)CH.sub.2CH.sub.2--.
18. A free-radially polymerizable composition comprising a mixture
of reaction products of i) at least one polyisocyanate; ii) at
least one isocyanate reactive perfluoropolyether compound; iii) at
least one isocyanate reactive compound comprising greater than 6
repeat units of ethylene oxide; and iv) at least one isocyanate
reactive non-fluorinated crosslinker comprising at least two
free-radically polymerizable groups.
19. The composition of claim 18 dispersed in an alcohol-containing
solvent.
20. The free-radically polymerizable coating of claim 24 wherein
ii) and iii) comprise alcohol isocyanate reactive groups.
Description
BACKGROUND OF THE INVENTION
[0001] Hardcoats have been used to protect the face of optical
displays. These hardcoats typically contain inorganic oxide
particles, e.g., silica, of nanometer dimensions dispersed in a
binder precursor resin matrix, and sometimes are referred to as
"ceramers".
[0002] U.S. Pat. No. 6,132,861 (Kang et al. '861); U.S. Pat. No.
6,238,798 B1 (Kang et al. '798); U.S. Pat. No. 6,245,833 B1 (Kang
et al. '833); U.S. Pat. No. 6,299,799 (Craig et al.) and Published
PCT Application No. WO 99/57185 (Huang et al.) describe ceramer
compositions containing blends of colloidal inorganic oxide
particles, a curable binder precursor and certain fluorochemical
compounds. These compositions are described as providing stain and
abrasion resistant hardcoats in a single layer coating.
[0003] U.S. Pat. No. 6,660,389 (Liu et al.) describes information
display protectors for display devices having an information
display area, comprising a stack of flexible substantially
transparent sheets, the sheets having on one side thereof an
adhesive layer and having on the other side thereof a hardcoat
layer comprising inorganic oxide particles dispersed in a binder
matrix and a low surface energy fluorinated compound, the stack
being cut so that the sheets will fit the information display area.
The low surface energy fluorinated compound can be part of the
hardcoat layer or can be a separate layer atop the hardcoat layer.
The protectors have very good scratch, smudge and glare resistance.
The stack of protectors can be stored, for example, on a personal
digital assistant or its cover or case.
[0004] WO 2005/111157 describes (Abstract) A hard coating
composition for use as a stain repellent single layer on an optical
display. The coating composition adds a monomer of a mono or
multi(methyl)acrylate bearing at least one monovalent
hexafluoropolypropylene oxide derivative and a free radically
reactive compatibilizer consisting of either a fluoroalkyl-group
containing acrylate compatibilizer or a fluoroalkylene-group
containing acrylate compatibilizer to a conventional
hydrocarbon-based hard coat formulation. The resultant coating is
substantially smooth and forms a durable surface layer that has low
surface energy that is stain and ink repellent.
[0005] WO2006/102383 describes various polymerizable
perfluoropolyether urethane additives and there use as hardcoats
for optical displays.
[0006] WO 03/002628 describes (Abstract) A
perfluoropolyether-containing composition which has an affinity for
nonfluorinated substrates and can form on the surface thereof a
film firmly adherent to the surface. It is a composition containing
carbon-carbon double bonds which comprises (A) a triisocyanate
obtained by trimerizing a diisocyanate and (B) a combination of at
least two compounds having active hydrogen, the component (B)
comprising (B-1) a perfluoropolyether having at least one active
hydrogen atom and (B-2) a monomer having an active hydrogen atom
and a carbon-carbon double bond.
SUMMARY OF THE INVENTION
[0007] Presently described are optical substrates having a surface
layer and optical displays comprising such optical substrates. The
surface layer comprises the reaction product of a polymerizable
mixture comprising at least one perfluoropolyether urethane
polymeric material comprising at least two free-radically
polymerizable groups and greater than 6 ethylene oxide repeat units
and at least one non-fluorinated crosslinker comprising at least
two free-radically polymerizable groups.
[0008] In another embodiment, a free-radically polymerizable
composition is described comprising a mixture of reaction products
of i) at least one polyisocyanate; ii) at least one isocyanate
reactive perfluoropolyether compound; iii) at least one isocyanate
reactive compound comprising greater than 6 repeat units of
ethylene oxide; and iv) at least one isocyanate reactive
non-fluorinated crosslinker comprising at least two free-radically
polymerizable groups. The composition may be a coating dispersed in
an alcohol-containing solvent that is particularly useful for
coating optical substrates such as polycarbonate, acrylic,
cellulose acetate, and cellulose triacetate.
[0009] Also described are certain multifunctional
perfluoropolyether urethane compositions that comprise the reaction
product of a polyisocyanate with an isocyanate reactive
perfluoropolyether compound, an isocyanate reactive multifunctional
hydrocarbon crosslinker, and an isocyanate reactive compound having
greater than 6 ethylene oxide repeat units. Preferred
multifunctional perfluoropolyether urethane compositions are set
forth in the claims.
[0010] In each of these embodiments, the perfluoropolyether
urethane polymeric material comprises at least two (meth)acrylate
groups such as a terminal group having at least two (meth)acrylate
groups. The perfluoropolyether urethane may comprise a monovalent
perfluoropolyether moiety such as
F(CF(CF.sub.3)CF.sub.2O).sub.aCF(CF.sub.3)-- wherein a ranges from
4 to 15. At least one (e.g. non-fluorinated) hydrocarbon
crosslinker that comprises at least three free-radically
polymerizable groups is typically employed. In some aspects, the
surface layer or polymerizable composition further comprises
inorganic oxide particles. In other aspects, a hardcoat layer
comprising inorganic oxide particles is disposed between the
substrate and an inorganic particle free surface layer.
DETAILED DESCRIPTION AND PREFERRED EMBODIMENTS
[0011] Presently described are optical displays including a light
transmissive optical substrate. The surface layer of the optical
substrate comprises the reaction product of a polymerizable mixture
comprising at least one free-radically polymerizable
perfluoropolyether urethane polymeric material having ethylene
oxide repeat units. In another embodiment, certain multifunctional
perfluoropolyether urethane compositions are described. In another
embodiment, coating compositions are described that comprise a
(e.g. ultraviolet) polymerizable mixture comprising the
perfluoropolyether urethane polymeric material dispersed in an
alcohol-containing solvent.
[0012] In one aspect a free-radically polymerizable coating
composition is described that comprises a mixture of reaction
products of
i) at least one polyisocyanate, ii) at least one isocyanate
reactive perfluoropolyether compound, iii) at least one isocyanate
reactive compound containing greater than 6 ethylene oxide repeat
units, and iv) at least one isocyanate reactive (e.g.
non-fluorinated) hydrocarbon crosslinker comprising two or more
free-radically polymerizable groups.
[0013] The perfluoropolyether compound (i.e. ii) and ethylene oxide
repeat unit containing compound (i.e. iii) preferably comprise a
(e.g. terminal) alcohol, thiol, or amine group. Typically both the
perfluoropolyether compound and the ethylene oxide compound contain
(e.g. terminal) reactive alcohol groups.
[0014] For embodiments wherein the perfluoropolyether compound,
ethylene oxide repeat unit containing compound, and hydrocarbon
crosslinker have monofunctional isocyanate reactivity the
isocyanate employed is typically at least trifunctional. However,
when one of more of the isocyanate reactive compounds have at least
difunctional isocyanate reactivity, difunctional isocyanates can be
employed.
[0015] The hydrocarbon crosslinker (i.e. iv) typically comprises
(meth)acryl groups such as (meth)acrylate groups. A substantial
excess of hydrocarbon crosslinker (i.e. iv) is typically employed
such that the perfluoropolyether urethane polymeric material as
well as other reaction products of the reaction mixture comprise
unreacted free-radically polymerizable groups which can be
subsequently cured for example by radiation (e.g. UV) curing.
[0016] Typically, the perfluoropolyether urethane composition is
made by first reacting a polyisocyanate with a perfluoropolyether
compound containing an alcohol, thiol, or amine group, followed by
reaction with one or more ethylene oxide compounds containing an
alcohol, thiol, or amine group. The perfluoropolyether urethane
additive is then combined with the (e.g. non-fluorinated)
isocyanate reactive multifunctional free-radically polymerizable
(e.g. (meth)acrylate) crosslinker. Alternatively, these
perfluoropolyether urethane additives can be formed by other
reaction sequences such as by first reacting the polyisocyanate
with the crosslinker, followed by the addition of the ethylene
oxide containing compound. In addition, the additives could be made
by reacting all three components concurrently.
[0017] Although these reaction sequences are generally conducted in
a solvent that does not contain hydroxyl groups (such as MEK) in
the presence of a catalyst such as an organotin compound, the
composition thus formed has improved compatibility with hydroxyl
group containing solvents, commonly know as alcohols. Alcohol based
coating compositions are especially useful for coating light
transmissive substrates such as polycarbonate, acrylic, cellulose
acetate, and cellulose triacetate which are susceptible to
swelling, cracking, or crazing by organic solvents such as ketones
(e.g. MEK), aromatic solvents (e.g. toluene), and esters (e.g.
acetate solvents).
