U.S. patent application number 11/821568 was filed with the patent office on 2008-12-25 for mixtures of polydiorganosiloxane polyamide-containing components and organic polymers.
Invention is credited to Jeffrey O. Ernslander, Danny L. Fleming, David S. Hays, Timothy J. Hebrink, Stephen A. Johnson, Audrey A. Sherman.
Application Number | 20080318065 11/821568 |
Document ID | / |
Family ID | 40136820 |
Filed Date | 2008-12-25 |
United States Patent
Application |
20080318065 |
Kind Code |
A1 |
Sherman; Audrey A. ; et
al. |
December 25, 2008 |
Mixtures of polydiorganosiloxane polyamide-containing components
and organic polymers
Abstract
This invention relates to a mixture of a polydiorganosiloxane
polyamide-containing material and an organic polymer.
Inventors: |
Sherman; Audrey A.; (St.
Paul, MN) ; Hays; David S.; (Woodbury, MN) ;
Johnson; Stephen A.; (Woodbury, MN) ; Hebrink;
Timothy J.; (Scandia, MN) ; Ernslander; Jeffrey
O.; (Afton, MN) ; Fleming; Danny L.;
(Stillwater, MN) |
Correspondence
Address: |
3M INNOVATIVE PROPERTIES COMPANY
PO BOX 33427
ST. PAUL
MN
55133-3427
US
|
Family ID: |
40136820 |
Appl. No.: |
11/821568 |
Filed: |
June 22, 2007 |
Current U.S.
Class: |
428/446 ;
528/32 |
Current CPC
Class: |
C08G 77/455 20130101;
C08L 23/06 20130101; C08L 2203/16 20130101; C09J 123/06 20130101;
C09D 123/06 20130101; B32B 2307/56 20130101; C08L 2205/03 20130101;
C08L 83/10 20130101; C08L 2207/066 20130101; C09J 7/38 20180101;
C08L 2201/08 20130101; B32B 27/283 20130101; C09D 123/08 20130101;
Y10T 428/2852 20150115; Y10T 428/31663 20150401; C09J 123/08
20130101; C08L 2205/06 20130101; C08L 23/08 20130101; C09J 2483/00
20130101; B32B 7/12 20130101; C09J 7/22 20180101; C09J 183/10
20130101; Y10T 428/24983 20150115 |
Class at
Publication: |
428/446 ;
528/32 |
International
Class: |
C08G 77/20 20060101
C08G077/20; B32B 27/28 20060101 B32B027/28 |
Claims
1. A mixture comprising: at least one copolymer comprising at least
two repeat units of Formula I-a: ##STR00014## wherein: each R.sup.1
is independently an aucyl, haloalkyl, aralkyl, alkenyl, aryl, or
aryl substituted with an alkyl, alkoxy, or halo; each Y is
independently an alkylene, aralkylene, or a combination thereof; G
is a divalent residue equal to a diamine of fonnula
R.sup.3HN--G--NHR.sup.3 minus the two--NHR.sup.3 groups; R.sup.3 is
hydrogen or alkyl or R.sup.3 taken together with G and to the
nitrogen to which they are both attached form a heterocyclic group;
each group B is independently a covalent bond, an alkylene of 4-20
carbons, an aralkylene, an arylene, or a combination thereof; n is
independently an integer of 0 to 1500; p is an integer of 1 to 10;
and at least one organic polymer selected from the group of a hot
melt processable thermoplastic, a hot melt processable elastomeric
thermoset, a silicone polymer, and mixtures thereof; wherein the at
least one organic polymer is not a copolymer comprising at least
two repeat units of Formula I-a, is not a rackifying resin, and is
not nylon in the form of fibers; and wherein the mixture does not
occur at the interface between two layers.
2. The mixture of claim 1, wherein the copolymer comprises at least
two repeat units of Formula I-b: ##STR00015## and wherein the at
least one organic polymer is not a copolymer comprising at least
two repeat units of Formula I-b.
3. The mixture of claim 2, wherein each R.sup.1 of the copolyiner
is methyl.
4. The mixture of claim 2, wherein at least 50 percent of the
R.sup.1 groups of the copolymer are phenyl, methyl, or combinations
thereof.
5. The mixture of claim 2, wherein each Y of the copolymer is an
alkylene having 1 to 10 carbon atoms, phenylene bonded to an
ailkylene having 1 to 10 carbon atoms, or phenylene bonded to a
first alkylene having 1 to 10 carbon atoms and to a second alkylene
having 1 to 10 carbon atoms.
6. The mixture of claim 5, wherein Y is an alkylene having 1 to 4
carbon atoms.
7. The mixture of claim 2, wherein the copolymer has a first repeat
unit where p is equal to 1 and a second repeat unit where p is at
least 2.
8. The mixture of claim 2, wherein G of the copolymer is an
alkylene, heteroalkylene, arylene, aralkylene,
polydiorganosiloxane, or a combination thereof.