[0018] One or more polyisocyanate materials are employed in the
preparation of the perfluoropolyether urethane. A variety of
polyisocyanates may be utilized as component i) in the preparation
of the perfluoropolyether urethane polymeric material.
[0019] "Polyisocyanate" means any organic compound that has two or
more reactive isocyanate (--NCO) groups in a single molecule such
as diisocyanates, triisocyanates, tetraisocyanates, etc., and
mixtures thereof. Cyclic and/or linear polyisocyanate molecules may
usefully be employed. For improved weathering and diminished
yellowing the polyisocyanate(s) of the isocyanate component is
typically aliphatic.
[0020] Useful aliphatic polyisocyanates include, for example,
bis(4-isocyanatocyclohexyl)methane (H.sub.12 MDI) such as available
from Bayer Corp., Pittsburgh, Pa. under the trade designation
"Desmodur W"; isophorone diisocyanate (IPDI) such as commercially
available from Huels America, Piscataway, N.J.; hexamethylene
diisocyanate (HDI) such as commercially available from Aldrich
Chemical Co., Milwaukee, Wis.; trimethyl hexamethylene diisocyanate
such as commercially available from Degussa, Corp., Dusseldorf,
Germany under the trade designation "Vestanate TMDI"; and
m-tetramethylxylene diisocyanate (TMXDI) such as commercially
available from Aldrich Chemical Co., Milwaukee, Wis. Although
typically less preferred, aromatic isocyanates such as
diphenylmethane diisocyanate (MDI) such as commercially available
from Bayer Corp., Pittsburgh, Pa. under the trade designation
"Mondur M"; toluene 2,4-diisocyanate (TDI) such as commercially
available from Aldrich Chemical Co., Milwaukee, Wis., and
1,4-phenylene diisocyanate are also useful.
[0021] Preferred polyisocyanates include derivatives of the
above-listed monomeric polyisocyanates. These derivatives include,
but are not limited to, polyisocyanates containing biuret groups,
such as the biuret adduct of hexamethylene diisocyanate (HDI)
available from Bayer Corp. under the trade designation "Desmodur
N-100", polyisocyanates based on HDI containing isocyanurate
groups, such as that available from Bayer Corp. under trade
designation "Desmodur N-3300", as well as polyisocyanates
containing urethane groups, uretdione groups, carbodiimide groups,
allophonate groups, and the like. These derivatives are preferred
as they are polymeric, exhibit very low vapor pressures and are
substantially free of isocyanate monomer.
[0022] Other polyisocyanates that may be used are available from
Bayer Polymers LLC of Pittsburgh, Pa. under the trade designations
"Desmodur TPLS2294", and "Desmodur N 3600"
[0023] Various isocyanate reactive perfluoropolyethers materials
can be utilized as component ii). The synthesis of various
perfluoropolyether materials having (e.g. terminal) isocyanate
reactive groups such as OH, SH or NHR wherein R is H of an alkyl
group of 1 to 4 carbon atoms is known. For example, a methyl ester
material (e.g. having an average molecular weight of 1,211 g/mol)
for preparation of the alcohol can be prepared according to the
method reported in U.S. Pat. No. 3,250,808 (Moore et al.), the
disclosure of which is incorporated herein by reference, with
purification by fractional distillation. Perfluoropolyether alcohol
materials can be made by a procedure similar to that described in
U.S. Publication No. 2004-0077775, filed May 24, 2002.
Perfluoropolyether alcohol materials having an SH group can be made
using this same process by use of aminoethane thiol rather than
aminoethanol. Perfluoropolyether amine materials can be synthesized
as described in US 2005/0250921.
[0024] One or more isocyanate reactive perfluoropolyether materials
are employed in the preparation of the perfluoropolyether urethane.
The perfluoropolyether urethane material is preferably prepared
from an isocyanate reactive HFPO-material. Unless otherwise noted,
"HFPO-" refers to the end group
F(CF(CF.sub.3)CF.sub.2O).sub.aCF(CF.sub.3)-- of the methyl ester
F(CF(CF.sub.3)CF.sub.2O).sub.aCF(CF.sub.3)C(O)OCH.sub.3, wherein
"a" averages 2 to 15. In some embodiments, a averages between 3 and
10 or a averages between 5 and 8. Such species generally exist as a
distribution or mixture of oligomers with a range of values for a,
so that the average value of a may be non-integer. For example, in
one embodiment, "a" averages 6.2. The molecular weight of the
HFPO-perfluoropolyether material varies depending on the number
("a") of repeat units from about 940 g/mole to about 1600 g/mole,
with 1100 g/mole to 1400 g/mole typically being preferred.
[0025] One or more isocyanate reactive ethylene oxide repeat unit
materials are employed in the preparation of the perfluoropolyether
urethane. The ethylene oxide containing isocyanate reactive
compound generally comprises greater than 6 repeat units of
ethylene oxide. The number of ethylene oxide repeat units may be at
least 7, 8, or 9 repeat units. In some embodiments, the isocyanate
reactive ethylene oxide containing compound has at least 10 repeat
units of ethylene oxide. For example, the number of repeat units
may be 11, 12, 13, 14, 15, 16, 17, 18, 19, or 20. Generally the
number of ethylene oxide repeat units does not exceed about 40 and
may be for example up to 25, 30, or 35 repeat units.
[0026] The ethylene oxide containing compounds may be represented
by the following formula:
X.sup.1(C.sub.2H.sub.4O).sub.jR.sup.j
wherein
X.sup.1 is OH, SH or NHR, where R is H or lower alkyl of 1 to 4
carbon atoms; and
[0027] R.sub.1 is H, --C(O)C(R.sub.2).dbd.CH.sub.2, where R.sub.2
is a lower alkyl of 1 to 4 carbon atoms or H or F, or a group
selected from alkyl, aryl, alkaryl, aralkyl, that can optionally be
substituted with a heteroatom, a heteoratom functional groups (such
as --OH --SH, and --NH.sub.2), or a (meth)acryl functional group;
and j ranges from 7 to 40.
[0028] The ethylene oxide containing compound may also comprise
other alkylene oxide compounds such as propylene oxide. In such
embodiment, a major amount of the alkylene oxide repeat units are
typically ethylene oxide repeat units.
[0029] Various isocyanate reactive non-fluorinated hydrocarbon
crosslinkers can be employed in the synthesis of the
perfluoropolyether urethane polymeric material. Such crosslinkers
comprise at least two and preferably three free-radically
polymerizable groups. The free-radically polymerizable groups are
preferably (meth)acryl and more preferably (meth)acrylate
groups.
[0030] Suitable isocyanate reactive non-fluorinated hydrocarbon
crosslinkers may be described by the formula:
HOQ(A).sub.p;
wherein
Q is a connecting group of valency at least 2;
A is a (meth)acryl functional group such as --XC(O)C(R2)=CH2,
where
[0031] X is O, S or NR, where R is H or lower alkyl of 1 to 4
carbon atoms, and [0032] R.sub.2 is a lower alkyl of 1 to 4 carbon
atoms or H or F; and p ranges from 2 to 6.
[0033] Q can comprise a straight chain, branched chain, or
cyclic-containing connecting group. Q can include an alkylene, an
arylene, an aralkylene, an alkarylene. Q can optionally include
heteroatoms such as O, N, and S, and combinations thereof. Q can
also optionally include a heteroatom-containing functional group
such as carbonyl or sulfonyl, and combinations thereof.
[0034] Exemplary isocyanate reactive crosslinkers include for
example 1,3-glycerol dimethacrylate available from Echo Resin Inc.
of Versailles, Mo. and pentaerythritol triacrylate, available from
Sartomer of Exton, Pa. under the trade designation "SR444C".
Additional useful isocyanate reactive (meth)acrylate crosslinkers
include hydantoin moiety-containing poly(meth)acrylates, for
example, as described in U.S. Pat. No. 4,262,072 (Wendling et
al.).
[0035] If the mole fraction of isocyanate groups is arbitrarily
given a value of 1.0, then the total mole fraction of isocyanate
reactive groups used in making the perfluoropolyether urethane
material is 1.0 or greater. Although, the polymerizable
compositions described herein typically comprise at least 0.2 mole
fraction of crosslinking agent(s), it is typically preferred to
maximize the concentration of isocyanate reactive hydrocarbon
crosslinker to improve the durability and compatibility with the
binder of the hardcoat. Accordingly, the total amount of
crosslinking agent(s) may comprise at least 0.5 mole fraction and
may be at least 0.6 mole fraction, at least 0.7 mole fraction, at
least 0.8 mole fraction, or at least 0.9 mole of the sum of the
isocyanate reactants. The mole fraction of the perfluoropolyether
reactant is typically at least 0.05 and no greater than 0.5. The
mole fraction of ethylene oxide repeat unit containing reactant is
also typically at least 0.05 and no greater than 0.5.