9. The mixture of claim 2, wherein n of the copolymer is at least
40.
10. The mixture of claim 2, wherein R.sup.3 of the copolymer is
hydrogen.
11. A composition comprising a mixture of claim 1 and at least one
tackifying material.
12. The composition of claim 11 wherein the tackifying material is
a silicate resin or an organic tackifier.
13. A composition comprising a mixture of claim 1 and one or more
additives tat are not hot melt processable.
14. A vibration damping constrained layer construction comprising
at least one substrate having a stiffness and at least one layer
comprising a tackified composition of claim 11, wherein the
tackified composition is fixed to the substrate.
15. A vibration damping composite comprising a flexible substrate
and coated thereon a mixture of claim 1.
16. A bi-directional vibration damping constrained layer
construction comprising at least two rigid members, each rigid
member having a broad surface proximate to a broad surface of
another rigid member and closely spaced therefrom and a tackified
composition of claim 11, wherein the tackified composition is
contained between the closely spaced rigid members and adhered to
the members.
17. A pressure sensitive adhesive article comprising a flexible
substrate and coated thereon a tackified composition of claim
11.
18. A pressure sensitive adhesive article comprising a layer
comprising a mixture of claim 1 having a surface that is non-tacky
and a surface that is tacky.
19. A release coated article comprising a flexible substrate and
coated thereon a mixture of claim 1.
20. An article comprising a mixture of claim 1.
21. The article of claim 20, further comprising a substrate,
wherein the mixture comprising the copolymer is in a layer adjacent
to the substrate.
22. The article of claim 21, further comprising a first substrate
and a second substrate, wherein the mixture comprising the
copolymer is in a layer positioned between the first substrate and
the second substrate.
23. A multilayer film comprising one or more layers comprising a
mixture of claim 1.
24. A process for producing the mixture of claim 1, wherein the
process comprises: continuously providing at least one
polydiorganosiloxane polyamide-containing component and at least
one organic polymer to a vessel; mixing the components to fonn a
mixture; and conveying the mixture from the vessel.
25. The process of claim 24 wherein the mixing is under
substantially solventless conditions.
26. A process for producing the mixture of claim 1, wherein the
process comprises: continuously providing reactant components for
making at least one polydiorganosiloxane polyamide and at least one
organic polymer that is not reactive with the reactant components;
mixing the components; allowing the reactant components to react to
form a polydiorganosiloxane amide segmented copolymer, and
conveying the mixture from the reactor.
27. The mixture according to claim 1 wherein the mixture comprises
0.05 to 80 weight % of the copolymer of Fonnula I-a.
28. The mixture according to claim 1 wherein the mixture comprises
0.05 to 2.5 weight % of the copolymer of Formula I-a.
29. The mixture according to claim 1 wherein the mixture is a
polymer processing aid.
30. A method for modifying the processability of a polymeric
material, the method comprising combining components comprising: an
organic polymer; and a copolymer comprising at least two repeat
units of Formula I-a: ##STR00016## wherein: each R.sup.1 is
independently an alkyl, haloalkyl, aralkyl, alkenyl, aryl, or aryl
substituted with an alkyl, alkoxy, or halo; each Y is independently
an alkylene, aralkylene, or a combination thereof; G is a divalent
residue equal to a diamine of formula R.sup.3HN--G--NHR.sup.3 minus
the two--NHR.sup.3 groups; R.sup.3 is hydrogen or alkyl or R.sup.3
taken together with G and to the nitrogen to which they are both
attached form a heterocyclic group; each group B is independently a
covalent bond, an alkylene of 4-20 carbons, an aralkylene, an
arylene, or a combination thereof; n is independently an integer of
0 to 1500; and p is an integer of 1 to 10.
31. The method of claim 30 wherein the copolymer comprises at least
two repeat units of Formula I-b: ##STR00017##
32. The method of claim 30 wherein the organic polymer is a
thermoplastic polymer.
33. The method of claim 32 wherein the thermoplastic polymer is hot
melt processable.
34. The method of claim 30 wherein combining components forms a
mixture.
35. The method of claim 34 further comprising extruding the
mixture.
36. The method of claim 35 wherein the mixture comprises 0.05 to
2.5 weight % of the copolymer of Formula I-a.
37. The method of claim 36 wherein the mixture comprises 0.05 to 1
weight % of the copolymer of Formula I-a.
38. The method of claim 37 wherein the mixture comprises 0.05 to
0.1 weight % of the copolymer of Formula I-a.
39. The method of claim 36, wherein the conditions for extruding
the mixture comprise conditions selected from the group consisting
of lower pressure, lower power, lower torque, lower temperature,
and combinations thereof, compared to conditions for extruding the
organic polymer without the copolymer of Formula I-a.
Description
TECHNICAL FIELD
[0001] This invention relates to a mixture of a
polydiorganosiloxane polyamide-containing material and an organic
polymer, in particular to mixtures that are useful as plastics,
release surfaces, pressure sensitive adhesives, hot melt adhesives,
vibration damping compositions, and the like.
BACKGROUND
[0002] Siloxane polymers have unique properties derived mainly from
the physical and chemical characteristics of the siloxane bond.
These properties include low glass transition temperature, thermal
and oxidative stability, resistance to ultraviolet radiation, low
surface energy and hydrophobicity, high permeability to many gases,
and biocompatibility. The siloxane polymers, however, often lack
tensile strength.
[0003] The low tensile strength of the siloxane polymers can be
improved by forming block copolymers. Some block copolymers contain
a "soft" siloxane polymeric block or segment and any of a variety
of "hard" blocks or segments. Polydiorganosiloxane polyamides and
polydiorganosiloxane polyamides are exemplary block copolymers.
[0004] Mixtures of polymeric components have also been used in
various applications. Enhanced peel adhesion performance has been
seen when acrylic pressure sensitive adhesives have been melt mixed
with thermoplastic elastomers and subsequently extrusion coated
onto various substrates. Polydiorganosiloxane polyamide has been
mixed in solvent with dielectric polymers to form dielectric layers
for the imaging sheets of an electrostatic printing process that
releases more easily from later applied toners. However, good
images result only when the polydiorganosiloxane polyamide contains
a non-polydiorganosiloxane hard segment of at least 50 weight
percent. A need still exists for other polymeric mixtures having a
variety of properties and applications.
SUMMARY
[0005] The present invention provides a mixture that includes:
[0006] at least one copolymer comprising at least two repeat units
of Formula I-a:
##STR00001##
wherein:
[0007] each R.sup.1 is independently an alkyl, haloalkyl, aralkyl,
alkenyl, aryl, or aryl substituted with an alkyl, alkoxy, or
halo;
[0008] each Y is independently an alkylene, aralkylene, or a
combination thereof;
[0009] G is a divalent residue equal to a diamine of formula
R.sup.3HN-G-NHR.sup.3 minus the two -NH R.sup.3 groups;
[0010] R.sup.3 is hydrogen or alkyl or R.sup.3 taken together with
G and to the nitrogen to which they are both attached form a
heterocyclic group;
[0011] each group B is independently a covalent bond, an alkylene
of 4-20 carbons, an aralkylene, an arylene, or a combination
thereof;
[0012] n is independently an integer of 0 to 1500; and
[0013] p is an integer of 1 to 10; and
[0014] at least one organic polymer selected from the group of a
hot melt processable thermoplastic, a hot melt processable
elastomeric thermoset, a silicone polymer, and mixtures
thereof;
[0015] wherein the at least one organic polymer is not a copolymer
comprising at least two repeat units of Formula I-a, is not a
tackifying resin, and is not nylon in the form of fibers; and
[0016] wherein the mixture does not occur at the interface between
two layers.
[0017] In certain embodiments, the copolymer includes at least two
repeat units of Formula I-b:
##STR00002##
and wherein the at least one organic polymer is not a copolymer
comprising at least two repeat units of Formula I-b.
[0018] In certain embodiments, each R.sup.1 of the copolymer is
methyl. In certain embodiments, at least 50 percent of the R.sup.1
groups of the copolymer are phenyl, methyl, or combinations
thereof.
[0019] In certain embodiments, each Y of the copolymer is an
alkylene having 1 to 10 carbon atoms, phenylene bonded to an
alkylene having 1 to 10 carbon atoms, or phenylene bonded to a
first alkylene having 1 to 10 carbon atoms and to a second alkylene
having 1 to 10 carbon atoms. In certain embodiments, Y is an
alkylene having 1 to 4 carbon atoms.
[0020] In certain embodiments, the copolymer has a first repeat
unit where p is equal to 1 and a second repeat unit where p is at
least 2.
[0021] In certain embodiments, G of the copolymer is an alkylene,
heteroalkylene, arylene, aralkylene, polydiorganosiloxane, or a
combination thereof.
[0022] In certain embodiments, n of the copolymer is at least
40.
[0023] In certain embodiments, R.sup.3 of the copolymer is
hydrogen.
[0024] In certain embodiments, mixtures of the present invention
can be further combined with at least one tackifying material. In
certain embodiments, the tackifying material is a silicate resin or
an organic tackifier.
[0025] In certain embodiments, mixtures of the present invention
can be further combined with additives that are not hot melt
processable.
[0026] In certain embodiments, the present invention provides a
vibration damping constrained layer construction that includes at
least one substrate having a stiffness and at least one layer
including a tackified composition described herein, wherein the
tackified composition is fixed to the substrate. In certain
embodiments, the present invention provides a vibration damping
composite including a flexible substrate coated thereon a mixture
of the present invention.