[0036] The reaction product generally includes a distribution of
various reaction products. In addition to the reaction product of
the polyisocyanate with all three reactants (ii, iii, and iv) the
reaction product of the polyisocyanate with two of the three as
well as reaction products of the polyisocyanate the individual
reactants are also present.
[0037] For example, one representative structure formed by the
reaction product of a biuret of HDI with one equivalent of HFPO
oligomer amidol HFPO--C(O)NHCH.sub.2CH.sub.2OH wherein "a" averages
2 to 15, and further with two equivalents of pentaerythritol
triacrylate is shown as follows
##STR00001##
[0038] In one preferred embodiment, the perfluoropolyether urethane
composition is of the formula:
Ri-(NHC(O)XQRf), --(NHC(O)OQ(A)p),
--(NHC(O)X.sup.j(C.sub.2H.sub.4O).sub.jR.sup.j,
wherein Ri is a residue of a multi-isocyanate;
X and X.sup.j are each independently O, S or NR, where R is H or
lower alkyl of 1 to 4 carbon atoms;
Q is independently a connecting group of valency at least 2;
Rf is a monovalent perfluoropolyether moiety composed of groups
comprising the formula A is a (meth)acryl functional group such as
--XC(O)C(R2)=CH2, where R2 is a lower alkyl of 1 to 4 carbon atoms
or H or F;
[0039] p is 2 to 6; j ranges from 7 to 40; and R.sup.j is H,
--C(O)C(R.sub.2).dbd.CH.sub.2, where R.sub.2 is a lower alkyl of 1
to 4 carbon atoms or H or F, or a group selected from alkyl, aryl,
alkaryl, aralkyl, that can optionally be substituted with a
heteroatom, heteoratom functional groups (such as --OH --SH, and
--NH.sub.2), or a (meth)acryl functional group.
[0040] Depending on the number of individual materials employed as
well as the functionality of the reactants, a variety of
perlfluoropolyether urethane materials can be prepared having at
least one of each of the unit of this formula.
[0041] Q in association with the Rf group is a straight chain,
branched chain, or cycle-containing connecting group. Q can include
an alkylene, an arylene, an aralkylene, an alkarylene. Q can
optionally include heteroatoms such as O, N, and S, and
combinations thereof. Q can also optionally include a
heteroatom-containing functional group such as carbonyl or
sulfonyl, and combinations thereof.
[0042] When X is O, Q is typically not methylene and thus contains
two or more carbon atoms. In some embodiments, X is S or NR. In
some embodiments, Q is an alkylene having at least two carbon
atoms. In other embodiments, Q is a straight chain, branched chain,
or cycle-containing connecting group selected from arylene,
aralkylene, and alkarylene. In yet other embodiments, Q contains a
heteroatom such as O, N, and S and/or a heteroatom containing
functional groups such as carbonyl and sulfonyl. In other
embodiments, Q is a branched or cycle-containing alkylene group
that optionally contains heteroatoms selected from O, N, S and/or a
heteroatom-containing functional group such as carbonyl and
sulfonyl. In some embodiments Q contains a nitrogen containing
group such an amide group such as --C(O)NHCH.sub.2CH.sub.2--,
--C(O)NH(CH.sub.2).sub.6--, and
--C(O)NH(CH.sub.2CH.sub.2O).sub.2CH.sub.2CH.sub.2--.
[0043] Various other reactants can be included in the preparation
of the perfluoropolyether urethane such as described in
WO2006/102383; incorporated herein by reference.
[0044] The perfluoropolyether urethane polymeric material described
herein may be employed alone or in combination with various other
fluorinated compounds having at least one moiety selected from
fluoropolyether, fluoroalkyl, and fluoroalkylene linked to at least
one free-radically reactive group. When a second fluorinated
compound is employed, it is typically preferred that such second
fluorinated compound also comprises an HFPO-moiety. Various
fluorinated materials that can be employed in combination with the
perfluoropolyether urethane polymeric material described are also
described in WO2006/102383.
[0045] The polymerizable perfluoropolyether urethane composition is
typically dispersed in a hardcoat composition in combination with a
(e.g. alcohol based) solvent, applied to an optical substrate and
photocured to form the easy to clean, stain and ink repellent light
transmissible surface layer. The hardcoat is a tough, abrasion
resistant layer that protects the optical substrate and the
underlying display screen from damage from causes such as
scratches, abrasion and solvents. Typically the hardcoat is formed
by coating a curable liquid ceramer composition onto the substrate
and curing the composition in situ to form a hardened film.
[0046] The surface energy can be characterized by various methods
such as contact angle and ink repellency, as determined by the test
methods described in the Examples. In this application, "stain
repellent" refers to a surface treatment exhibiting a static
contact angle with water of at least 70 degrees. More preferably,
the contact angle is at least 80 degrees and most preferably at
least 90 degrees. Alternatively, or in addition thereto, the
advancing contact angle with hexadecane is at least 50 degrees and
more preferably at least 60 degrees. Low surface energy results in
anti-soiling and stain repellent properties as well as rendering
the exposed surface easy to clean.
[0047] Another indicator of low surface energy relates to the
extent to which ink from a pen or marker beads up when applied to
the exposed surface. The surface layer and articles exhibit "ink
repellency" when ink from pens and markers beads up into discrete
droplets and can be easily removed by wiping the exposed surface
with tissues or paper towels, such as tissues available from the
Kimberly Clark Corporation, Roswell, Ga. under the trade
designation "SURPASS FACIAL TISSUE." Durability can be defined in
terms of results from a modified oscillating sand test (Method ASTM
F 735-94) carried out at 250 rpm for 5 minutes as described in the
Test Methods of this application. Preferably, a durable coating
exhibits an ink repellency loss value of 65 mm (75% loss) or less,
more preferably 40 mm (45% loss) or less, most preferably 0 mm (no
loss) of ink repellency (IR) in this test.
[0048] The perfluoropolyether urethane polymeric material described
herein can be employed as the sole fluorinated component of a
one-layer hardcoat composition. For embodiments wherein high
durability is desired, the hardcoat composition typically further
comprises (e.g. surface modified) inorganic particles. The
thickness of the hardcoat surface layer is typically at least 0.5
microns, preferably at least 1 micron, and more preferably at least
2 microns. The thickness of the hardcoat layer is generally no
greater than 25 microns. Preferably the thickness ranges from 3
microns to 5 microns.
[0049] Alternatively, an inorganic particle free perfluoropolyether
urethane polymer containing surface layer may be employed alone for
uses where durability is not required. In yet other embodiments, an
inorganic particle free perfluoropolyether urethane polymer
containing surface layer may be provided in combination with an
inorganic particle containing hardcoat layer disposed between the
substrate and the surface layer. This will be referred to as a
two-layer hardcoat. In these embodiments, the surface layer
preferably has a thickness ranging from about 10 to 200
nanometers.
[0050] For one-layer hardcoat embodiments, the total of all
(per)fluorinated compounds, (e.g. the perfluoropolyether
urethane(s) alone or in combination with other fluorinated
compounds) ranges from 0.01% to 10%, and more preferably from 0.1%
to 1%, of the total solids of the hardcoat composition. For
two-layer hardcoat embodiments the amount of perfluoropolyether
urethane(s) in the coating compositions ranges from 0.01 to 50 wt-%
solids, and more preferably from 1 to 25 wt-% solids.
[0051] A variety of binder precursors that form a crosslinked
polymeric matrix upon curing can be employed in the hardcoat. The
isocyanate reactive non-fluorinated crosslinking materials
previously described are suitable binder precursors.
[0052] Di(meth)acryl binder precursors include for example
1,3-butylene glycol diacrylate, 1,4-butanediol diacrylate,
1,6-hexanediol diacrylate, 1,6-hexanediol monoacrylate
monomethacrylate, ethylene glycol diacrylate, alkoxylated aliphatic
diacrylate, alkoxylated cyclohexane dimethanol diacrylate,
alkoxylated hexanediol diacrylate, alkoxylated neopentyl glycol
diacrylate, caprolactone modified neopentylglycol hydroxypivalate
diacrylate, caprolactone modified neopentylglycol hydroxypivalate
diacrylate, cyclohexanedimethanol diacrylate, diethylene glycol
diacrylate, dipropylene glycol diacrylate, ethoxylated bisphenol A
diacrylate, hydroxypivalaldehyde modified trimethylolpropane
diacrylate, neopentyl glycol diacrylate, polyethylene glycol
diacrylate, propoxylated neopentyl glycol diacrylate, tetraethylene
glycol diacrylate, tricyclodecanedimethanol diacrylate, triethylene
glycol diacrylate, tripropylene glycol diacrylate.