[0027] In certain embodiments, the present invention provides a
bidirectional vibration damping constrained layer construction that
includes at least two rigid members, each rigid member having a
broad surface proximate to a broad surface of another rigid member
and closely spaced therefrom and a tackified composition described
herein, wherein the tackified composition is contained between the
closely spaced rigid members and adhered to the members.
[0028] In certain embodiments, the present invention provides a
pressure sensitive adhesive article including a flexible substrate
and coated thereon a tackified composition described herein.
[0029] In certain embodiments, the present invention provides a
pressure sensitive adhesive article that includes a layer made of a
mixture described herein having a surface that is non-tacky and a
surface that is tacky.
[0030] In certain embodiments, the present invention provides a
release coated article that includes a flexible substrate and
coated thereon a mixture described herein.
[0031] In certain embodiments, the present invention provides an
article that includes a mixture described herein. In certain
embodiments, the article further includes a substrate, wherein the
mixture that includes the copolymer is in a layer adjacent to the
substrate. In certain embodiments, the article further includes a
first substrate and a second substrate, wherein the mixture that
includes the copolymer is in a layer positioned between the first
substrate and the second substrate.
[0032] In certain embodiments, the present invention provides a
multilayer film including one or more layers including a mixture
described herein.
[0033] In certain embodiments, the present invention provides a
process for producing a mixture, wherein the process includes:
continuously providing at least one polydiorganosiloxane
polyamide-containing component and at least one organic polymer to
a vessel; mixing the components to form a mixture; and conveying
the mixture from the vessel.
[0034] In certain embodiments, the mixing is under substantially
solventless conditions.
[0035] In certain embodiments, the present invention provides a
process for producing a mixture, wherein the process includes:
continuously providing reactant components for making at least one
polydiroganosiloxane polyamide and at least one organic polymer
that is not reactive with the reactant components; mixing the
components; allowing the reactant components to react to form a
polydiorganosiloxane amide segmented copolymer, and conveying the
mixture from the reactor.
[0036] These thermoplastic mixtures can be conceived for use in
numerous applications: in sealants, adhesives, as material for
fibers, as plastic additives, e.g., as impact modifiers or flame
retardants, as material for defoamer formulations, as a
high-performance polymer (thermoplastic, thermoplastic elastomer,
elastomer), as packaging material for electronic components, in
insulating materials or shielding materials, in cable sheathing, in
antifouling materials, as an additive for scouring, cleaning or
polishing products, as an additive for bodycare compositions, as a
coating material for wood, paper, and board, as a mold release
agent, as a biocompatible material in medical applications such as
contact lenses, as a coating material for textile fibers or textile
fabric, as a coating material for natural substances such as
leather and furs, for example, as a material for membranes and as a
material for photoactive systems, for example, for lithographic
techniques, optical data securement or optical data
transmission.
Definitions
[0037] The terms "comprises" and variations thereof do not have a
limiting meaning where these terms appear in the description and
claims.
[0038] The words "preferred" and "preferably" refer to embodiments
of the invention that may afford certain benefits, under certain
circumstances. However, other embodiments may also be preferred,
under the same or other circumstances.
[0039] Furthermore, the recitation of one or more preferred
embodiments does not imply that other embodiments are not useful,
and is not intended to exclude other embodiments from the scope of
the invention.
[0040] The terms "a", "an", and "the" are used interchangeably with
"at least one" to mean one or more of the elements being
described.
[0041] As used herein, the term "or" is generally employed in its
sense including "and/or" unless the content clearly dictates
otherwise.
[0042] The term "and/or" means one or all of the listed elements or
a combination of any two or more of the listed elements.
[0043] The term "alkenyl" refers to a monovalent group that is a
radical of an alkene, which is a hydrocarbon with at least one
carbon-carbon double bond. The alkenyl can be linear, branched,
cyclic, or combinations thereof and typically contains 2 to 20
carbon atoms. In some embodiments, the alkenyl contains 2 to 18, 2
to 12, 2 to 10, 4 to 10, 4 to 8, 2 to 8, 2 to 6, or 2 to 4 carbon
atoms. Exemplary alkenyl groups include ethenyl, n-propenyl, and
n-butenyl.
[0044] The tern "alkyl" refers to a monovalent group that is a
radical of an alkane, which is a saturated hydrocarbon. The alkyl
can be linear, branched, cyclic, or combinations thereof and
typically has 1 to 20 carbon atoms. In some embodiments, the alkyl
group contains 1 to 18, 1 to 12, 1 to 10, 1 to 8, 1 to 6, or 1 to 4
carbon atoms. Examples of alkyl groups include, but are not limited
to, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl,
tert-butyl, n-pentyl, n-hexyl, cyclohexyl, n-heptyl, n-octyl, and
ethylhexyl.
[0045] The term "alkylene" refers to a divalent group that is a
radical of an alkane. The alkylene can be straight-chained,
branched, cyclic, or combinations thereof. The alkylene often has 1
to 20 carbon atoms. In some embodiments, the alkylene contains 1 to
18, 1 to 12, 1 to 10, 1 to 8, 1 to 6, or 1 to 4 carbon atoms. The
radical centers of the alkylene can be on the same carbon atom
(i.e., an alkylidene) or on different carbon atoms.
[0046] The term "alkoxy" refers to a monovalent group of formula
--OR where R is an alkyl group.
[0047] The term "alkoxycarbonyl" refers to a monovalent group of
formula --(CO)OR where R is an alkyl group and (CO) denotes a
carbonyl group with the carbon attached to the oxygen with a double
bond.
[0048] The term "aralkyl" refers to a monovalent group of formula
--R.sup.a--Ar where R.sup.a is an alkylene and Ar is an aryl group.
That is, the aralkyl is an alkyl substituted with an aryl.
[0049] The term "aralkylene" refers to a divalent group of formula
--R.sup.a--Ar.sup.a-- where R.sup.a is an alkylene and Ar.sup.a is
an arylene (i.e., an alkylene is bonded to an arylene).
[0050] The term "aryl" refers to a monovalent group that is
aromatic and carbocyclic. The aryl can have one to five rings that
are connected to or fused to the aromatic ring. The other ring
structures can be aromatic, non-aromatic, or combinations thereof.
Examples of aryl groups include, but are not limited to, phenyl,
biphenyl, terphenyl, anthryl, naphthyl, acenaphthyl,
anthraquinonyl, phenanthryl, anthracenyl, pyrenyl, perylenyl, and
fluorenyl.
[0051] The tern "arylene" refers to a divalent group that is
carbocyclic and aromatic. The group has one to five rings that are
connected, fused, or combinations thereof. The other rings can be
aromatic, non-aromatic, or combinations thereof. In some
embodiments, the arylene group has up to 5 rings, up to 4 rings, up
to 3 rings, up to 2 rings, or one aromatic ring. For example, the
arylene group can be phenylene.
[0052] The term "aryloxy" refers to a monovalent group of formula
--OAr where Ar is an aryl group.
[0053] The tern "carbonyl" refers to a divalent group of formula
--(CO)-- where the carbon atom is attached to the oxygen atom with
a double bond.
[0054] The term "halo" refers to fluoro, chloro, bromo, or
iodo.
[0055] The term "haloalkyl" refers to an alkyl having at least one
hydrogen atom replaced with a halo. Some haloalkyl groups are
fluoroalkyl groups, chloroalkyl groups, or bromoalkyl groups.
[0056] The term "heteroalkylene" refers to a divalent group that
includes at least two alkylene groups connected by a thio, oxy, or
--NR-- where R is alkyl. The heteroalkylene can be linear,
branched, cyclic, or combinations thereof and can include up to 60
carbon atoms and up to 15 heteroatoms. In some embodiments, the
heteroalkylene includes up to 50 carbon atoms, up to 40 carbon
atoms, up to 30 carbon atoms, up to 20 carbon atoms, or up to 10
carbon atoms. Some heteroalkylenes are polyalkylene oxides where
the heteroatom is oxygen.
[0057] The term "oxalyl" refers to a divalent group of formula
--(CO)--(CO)-- where each (CO) denotes a carbonyl group.
[0058] The terms "oxalylamino" and "aminoxalyl" are used
interchangeably to refer to a divalent group of formula
--(CO)--(CO)--NH-- where each (CO) denotes a carbonyl.
[0059] The tern "aminoxalylamino" refers to a divalent group of
formula --NH--(CO)--(CO)--NR.sup.d-- where each (CO) denotes a
carbonyl group and R.sup.d is hydrogen, alkyl, or part of a
heterocyclic group along with the nitrogen to which they are both
attached. In most embodiments, R.sup.d is hydrogen or alkyl. In
many embodiments, R.sup.d is hydrogen.
[0060] The terms "polymer" and "polymeric material" refer to both
materials prepared from one monomer such as a homopolyiner or to
materials prepared from two or more monomers such as a copolymer,
terpolymer, or the like. Likewise, the term "polymerize" refers to
the process of making a polymeric material that can be a
homopolymer, copolymer, terpolymer, or the like. The terms
"copolymer" and "copolymeric material" refer to a polymeric
material prepared from at least two monomers.
[0061] The term "polydiorganosiloxane" refers to a divalent segment
of formula
##STR00003##
where each R.sup.1 is independently an alkyl, haloalkyl, aralkyl,
alkenyl, aryl, or aryl substituted with an alkyl, alkoxy, or halo;
each Y is independently an alkylene, aralkylene, or a combination
thereof; and subscript n is independently an integer of 0 to
1500.
[0062] The terms "room temperature" and "ambient temperature" are
used interchangeably to mean temperatures in the range of
20.degree. C. to 25.degree. C.