[0053] Tri(meth)acryl binder precursore include for example
glycerol triacrylate, trimethylolpropane triacrylate, ethoxylated
trimethylolpropane triacrylates (e.g. having 3 to 20 ethoxylate
repeat), propoxylated glyceral triacrylates, trimethylolpropane
triacrylate, tris(2-hydroxyethyl)isocyanurate triacrylate. Higher
functionality (meth)acryl containing compounds include for example
ditrimethylolpropane tetraacrylate, dipentaerythritol
pentaacrylate, ethoxylated pentaerythritol tetraacrylate,
caprolactone modified dipentaerythritol hexaacrylate.
[0054] One commercially available form of pentaerythritol
triacrylate ("PET3A") is SR444C and one commercially available form
of pentaerythritol tetraacrylate ("PET4A") is SR295, each available
from Sartomer Company of Exton, Pa.
[0055] Oligomeric (meth)acryl such as urethane acrylates, polyester
acrylates, epoxy acrylates; and polyacrylamide analogues of the
foregoing can also be employed as the binder.
[0056] In one embodiment, the binder may comprise one or more
N,N-disubstituted acrylamide and or N-substituted-N-vinyl-amide
monomers as described in Bilkadi et al. The hardcoat may be derived
from a ceramer composition containing about 20 to about 80%
ethylenically unsaturated monomers and about 5 to about 40%
N,N-disubstituted acrylamide monomer or N-substituted-N-vinyl-amide
monomer, based on the total weight of the solids in the ceramer
composition.
[0057] To facilitate curing, polymerizable compositions described
herein may further comprise at least one free-radical thermal
initiator and/or photoinitiator. Typically, if such an initiator
and/or photoinitiator are present, it comprises less than about 10
percent by weight, more typically less than about 5 percent of the
polymerizable composition, based on the total weight of the
polymerizable composition. Free-radical curing techniques are well
known in the art and include, for example, thermal curing methods
as well as radiation curing methods such as electron beam or
ultraviolet radiation. Further details concerning free radical
thermal and photopolymerization techniques may be found in, for
example, U.S. Pat. No. 4,654,233 (Grant et al.); U.S. Pat. No.
4,855,184 (Klun et al.); and U.S. Pat. No. 6,224,949 (Wright et
al.).
[0058] Useful free-radical thermal initiators include, for example,
azo, peroxide, persulfate, and redox initiators, and combinations
thereof.
[0059] Useful free-radical photoinitiators include, for example,
those known as useful in the UV cure of acrylate polymers such as
described in WO2006/102383.
[0060] The polymerizable composition for use as the surface layer
or an underlying hardcoat layer preferably contains surface
modified inorganic particles that add mechanical strength and
durability to the resultant coating.
[0061] A variety of inorganic oxide particles can be used in the
hardcoat. The inorganic oxide particles can consist essentially of
or consist of a single oxide such as silica, or can comprise a
combination of oxides, such as silica and aluminum oxide, or a core
of an oxide of one type (or a core of a material other than a metal
oxide) on which is deposited an oxide of another type. Silica is a
common inorganic particle. The inorganic oxide particles are often
provided in the form of a sol containing a colloidal dispersion of
inorganic oxide particles in liquid media. The sol can be prepared
using a variety of techniques and in a variety of forms including
hydrosols (where water serves as the liquid medium), organosols
(where organic liquids so serve), and mixed sols (where the liquid
medium contains both water and an organic liquid), e.g., as
described in U.S. Pat. No. 5,648,407 (Goetz et al.); U.S. Pat. No.
5,677,050 (Bilkadi et al.) and U.S. Pat. No. 6,299,799 (Craig et
al.), the disclosure of which is incorporated by reference herein.
Aqueous sols (e.g. of amorphous silica) can be employed. Sols
generally contain at least 2 wt-%, at least 10 wt-%, at least 15
wt-%, at least 25 wt-%, and often at least 35 wt-% colloidal
inorganic oxide particles based on the total weight of the sol. The
amount of colloidal inorganic oxide particle is typically no more
than 50 wt-% (e.g. 45 wt-%). The surface of the inorganic particles
can be "acrylate functionalized" as described in Bilkadi et al. The
sols can also be matched to the pH of the binder, and can contain
counter ions or water-soluble compounds (e.g., sodium aluminate),
all as described in Kang et al. '798.
[0062] Various high refractive index inorganic oxide particles can
be employed such as for example zirconia ("ZrO.sub.2"), titania
("TiO.sub.2"), antimony oxides, alumina, tin oxides, alone or in
combination. Mixed metal oxide may also be employed. Zirconias for
use in the high refractive index layer are available from Nalco
Chemical Co. under the trade designation "Nalco OOSSOO8" and from
Buhler AG Uzwil, Switzerland under the trade designation "Buhler
zirconia Z-WO sol". Zirconia nanoparticle can also be prepared such
as described in U.S. patent application Ser. No. 11/027,426 filed
Dec. 30, 2004 and U.S. Pat. No. 6,376,590.
[0063] The inorganic nanoparticles are preferably treated with a
surface treatment agent. Surface-treating the nano-sized particles
can provide a stable dispersion in the polymeric resin. Preferably,
the surface-treatment stabilizes the nanoparticles so that the
particles will be well dispersed in the polymerizable resin and
results in a substantially homogeneous composition. Furthermore,
the nanoparticles can be modified over at least a portion of its
surface with a surface treatment agent so that the stabilized
particle can copolymerize or react with the polymerizable resin
during curing. The incorporation of surface modified inorganic
particles is amenable to covalent bonding of the particles to the
free-radically polymerizable organic components, thereby providing
a tougher and more homogeneous polymer/particle network.
[0064] In general, a surface treatment agent has a first end that
will attach to the particle surface (covalently, ionically or
through strong physisorption) and a second end that imparts
compatibility of the particle with the resin and/or reacts with
resin during curing. Examples of surface treatment agents include
alcohols, amines, carboxylic acids, sulfonic acids, phosphonic
acids, silanes and titanates. The preferred type of treatment agent
is determined, in part, by the chemical nature of the metal oxide
surface. Silanes are preferred for silica and other for siliceous
fillers. Silanes and carboxylic acids are preferred for metal
oxides such as zirconia. The surface modification can be done
either subsequent to mixing with the monomers or after mixing. It
is preferred in the case of silanes to react the silanes with the
particle or nanoparticle surface before incorporation into the
resin. The required amount of surface modifier is dependant upon
several factors such as particle size, particle type, modifier
molecular wt, and modifier type. In general, it is preferred that
approximately a monolayer of modifier is attached to the surface of
the particle. The attachment procedure or reaction conditions
required also depend on the surface modifier used. For silanes it
is preferred to surface treat at elevated temperatures under acidic
or basic conditions for from 1-24 hr approximately. Surface
treatment agents such as carboxylic acids may not require elevated
temperatures or extended time.
[0065] Representative embodiments of surface treatment agents
suitable for the compositions include compounds such as, for
example, isooctyl trimethoxy-silane,
N-(3-triethoxysilylpropyl)methoxyethoxyethoxyethyl carbamate,
N-(3-triethoxysilylpropyl)methoxyethoxyethoxyethyl carbamate,
3-(methacryloyloxy)propyltrimethoxysilane,
3-acryloxypropyltrimethoxysilane,
3-(methacryloyloxy)propyltriethoxysilane,
3-(methacryloyloxy)propylmethyldimethoxysilane,
3-(acryloyloxypropyl)methyldimethoxysilane,
3-(methacryloyloxy)propyldimethylethoxysilane,
3-(methacryloyloxy)propyldimethylethoxysilane,
vinyldimethylethoxysilane, phenyltrimethoxysilane,
n-octyltrimethoxysilane, dodecyltrimethoxysilane,
octadecyltrimethoxysilane, propyltrimethoxysilane,
hexyltrimethoxysilane, vinylmethyldiacetoxysilane,
vinylmethyldiethoxysilane, vinyltriacetoxysilane,
vinyltriethoxysilane, vinyltriisopropoxysilane,
vinyltrimethoxysilane, vinyltriphenoxysilane,
vinyltri-t-butoxysilane, vinyltris-isobutoxysilane,
vinyltriisopropenoxysilane, vinyltris(2-methoxyethoxy)silane,
styrylethyltrimethoxysilane, mercaptopropyltrimethoxysilane,
3-glycidoxypropyltrimethoxysilane, acrylic acid, methacrylic acid,
oleic acid, stearic acid, dodecanoic acid,
2-[2-(2-methoxyethoxy)ethoxy]acetic acid (MEEAA),
beta-carboxyethylacrylate (BCEA), 2-(2-methoxyethoxy)acetic acid,
methoxyphenyl acetic acid, and mixtures thereof.