[0063] Unless otherwise indicated, all numbers expressing feature
sizes, amounts, and physical properties used in the specification
and claims are to be understood as being modified in all instances
by the term "about." Accordingly, unless indicated to the contrary,
the numbers set forth are approximations that can vary depending
upon the desired properties using the teachings disclosed
herein.
[0064] The above summary of the present invention is not intended
to describe each disclosed embodiment or every implementation of
the present invention. The description that follows more
particularly exemplifies illustrative embodiments. In several
places throughout the application, guidance is provided through
lists of examples, which can be used in various combinations. In
each instance, the recited list serves only as a representative
group and should not be interpreted as an exclusive list.
DETAILED DESCRIPTION OF ILLUSTRATIVE EMBODIMENTS
[0065] Mixtures containing polydiorganosiloxane polyamide block
copolymers and organic polymers, methods of making the mixtures,
compositions including the mixtures, and uses thereof are provided.
The polydiorganosiloxane polyamide block copolymers are mixed with
a variety of organic polymers including hot melt processable
thermoplastic polymers (which may be elastomeric or
nonelastomeric), hot melt processable elastomeric thermoset
polymers, silicone polymers, or mixtures thereof.
[0066] The polydiorganosiloxane polyamide copolymers, which are of
the (AB).sub.n type, are the condensation reaction product of (a) a
diamine having primary or secondary amino groups with (b) a
precursor having at least one polydiorganosiloxane segment and at
least two dicarboxamido ester groups (preferably oxalylamido ester
groups). The copolymers have many of the desirable features of
polysiloxanes such as low glass transition temperatures, thermal
and oxidative stability, resistance to ultraviolet radiation, low
surface energy and hydrophobicity, and high permeability to many
gases. Additionally, the copolymers can have improved mechanical
strength and elastomeric properties compared to polysiloxanes. At
least some of the copolymers are optically clear, have a low
refractive index, or both. Accordingly, at least some of the
polymeric mixtures have similar properties.
[0067] The polymeric mixtures can be hot melt processable mixtures
in that both the polydiorganosiloxane polyamide block copolymers
and the organic polymers can be hot melt processed, i.e., can be
processed by heating to a flowable melt state. Although hot melt
processing is preferred for certain embodiments, it is not
required, as these components (even though they are hot melt
processable) can be mixed using solvents.
[0068] The relative amounts of these components in a given
polymeric mixture or composition containing the mixture depend upon
the particular rheological and mechanical properties sought, as
well as the individual components themselves (e.g. the molecular
weight of the organic polymer, the degree of polymerization of the
polydiorganosiloxane polyamide copolymer). In general, however
preferred compositions contain at least 0.1 percent by weight
(wt-%) of the organic polymer, and no more than 99.9 wt-% of said
polymer.
Organic Polymer Component
[0069] The organic polymer component is a hot melt processable
thermoplastic polymer (which may be elastomeric or nonelastomeric),
a hot melt processable elastomeric thermoset polymer, a silicone
polymer, or mixtures thereof, excluding polydiorganosiloxane
compounds as described herein (e.g., those of Formulas I-a and
I-b). By "hot melt processable" it is meant that the polymer will
melt and flow at a temperature at which the polydiorganosiloxane
compounds of Formulas I-a and I-b will melt and flow. The silicone
polymers are not "hot melt processable" per se since they are
typically fluidic polymers with very low Tg values at room
temperature, and flow at room temperature and above without the
need for elevated temperatures.
[0070] The organic polymer may be solvent or melt mixed with the
polydiorganosiloxane polyamide segmented copolymer. The organic
polymer may be a polydiorganosiloxane polyamide-containing
component or a polymer that does not contain polydiorganosiloxane
segments; however it is not a polydiorganosiloxane polyamide
compound of Formulas I-a or I-b.
[0071] At use temperature the mixtures generally have at least two
domains, one discontinuous and the other continuous, because of the
general immiscibility of the polydiorganosiloxane
polyamide-containing component with the organic polymer. Of course,
the mixture may contain more than one polydiorganosiloxane
polyamide compound and more than one organic polymer.
[0072] Thermoplastic materials are generally materials that flow
when heated sufficiently above their glass transition point and
become solid when cooled. They may also have elastomeric
properties.
[0073] Such mixtures do not include tackifying resins as the
organic polymer, and do not include nylon in the form of fibers as
the organic polymer, although nylon in other forms may be used.
Furthermore, such mixtures are not at the interface between two
layers.
[0074] Thermoplastic materials useful in the present invention that
are generally considered nonelastomeric include, for example,
polyolefins such as isotactic polypropylene, low density
polyethylene, linear low density polyethylene, very low density
polyethylene, medium density polyethylene, high density
polyethylene, polybutylene, nonelastomeric polyolefin copolymers or
terpolymers, such as ethylene/propylene copolymer and blends
thereof; ethylene-vinyl acetate copolymers such as that available
under the trade designation ELVAX 260, available from DuPont
Chemical Co.; ethylene acrylic acid copolymers; ethylene
methacrylic acid copolymers such as that available under the trade
designation SURLYN 1702, available from DuPont Chemical Co.;
polymethylmethacrylate; polystyrene; ethylene vinyl alcohol;
polyester; amorphous polyester; polyamides; fluorinated
thermoplastics, such a polyvinylidene fluoride,
polytetrafluoroethylene, fluorinated ethylene/propylene copolymers
and fluorinated ethylene/propylene copolymers; halogenated
thermoplastics, such as a chlorinated polyethylene. Any single
thermoplastic material can be mixed with at least one
polydiorganosiloxane polyamide-containing component. Alternatively,
a mixture of thermoplastic materials may be used.
[0075] Thermoplastic materials that have elastomeric properties are
typically called thermoplastic elastomeric materials. Thermoplastic
elastomeric materials are generally defined as materials that act
as though they were covalently cross-linked, exhibiting high
resilience and low creep, yet flow when heated above their
softening point. Thermoplastic elastomeric materials useful in the
present invention include, for example, linear, radial, star and
tapered styrene-isoprene block copolymers such as that available
under the trade designation KRATON D1107P from Shell Chemical Co.
of Houston, Tex. and that available under the trade designation
EUROPRENE SOL TE 9110 from EniChem Elastomers Americas, Inc. of
Houston, Tex.; linear styrene-(ethylene-butylene) block copolymers
such as that available under the trade designation KRATON G 1657
from Shell Chemical Co.; linear styrene-(ethylene-propylene) block
copolymers such as that available under the trade designation
KRATON G1657X from Shell Chemical Co.; linear, radial, and star
styrene-butadiene block copolymers such as that available under the
trade designation KRATON D1118X from Shell Chemical Co. and that
available under the trade designation EUROPRENE SOL TE 6205 from
EniChem Elastomers Americas, Inc.; polyetheresters such as that
available under the trade designation HYTREL G3548 from DuPont,
elastomeric ethylene-propylene copolymers; thermoplastic
elastomeric polyurethanes such as that available under the trade
designation MORTHANE URETHENE PE44-203 from Morton International,
Inc., Chicago, Ill.; self-tacky or tackified polyacrylates
including C.sub.3 to C.sub.12 alkylesters that may contain other
comonomers, such as for example, isooctyl acrylate and from 0 to 20
weight percent acrylic acid; polyvinylethers;
poly-.alpha.-olefin-based thermoplastic elastomeric materials such
as those represented by the formula --(CH.sub.2CHR).sub.x where R
is an alkyl group containing 2 to 10 carbon atoms and
poly-.alpha.-olefins based on metallocene catalysis such as that
available under the trade designation ENGAGE EG8200, an
ethylene/poly-.alpha.-olefin copolymer, available from Dow Plastics
Co. of Midland, Mich.; as well as polydiorganosiloxane
polyurea-urethanes, available from Wacker Chemie AG, Germany under
the trade designation GENIOMER.
[0076] Thermoset elastomers (i.e., elastomeric thermosets) are
materials that change irreversibly under the influence of heat from
a fusible and soluble material into one that is infusible and
insoluble through the formation of a covalently cross-linked,
thermally stable network. Thermoset elastomers useful in the
present invention include, for example, natural rubbers such as
CV-60, a controlled viscosity grade available from Goodyear
Chemical, Akron, Ohio, and SMR-5, a ribbed smoked sheet rubber;
butyl rubbers, such as Exxon Butyl 268 available from Exxon
Chemical Co.; synthetic polyisoprenes such as that available under
the trade designation CARIFLEX IR309 from Royal Dutch Shell of
Netherlands and that available under the trade designation NATSYN
2210 from Goodyear Tire and Rubber Co.; styrene-butadiene random
copolymer rubbers such as that available under the trade
designation AMERIPOL 1011A from BF Goodrich of Akron, Ohio;
polybutadienes; polyisobutylenes such as that available under the
trade designation VISTANEX MM L-80 from Exxon Chemical Co.;
polyurethanes such as, for example, polyoctadecyl carbamate
disclosed in U.S. Pat. No. 2,532,011; amorphous
poly-.alpha.-olefins such as C.sub.4-C.sub.10 linear or branched
poly-.alpha.-olefins; polydiorganosiloxane polyurea-containing
components, such as those disclosed in U.S. Pat. No. 5,214,119.
[0077] Suitable silicone polymers are typically fluids and may be
curable (through incorporation of suitable functional groups such
as hydroxyl groups or ethylenically unsaturated groups, e.g.,
acrylate groups) or substantially noncurable. Examples of suitable
silicone fluids are described in, for example, International
Publication No. WO 97/40103, U.S. Pat. No. 6,441,118, U.S. Pat. No.