[0066] The surface modification of the particles in the colloidal
dispersion can be accomplished in a variety known ways, such as
described in U.S. patent application Ser. No. 11/027,426 filed Dec.
30, 2004; U.S. Pat. No. 6,376,590.
[0067] A combination of surface modifying agents can be useful,
wherein at least one of the agents has a functional group
co-polymerizable with a hardenable resin. Combinations of surface
modifying agent can result in lower viscosity. For example, the
polymerizing group can be ethylenically unsaturated or a cyclic
function subject to ring opening polymerization. An ethylenically
unsaturated polymerizing group can be, for example, an acrylate or
methacrylate, or vinyl group. A cyclic functional group subject to
ring opening polymerization generally contains a heteroatom such as
oxygen, sulfur or nitrogen, and preferably a 3-membered ring
containing oxygen such as an epoxide.
[0068] A preferred combination of surface modifying agent includes
at least one surface modifying agent having a functional group that
is copolymerizable with the organic component of the polymerizable
resin and a second amphiphilic modifying agent, such as a polyether
silane, that may act as a dispersant. The second modifying agent is
preferably a polyalkyleneoxide containing modifying agent that is
optionally co-polymerizable with the organic component of the
polymerizable composition.
[0069] Surface modified colloidal nanoparticles can be
substantially fully condensed. Non-silica containing fully
condensed nanoparticles typically have a degree of crystallinity
(measured as isolated metal oxide particles) greater than 55%,
preferably greater than 60%, and more preferably greater than 70%.
For example, the degree of crystallinity can range up to about 86%
or greater. The degree of crystallinity can be determined by X-ray
diffraction techniques. Condensed crystalline (e.g. zirconia)
nanoparticles have a high refractive index whereas amorphous
nanoparticles typically have a lower refractive index.
[0070] The inorganic particles preferably have a substantially
monodisperse size distribution or a polymodal distribution obtained
by blending two or more substantially monodisperse distributions.
Alternatively, the inorganic particles can be introduced having a
range of particle sizes obtained by grinding the particles to a
desired size range. The inorganic oxide particles are typically
non-aggregated (substantially discrete), as aggregation can result
in optical scattering (haze) or precipitation of the inorganic
oxide particles or gelation. The inorganic oxide particles are
typically colloidal in size, having an average particle diameter of
5 nanometers to 100 nanometers. The particle size of the high index
inorganic particles is preferably less than about 50 nm in order to
provide sufficiently transparent high-refractive index coatings.
The average particle size of the inorganic oxide particles can be
measured using transmission electron microscopy to count the number
of inorganic oxide particles of a given diameter.
[0071] The optical film having a perfluoropolyether urethane
containing surface layer as described herein may have a gloss or
matte surface. Matte films typically have lower transmission and
higher haze values than typical gloss films. For examples the haze
is generally at least 5%, 6%, 7%, 8%, 9%, or 10% as measured
according to ASTM D1003. Whereas gloss surfaces typically have a
gloss of at least 130 as measured according to ASTM D 2457-03 at
60.degree.; matte surfaces have a gloss of less than 120.
[0072] A particulate matting agent can be incorporated into the
polymerizable composition in order to impart anti-glare properties
to the surface layer. The particulate matting agent also prevents
the reflectance decrease and uneven coloration caused by
interference with an associated hard coat layer.
[0073] Exemplary systems incorporating matting agents into a hard
coating layer, but having a different hard coating composition, are
described, for example, in U.S. Pat. No. 6,693,746, and herein
incorporated by reference. Further, exemplary matte films are
commercially available from U.S.A. Kimoto Tech of Cedartown, Ga.,
under the trade designation "N4D2A."
[0074] The amount of particulate matting agent added is between
about 0.5 and 10% of the total solids of the composition, depending
upon the thickness of the layer, with a preferred amount around
2%.
[0075] The average particle diameter of the particulate matting
agent has a predefined minimum and maximum that is partially
dependent upon the thickness of the layer. However, generally
speaking, average particle diameters below 1.0 microns do not
provide the degree of anti-glare sufficient to warrant inclusion,
while average particle diameters exceeding 10.0 microns deteriorate
the sharpness of the transmission image. The average particle size
is thus preferably between about 1.0 and 10.0 microns, and more
preferably between 1.7 and 3.5 microns, in terms of the
number-averaged value measured by the Coulter method.
[0076] As the particulate matting agent, inorganic particles or
resin particles are used including, for example, amorphous silica
particles, TiO.sub.2 particles, Al.sub.2O.sub.3 particles,
cross-linked acrylic polymer particles such as those made of
cross-linked poly(methyl methacrylate), cross-linked polystyrene
particles, melamine resin particles, benzoguanamine resin
particles, and cross-linked polysiloxane particles. By taking into
account the dispersion stability and sedimentation stability of the
particles in the coating mixture for the anti-glare layer and/or
the hard coat layer during the manufacturing process, resin
particles are more preferred, and in particular cross-linked
polystyrene particles are preferably used since resin particles
have a high affinity for the binder material and a small specific
gravity.
[0077] As for the shape of the particulate matting agent, spherical
and amorphous particles can be used. However, to obtain a
consistent anti-glare property, spherical particles are desirable.
Two or more kinds of particulate materials may also be used in
combination.
[0078] One commercially available silica particulate matting agent
having an average particle size of 3.5 microns is commercially
available from W.R. Grace and Co., Columbia, Md. under the trade
designation "Syloid C803".
[0079] Other types of inorganic particles can also be incorporated
into the hardcoat compositions. Particularly preferred are
conducting metal oxide nanoparticles such as antimony tin oxide,
fluorinated tin oxide, vanadium oxide, zinc oxide, antimony zinc
oxide, and indium tin oxide. They can also be surface treated with
materials such as 3-methacryloxypropyltrimethoxysilane. These
particles can provide constructions with antistatic properties.
This is desirable to prevent static charging and resulting
contamination by adhesion of dust and other unwanted debris during
handling and cleaning of the film. Preferably, such metal oxide
particles are incorporated into the top (thin) layer of the
two-layer constructions of this invention, in which the fluorinated
hardcoat is applied to a hydrocarbon-based hardcoat. Examples of
conducting metal oxide nanoparticles useful in this embodiment
include antimony double oxide available from Nissan Chemical under
the trade designations Celnax CXZ-2101P and CXZ-2101P-F2.
[0080] The perfluoropolyether urethane polymeric material alone or
in combination with the hardcoat composition can be dispersed in a
solvent to form a dilute coating composition. The amount of solids
in the coating composition is typically at least 20 wt-% and
usually no greater than about 50 wt-%. For some optical substrate
such as polycarbonate, acrylic, cellulose acetate, and cellulose
triacetate, it is preferred to employ an alcohol based solvent
including for example methanol, ethyl alcohol, isopropyl alcohol,
propanol, etc. as well as glycol ethers such as propylene glycol
monomethyl ether or ethylene glycol monomethyl ether, etc. For such
optical substrates, the coating compositions may contain
predominantly alcohol solvent(s). For other uses, however, alcohol
based solvent(s) may be combined with other (i.e. non-alcohol)
solvents.
[0081] Thin coating layers can be applied to the optical substrate
using a variety of techniques, including dip coating, forward and
reverse roll coating, wire wound rod coating, and die coating. Die
coaters include knife coaters, slot coaters, slide coaters, fluid
bearing coaters, slide curtain coaters, drop die curtain coaters,
and extrusion coaters among others. Many types of die coaters are
described in the literature such as by Edward Cohen and Edgar
Gutoff, Modern Coating and Drying Technology, VCH Publishers, NY
1992, ISBN 3-527-28246-7 and Gutoff and Cohen, Coating and Drying
Defects: Troubleshooting Operating Problems, Wiley Interscience, NY
ISBN 0-471-59810-0.
[0082] A die coater generally refers to an apparatus that utilizes
a first die block and a second die block to form a manifold cavity
and a die slot. The coating fluid, under pressure, flows through
the manifold cavity and out the coating slot to form a ribbon of
coating material. Coatings can be applied as a single layer or as
two or more superimposed layers. Although it is usually convenient
for the substrate to be in the form of a continuous web, the
substrate may also be a succession of discrete sheets.
[0083] The term "optical display", or "display panel", can refer to
any conventional optical displays, including but not limited to
multi-character multi-line displays such as liquid crystal displays
("LCDs"), plasma displays, front and rear projection displays,
cathode ray tubes ("CRTs"), and signage, as well as
single-character or binary displays such as light emitting diodes
("LEDs"), signal lamps, and switches. The exposed surface of such
display panels may be referred to as a "lens." The invention is
particularly useful for displays having a viewing surface that is
susceptible to being touched or contacted by ink pens, markers and
other marking devices, wiping cloths, paper items and the like. The
protective coatings of the invention can be employed in a variety
of portable and non-portable information display articles. These
articles include PDAs, cell phones (including combination PDA/cell
phones), LCD televisions (direct lit and edge lit), touch sensitive
screens, wrist watches, car navigation systems, global positioning
systems, depth finders, calculators, electronic books, CD and DVD
players, projection television screens, computer monitors, notebook
computer displays, instrument gauges, instrument panel covers,
signage such as graphic displays and the like. The viewing surfaces
can have any conventional size and shape and can be planar or
non-planar, although flat panel displays are preferred. The coating
composition or coated film, can be employed on a variety of other
articles as well such as for example camera lenses, eyeglass
lenses, binocular lenses, mirrors, retroreflective sheeting,
automobile windows, building windows, train windows, boat windows,
aircraft windows, vehicle headlamps and taillights, display cases,
road pavement markers (e.g. raised) and pavement marking tapes,
overhead projectors, stereo cabinet doors, stereo covers, watch
covers, as well as optical and magneto-optical recording disks, and
the like.
[0084] A variety of substrates can be utilized in the articles of
the invention. Suitable substrate materials include glass as well
as thermosetting or thermoplastic polymers such as polycarbonate,
poly(meth)acrylate (e.g., polymethyl methacrylate or "PMMA"),
polyolefins (e.g., polypropylene or "PP"), polyurethane, polyesters
(e.g., polyethylene terephthalate or "PET"), polyamides,
polyimides, phenolic resins, cellulose diacetate, cellulose
triacetate, polystyrene, styrene-acrylonitrile copolymers, epoxies,
and the like. Typically the substrate will be chosen based in part
on the desired optical and mechanical properties for the intended
use. Such mechanical properties typically will include flexibility,
dimensional stability and impact resistance. The substrate
thickness typically also will depend on the intended use. For most
applications, a substrate thickness of less than about 0.5 mm is
preferred, and is more preferably about 0.02 to about 0.2 mm.
Self-supporting polymeric films are preferred. Films made from
polyesters such as PET or polyolefins such as PP (polypropylene),
PE (polyethylene) and PVC (polyvinyl chloride) are particularly
preferred. The polymeric material can be formed into a film using
conventional filmmaking techniques such as by extrusion and
optional uniaxial or biaxial orientation of the extruded film. The
substrate can be treated to improve adhesion between the substrate
and the hardcoat layer, e.g., chemical treatment, corona treatment
such as air or nitrogen corona, plasma, flame, or actinic
radiation. If desired, an optional tie layer or primer can be
applied to the substrate and/or hardcoat layer to increase the
interlayer adhesion.
[0085] Various light transmissive optical films are known including
but not limited to, multilayer optical films, microstructured films
such as retroreflective sheeting and brightness enhancing films,
(e.g. reflective or absorbing) polarizing films, diffusive films,
as well as (e.g. biaxial) retarder films and compensator films such
as described in U.S. Patent Application Publication No.
2004/0184150.
[0086] As described is U.S. Patent Application Publication
2003/0217806, multilayer optical films provide desirable
transmission and/or reflection properties at least partially by an
arrangement of microlayers of differing refractive index. The
microlayers have different refractive index characteristics so that
some light is reflected at interfaces between adjacent microlayers.
The microlayers are sufficiently thin so that light reflected at a
plurality of the interfaces undergoes constructive or destructive
interference in order to give the film body the desired reflective
or transmissive properties. For optical films designed to reflect
light at ultraviolet, visible, or near-infrared wavelengths, each
microlayer generally has an optical thickness (i.e., a physical
thickness multiplied by refractive index) of less than about 1
.mu.m. However, thicker layers can also be included, such as skin
layers at the outer surfaces of the film, or protective boundary
layers disposed within the film that separate packets of
microlayers. Multilayer optical film bodies can also comprise one
or more thick adhesive layers to bond two or more sheets of
multilayer optical film in a laminate.
[0087] Further details of suitable multilayer optical films and
related constructions can be found in U.S. Pat. No. 5,882,774
(Jonza et al.), and PCT Publications WO 95/17303 (Ouderkirk et al.)
and WO 99/39224 (Ouderkirk et al.). Polymeric multilayer optical
films and film bodies can comprise additional layers and coatings
selected for their optical, mechanical, and/or chemical properties.
See U.S. Pat. No. 6,368,699 (Gilbert et al.). The polymeric films
and film bodies can also comprise inorganic layers, such as metal
or metal oxide coatings or layers
[0088] Various permanent and removable grade adhesive compositions
may be coated on the opposite side (i.e. to the hardcoat) of the
substrate so the article can be easily mounted to a display
surface. Suitable adhesive compositions include (e.g. hydrogenated)
block copolymers such as those commercially available from Kraton
Polymers of Westhollow, Tex. under the trade designation "Kraton
G-1657", as well as other (e.g. similar) thermoplastic rubbers.
Other exemplary adhesives include acrylic-based, urethane-based,
silicone-based, and epoxy-based adhesives. Preferred adhesives are
of sufficient optical quality and light stability such that the
adhesive does not yellow with time or upon weather exposure so as
to degrade the viewing quality of the optical display. The adhesive
can be applied using a variety of known coating techniques such as
transfer coating, knife coating, spin coating, die coating and the
like. Exemplary adhesives are described in U.S. Patent Application
Publication No. 2003/0012936. Several of such adhesives are
commercially available from 3M Company, St. Paul, Minn. under the
trade designations 8141, 8142, and 8161.
Glossary
[0089] For the following defined terms, these definitions shall be
applied, unless a different definition is given in the claims or
elsewhere in the specification.
[0090] "Free-radically polymerizable" refers to the ability of
monomers, oligomers, polymers or the like to participate in
crosslinking reactions upon exposure to a suitable source of free
radicals.
[0091] "(Meth)acryl" refers to functional groups including
acrylates, methacrylates, acrylamides, methacrylamides,
alpha-fluoroacrylates, thioacrylates and thio-methacrylates. A
preferred (meth)acryl group is acrylate.
[0092] "Monovalent perfluoropolyether moiety" refers to a
perfluoropolyether chain having one end terminated by a
perfluoroalkyl group.
[0093] Unless otherwise noted, "HFPO-" refers to the end group
F(CF(CF.sub.3)CF.sub.2O)aCF(CF.sub.3)-- of the methyl ester
F(CF(CF.sub.3)CF.sub.2O)aCF(CF.sub.3)C(O)OCH3, wherein "a" averages
2 to 15. In some embodiments, a averages between 3 and 10 or a
averages between 5 and 8. Such species generally exist as a
distribution or mixture of oligomers with a range of values for a,
so that the average value of a may be non-integer. In one
embodiment a averages 6.2. This methyl ester has an average
molecular weight of 1,211 g/mol, and can be prepared according to
the method reported in U.S. Pat. No. 3,250,808 (Moore et al.), the
disclosure of which is incorporated herein by reference, with
purification by fractional distillation.
[0094] The recitation of numerical ranges by endpoints includes all
numbers subsumed within the range (e.g. the range 1 to 10 includes
1, 1.5, 3.33, and 10).
[0095] Objects and advantages of this invention are further
illustrated by the following examples, but the particular materials
and amounts thereof recited in these examples, as well as other
conditions and details, should not be construed to unduly limit
this invention.
EXAMPLES
Test Methods
[0096] 1. Spots: The number of spots was determined visually in a
25 cm.sup.2 area by counting the number of spots with the coating
held against a black background. When the composition includes a
particulate matting agent such as silica, the spots are white in
appearance and can be more easily detected.
[0097] 2. Contact Angle: Measurements were made using deionized
water filtered through a filtration system obtained from Millipore
Corporation (Billerica, Mass.), on a PgX Goniometer contact angle
analyzer available as product number PGX from FIBRO System AB,
Sweden. Reported values are the averages of measurements on at
least three drops. Drop volumes were 5 .mu.L for static
measurements.
[0098] 3. Durability of Ink Repellency was assessed using a
modified Oscillating Sand Method (ASTM F 735-94). An orbital shaker
was used (VWR DS-500E, from VWR Bristol, Conn.). A disk of diameter
89 mm was cut from the sample, placed in a 16 ounce jar lid (jar
W216922 from Wheaton, Millville, N.J.), and covered with 40 grams
of 20-30 mesh Ottawa sand (VWR, Bristol, Conn.). The jar was capped
and placed in the shaker set at 250 rpm for 5 minutes. After
shaking, a Sharpie permanent marker was used to draw a line across
the diameter of the disk surface. The portion of the ink line that
did not bead up was measured. A measure of 89 mm is equal to 100%
ink repellency loss; a measure of 0 mm would be perfect durability
or 0% ink repellency (IR) loss.
Synthesis of Perfluoropolyether Alcohol Starting Materials
[0099] HFPO--C(O)N(H)CH.sub.2CH.sub.2OH of different molecular
weights (938.5, 1314, 1344, and 1547.2) were made by a procedure
similar to that described in U.S. Publication No. 2004-0077775,
(Docket Number 57823), entitled "Fluorochemical Composition
Comprising a Fluorinated Polymer and Treatment of a Fibrous
Substrate Therewith," filed on May 24, 2002, for Synthesis of
HFPO-oligomer alcohols with the exception that HFPO methyl ester
F(CF(CF.sub.3)CF.sub.2O)aCF(CF.sub.3)C(O)CH.sub.3 with a=6.2 was
replaced with F(CF(CF3)CF2O)aCF(CF3)C(O)OCH3 wherein a=4.41, 6.67,
6.85, and 8.07 respectively.
[0100] The methyl ester material for preparation of the alcohol can
be prepared according to the method reported in U.S. Pat. No.
3,250,808 (Moore et al.), the disclosure of which is incorporated
herein by reference, with purification by fractional
distillation.
[0101] 1. HFPO--C(O)N(H)(CH.sub.2CH.sub.2O).sub.3H, MW 1329 was
prepared according to the procedures for
HFPO--C(O)N(H)CH.sub.2CH.sub.2OH, using
F(CF(CF.sub.3)CF.sub.2O)aCF(CF.sub.3)C(O)CH.sub.3 with a=6.2 (1211
MW) and substituting H.sub.2N(CH.sub.2CH.sub.2O).sub.3H for
H.sub.2NCH.sub.2CH.sub.2OH.
[0102] 2. HFPO--C(O)N(H)(CH.sub.2).sub.6OH, MW 1297 was prepared
according to the procedures for HFPO--C(O)N(H)CH.sub.2CH.sub.2OH,
using F(CF(CF.sub.3)CF.sub.2O)aCF(CF.sub.3)C(O)CH.sub.3 with a=6.2
(1211 MW) and substituting H.sub.2N(CH.sub.2).sub.6OH for
H.sub.2NCH.sub.2CH.sub.2OH
[0103] Polyisocyanate was obtained from Bayer Polymers LLC, of
Pittsburgh, Pa. under the trade designation "Desmodur N100".
("DesN100")
[0104] Polyisocyanate was obtained from Bayer Polymers LLC, of
Pittsburgh, Pa. under the trade designation "Desmodur N3300".
("DesN3300")
[0105] Pentaerythritol triacrylate ("PET3A"), under the trade
designation "SR444C", was obtained from Sartomer Company of Exton,
Pa.
[0106] 2,6-di-t-butyl-4-methylphenol (BHT) and dibutyltin dilaurate
(DBTDL) are each available from Sigma Aldrich of Milwaukee,
Wis.
Synthesis of Perfluoropolyether Urethane Multiacrylate
Example 1
Preparation of Des N100/0.85 PET3A/0.10
HFPO--C(O)NHCH.sub.2CH.sub.2OH/0.10
C.sub.18H.sub.37(OCH.sub.2CH.sub.2).sub.10OH
[0107] A 500 ml roundbottom flask equipped with magnetic stir bar
was charged with 25.0 g (0.131 eq, 191 EW, 1.0 mole fraction) Des
N100, 106.75 g methyl ethyl ketone (MEK), and 0.05 g BHT. The
reaction was swirled to dissolve all the reactants, the flask was
placed in a oil bath at 55 degrees Celsius, and fitted with a
condenser under dry air. Sixty-five microliters of a 10% dibutyltin
dilaurate solution in MEK was added to the reaction. Over 20 min,
17.59 g (0.0131 eq, 1344 EW, 0.10 mole fraction)
[0108]
F(CF(CF.sub.3)CF.sub.2O).sub.6.85CF(CF.sub.3)C(O)NHCH.sub.2CH.sub.2-
OH was added to the reaction via addition funnel. Two hours after
the addition was complete, 9.07 g (0.0131 eq, 692.6 EW, 0.10 mole
fraction) C.sub.18H.sub.37(OCH.sub.2CH.sub.2).sub.10OH (Brij 76)
was added over 20 min. After reaction overnight, the following
afternoon, 54.99 g (0.1115 eq, at 494.3 EW, 0.85 mole fraction) of
Sartomer SR444C was added in one portion to the reaction which was
allowed to proceed overnight. (The actual OH equivalent weight of
the SR444C was 421.8, but 494.3 is used in calculations for all
lots of SR444C, so that for any given material made, the weight
percentage of SR444C will remain constant). The reaction was
monitored by FTIR and initially showed an isocyanate absorption at
2273 cm.sup.-1. This absorption was gone after reaction overnight,
and 7.40 g of MEK was added to compensate for MEK lost during the
reaction to adjust the final solids to 50% solids.
[0109] The perfluoropolyether urethane multiacrylates of
Preparations 2-14, C1 and C2 were made by substantially the same
procedure with 1.0 mole fraction (Des N100) isocyanate, the
HFPO-alcohol at 0.10 mole fraction and each of the modifying
alcohols at the mole fractions indicated in column 5 of the
following Table 1. The HFPO--C(O)NHCH.sub.2CH.sub.2OH amidol of
1344 molecular weight was used for Example numbers C1, C3, 2, 3, 4,
5; whereas the HFPO--C(O)NHCH.sub.2CH.sub.2OH amidol of 1314
molecular weight was used for C2.
TABLE-US-00001 PET3A/ Alcohol Ex. Trade Modifying Alcohol Mole No.
Designation Supplier, location Molecular Weight Fraction C1 None
0.95/0.0 C2 Aldrich, HO(CH.sub.2).sub.10OH 0.75/0.2 St. Louis, MO 1
10 decane diol Mn = 174.3 g/mole C3 Bisomer Cognis, Cincinnati,
HO(CH.sub.2CH.sub.2O).sub.6C(O)CH.dbd.C.sub.2 0.75/0.2 PEA6 OH
Polyethylene glycol (6) monoacrylate 2 MA-100 Nippon Nyukazai,
HO(CH.sub.2CH.sub.2O).sub.10C(O)CH(CH.sub.3).dbd.CH2 0.85/0.1
Tokyo, Japan Hydroxyl alkylene oxide methacrylate Mn = 517 g/mole 3
NOVEL II Sasol North 50:50 blend of 0.85/0.1 810-10-10 America,
Huston, HO--(CH.sub.2CH.sub.2O).sub.10C.sub.8H.sub.17 and TX.
HO--(CH.sub.2CH.sub.2O).sub.10C.sub.10H.sub.21 Mn = 592.4 g/mole 4
CALGENE Lambent C.sub.11H.sub.23C(O)(CH.sub.2CH.sub.2O).sub.10 OH
0.85/0.1 40-L Technologies, Mn = 640 g/mole Gurnee, IL 5 Brij 78
Uniqema, New C.sub.18H.sub.37(OCH.sub.2CH.sub.2).sub.20OH 0.85/0.1
Castle, DE Mn = 1058.5 g/mole
Ex. 6 and C4
1.0 DES N3300/PET3A/0.1
HFPOC(O)NHCH.sub.2CH.sub.2OH/C.sub.18H.sub.37(OCH.sub.2CH.sub.2).sub.20OH
[0110] Brij 78 at 50% solids in MEK. Both made with SR444C 421.8
EW., HFPOC(O)NHCH.sub.2CH.sub.2OH MW 1314, DES N3300 has an
equivalent weight of 193.
TABLE-US-00002 Example No. PET3A/Alcohol Mole Fraction C4 0.95/0.0
6 0.85/0.10
Ex. 7 and C5
1.0 DES N100/PET3A/0.1 HFPOC(O)NHCH.sub.2CH.sub.2OH
C.sub.18H.sub.37(OCH.sub.2CH.sub.2).sub.20OH
[0111] Brij 78 at 50% solids in MEK. Both made with SR444C 421.8
EW., HFPOC(O)NHCH.sub.2CH.sub.2OH MW 938.5.
TABLE-US-00003 Example No. PET3A/Alcohol Mole Fraction C5 0.95/0.0
7 0.85/0.10
Ex. 8 and C6
1.0 DES N100/PET3A/0.1
HFPOC(O)NH(CH.sub.2CH.sub.2O).sub.3H/C.sub.18H.sub.37(OCH.sub.2CH.sub.2).-
sub.20OH
[0112] Brij 78 at 50% solids in MEK.
[0113] Both made with SR444C 421.8 EW.,
HFPOC(O)NH(CH.sub.2CH.sub.2O).sub.3H MW 1329
TABLE-US-00004 Example No. PET3A/Alcohol Mole Fraction C6 0.95/0.0
8 0.85/0.10
Ex. 9 and 10
1.0 DES N100/0.1 PET3A/0.1 HFPOC(O)NHCH.sub.2CH.sub.2OH/Modifying
Alcohol
[0114] at 50% solids in MEK. Both made with SR444C 421.8 EW.,
HFPOC(O)NHCH.sub.2CH.sub.2OH MW 1314
TABLE-US-00005 PET3A/ Alcohol Trade Supplier, Modifying Alcohol,
Mole Example No. Designation location Molecular Weight Fraction 9
"Carbowax Dow Chemical CH.sub.3--(OCH.sub.2CH.sub.2).sub.13--OH
0.85/0.1 MPEG 550" Co., Midland, MI Mn = 553 g/mole 10 "Carbowax
Dow Chemical H--(OCH.sub.2CH.sub.2).sub.20--OH 0.85/0.20 PEG 900"
Co., Mn = 900 g/mole Midland, MI
[0115] The perfluoropolyether urethane multiacrylates of Examples
11-12 and C7 and C8 were made by substantially the same procedure
with 1.0 mole fraction (Des N100) isocyanate and the HFPO-alcohol
(MW=1314) amounts indicated in column 2 and the modifying alcohols
indicated in column 3, at the ew amounts indicated in column 4 of
the following Table 3:
TABLE-US-00006 Example HFPO PET3A/Alcohol No. Mole fraction
Modifying Alcohol Mole Fractions C7 0.25 None 0.8/0.0 11 0.25
C.sub.18H.sub.37(OCH.sub.2CH.sub.2).sub.20OH 0.65/0.15 Brij 78 12
0.25 C.sub.18H.sub.37(OCH.sub.2CH.sub.2).sub.20OH 0.55/0.25 Brij
78
Ex. 13 and C8
1.0 DES N100/PET3A/0.1
HFPOC(O)NHCH.sub.2CH.sub.2OH/C.sub.18H.sub.37(OCH.sub.2CH.sub.2).sub.20OH
[0116] Brij 78 at 50% solids in MEK. Both made with SR444C 421.8
EW., HFPOC(O)NHCH.sub.2CH.sub.2OH MW 1547
TABLE-US-00007 Example PET3A/Alcohol No. Mole Fraction C8 0.95/0.0
13 0.85/0.10
Ceramer Hardcoat Comprising the Perfluoropolyether Urethane
Multiacrylates
[0117] The ceramer hardcoat base compositions ("HCB-1", "HCB-2" and
"HCB-3") used in the examples were made as described in column 10,
line 25-39 and Example 1 of U.S. Pat. No. 5,677,050 to Bilkadi, et
al. with the following (wt-% solids) additions:
TABLE-US-00008 Material HCB-1 HCB-2 HCB-3 Example 1, No. 5,677,050
(solids) 94.4 Syloid C803 (silica) 2.8 2.75 2.7 Disperbyk 163
(dispersant) 2.8 2.75 2.7 Sartomer SR 295 46.75 Sartomer SR 238
46.75 Irgacure 819 1.0 SM Zirconia 74.1 Irgacure 184 1.4 Sartomer
399 19.1
[0118] Syloid C 803 is a fine silica from W.R. Grace and Co.,
Columbia, Md. Disperbyk 163 is a dispersant from Byk-Chemie USA,
Wallingford, Conn. Irgacure 819 and 184 are photoinitiators from
Ciba Specialty Chemicals, Tarrytown, N.Y. Sartomer SR 295, SR238,
SR399 are all multifunctional acrylate monomers from Sartomer
Corp., West Chester, Pa.
[0119] ZrO.sub.2 sols (40.8% solids in water) was prepared were
prepared in accordance with the procedures described in U.S. patent
application Ser. No. 11/079,832 filed Mar. 14, 2005 that claims
priority to U.S. patent application Ser. No. 11/078,468 filed Mar.
11, 2005. The resulting ZrO.sub.2 sols were evaluated with Photo
Correlation Spectroscopy (PCS), X-Ray Diffraction and Thermal
Gravimetric Analysis as described in U.S. patent application Ser.
Nos. 11/079,832 and 11/078,468. The ZrO.sub.2 sols used in the
examples had properties in the ranges that follow:
TABLE-US-00009 PCS Data Intensity Volume- (Intensity- Dispersion
avg size avg size avg)/(Volume- Index (nm) (nm) avg) 1.0 2.4 23.0
37.0 8.0 18.8 1.84 2.97
TABLE-US-00010 Relative Intensities Apparent Crystallite Size (nm)
Weighted Cubic/ (C, T) M M Avg M Avg XRD Tetragonal Monoclinic (1 1
1) (-1 1 1) (1 1 1) Size % C/T Size 100 6 12 7.0 8.5 3.0 6.0 4.0
11.0 4.5 8.3 89% 94% 7.0 8.4
Surface Modified Zirconia Nanoparticles (SM Zirconia)
[0120] 20.4 lbs of an aqueous dispersion of 10 nm zirconia
nanoparticles (40.8% solids in water) was added to a 10 gallon
reactor. 12.9 lbs additional water and 33.3 lbs
1-methoxy-2-propanol were added to the reactor with stirring. 2.5
lbs of 3-methacryloxypropyltrimethoxysilane was added slowly to the
reactor with stirring. 0.021 lbs of a 5% solution in water of
Prostab 5198 was added to the reactor with stirring. The mixture
was stirred 18 hours at 80.degree. C.
[0121] The reaction mixture was heated under vacuum (24-40 torr)
and the 1-methoxy-2-propanol/water azeotrope was distilled off to
remove substantially all of the water, while slowly adding 70.5 lbs
of additional 1-methoxy-2-propanol. 0.4 lbs of 30% ammonium
hydroxide was added to the reaction mixture, then the reaction was
concentrated to 59.2% solids by distilling off
1-methoxy-2-propanol. The surface modification reaction resulted in
a mixture containing 59.2% surface modified zirconia
(ZrO.sub.2-SM), by weight, in 1-methoxy-2-propanol. The final
mixture was filtered through a 1 micron filter.
Coating and Curing of Hardcoat Composition on Optical Film
[0122] Solutions were prepared at 30% solids in a solvent blend of
1:1 isopropanol:propylene glycol methyl ether and coated to yield a
dry thickness of about 4 microns using a number 12 wire wound rod
onto 5-mil Melinex 618 film. The coatings were dried in a 100
degree Celsius oven for 2 minutes and then placed on a conveyer
belt coupled to a ultraviolet ("UV") light curing device and UV
cured under nitrogen using a Fusion 500 watt H bulb at 30 ft/min.
The values reported in the Tables refer to the percent solids of
each component of the dried coating. The coatings were then
visually inspected for surface smoothness (dewetting). The coatings
were also tested for durability of ink repellency. Results are
shown in Tables 4 and 5.
TABLE-US-00011 TABLE 4 Hardcoat Composition Comprising
Perfluoropolyether (PFPE) Urethane Additive Wt-% solids Wt-% HCB-1
Solids PFPE Spots in PFPE Urethane (per Contact coating Urethane
Sample # Example No. cm.sup.2) Angle HC-1 99.4 0.6 27 C1 1.2 100
HC-2 99.4 0.6 91 C2 0.32 100 HC-3 99.4 0.6 38 C3 0.36 105 Ex. 14
99.4 0.6 42 2 0.2 105 Ex. 15 99.4 0.6 47 1 0.04 102 Ex. 16 99.4 0.6
48 3 0.08 102 Ex. 17 99.4 0.6 49 4 0.04 105 Ex. 18 99.4 0.6 53 5 0
103 HC-4 99.4 0.6 70 C4 1.6 104 Ex. 19 99.4 0.6 71 6 0.8 102 HC-5
99.4 0.6 72 C5 0.04 95 Ex. 20 99.4 0.6 73 7 0.04 94 HC-6 99.4 0.6
74 C6 0.28 103 Ex. 21 99.4 0.6 75 8 0.04 102 Ex. 22 99.4 0.6 78 9
0.04 105 Ex. 23 99.4 0.6 79 10 0.12 100 HC-7 99.4 0.6 82 C7 2.8 103
Ex. 24 99.4 0.6 83 11 2.8 103 Ex. 25 99.4 0.6 84 12 0.88 94 HC-8
99.4 0.6 85 C8 0.16 106 Ex. 26 99.4 0.6 86 13 0.04 102 HCB-2 HC-9
99.4 0.6 27 C1 0.36 102 Ex. 27 99.4 0.6 53 5 0.16 93 HCB-3 HC-10
99.4 0.6 27 C1 0.6 103 Ex. 28 99.4 0.6 53 5 0.24 94
[0123] Examples 16-18 were tested for Durability of Ink
Repellency.
[0124] The results are as follows:
TABLE-US-00012 Durability of Ink Repellency (% loss) HC1 0
Comparative Example 16 0 Example 17 11 Example 18 34
* * * * *