5,091,483, and U.S. Pat. Pub. No. 2005/0136266. Particularly
preferred silicone polymers are moisture-curable silicone fluids,
e.g., hydroxyl-terminated polydiorganosiloxanes or nonreactive
silicone fluids such as that available under the trade designation
47V1000 RHODORSIL from Rhodia Silicones. Any of the
hydroxyl-terminated polydiorganosiloxanes typically used in known
silicone sealing and adhesive compositions may be used in the
compositions of the present invention. Examples of suitable
commercially available silicone fluids include those available
under the trade designation MASIL from Lubruzol Corp. (Ohio) and
Wacker Chemie AG (Germany).
Polydiorginosiloxane Polyamide-Containing Component
[0078] A linear, polydiorganosiloxane polyamide block copolymer
useful in mixtures of the present invention contains at least two
repeat units of Formula I-a:
##STR00004##
In this formula (I-a), each R.sup.1 is independently an alkyl,
haloalkyl, aralkyl, alkenyl, aryl, or aryl substituted with an
alkyl, alkoxy, or halo. Each Y is independently an alkylene,
aralkylene, or a combination thereof. Subscript n is independently
an integer of 0 to 1500 and subscript p is an integer of 1 to 10.
Group G is a divalent group that is the residue unit that is equal
to a diamine of formula R.sup.3HN-G-NHR.sup.3 minus the two
--NHR.sup.3 groups (i.e., amino groups) where R.sup.3 is hydrogen,
alkyl, or forms a heterocyclic group when taken together with G and
with the nitrogen to which it is attached. Each group B is
independently a covalent bond, an alkylene of 4-20 carbons, an
aralkylene, an arylene, or a combination thereof. When each group B
is a covalent bond, the polydiorganosiloxane polyamide block
copolymer of Formula I-a is referred to as a polydiorganosiloxane
polyoxamide block copolymer, and preferably as the Formula I-b
shown below. Each asterisk (*) indicates the position of attachment
of the repeating unit to another group such as another repeat unit
of Formula I-a.
[0079] A preferred linear, polydiorganosiloxane polyamide block
copolymer useful in mixtures of the present invention contains at
least two repeat units of Formula I-b:
##STR00005##
In this Formula I-b, each R.sup.1 is independently an alkyl,
haloalkyl, aralkyl, alkenyl, aryl, or aryl substituted with an
alkyl, alkoxy, or halo. Each Y is independently an alkylene,
aralkylene, or a combination thereof. Subscript n is independently
an integer of 0 to 1 500 and the subscript p is an integer of 1 to
10. Group G is a divalent group that is the residue unit that is
equal to a diamine of formula R.sup.3HN-G-NHR.sup.3 minus the two
--NHR.sup.3 groups. Group R.sup.3 is hydrogen or alkyl (e.g., an
alkyl having 1 to 10, 1 to 6, or 1 to 4 carbon atoms) or R.sup.3
taken together with G and with the nitrogen to which they are both
attached forms a heterocyclic group (e.g., R.sup.3HN-G-NHR.sup.3 is
piperazine or the like). Each asterisk (*) indicates a site of
attachment of the repeat unit to another group in the copolymer
such as, for example, another repeat unit of Formula I-b.
[0080] Suitable alkyl groups for R.sup.1 in Formula I (I-a or I-b)
typically have 1 to 10, 1 to 6, or 1 to 4 carbon atoms. Exemplary
alkyl groups include, but are not limited to, methyl, ethyl,
isopropyl, n-propyl, n-butyl, and iso-butyl. Suitable haloalkyl
groups for R.sup.1 often have only a portion of the hydrogen atoms
of the corresponding alkyl group replaced with a halogen. Exemplary
haloalkyl groups include chloroalkyl and fluoroalkyl groups with 1
to 3 halo atoms and 3 to 10 carbon atoms. Suitable alkenyl groups
for R.sup.1 often have 2 to 10 carbon atoms. Exemplary alkenyl
groups often have 2 to 8, 2 to 6, or 2 to 4 carbon atoms such as
ethenyl, n-propenyl, and n-butenyl. Suitable aryl groups for
R.sup.1 often have 6 to 12 carbon atoms. Phenyl is an exemplary
aryl group. The aryl group can be unsubstituted or substituted with
an alkyl (e.g., an alkyl having 1 to 10 carbon atoms, 1 to 6 carbon
atoms, or 1 to 4 carbon atoms), an alkoxy (e.g., an alkoxy having 1
to 10 carbon atoms, 1 to 6 carbon atoms, or 1 to 4 carbon atoms),
or halo (e.g., chloro, broino, or fluoro). Suitable aralkyl groups
for R.sup.1 usually have an alkylene group with 1 to 10 carbon
atoms and an aryl group with 6 to 12 carbon atoms. In some
exemplary aralkyl groups, the aryl group is phenyl and the alkylene
group has 1 to 10 carbon atoms, 1 to 6 carbon atoms, or 1 to 4
carbon atoms (i.e., the structure of the aralkyl is alkylene-phenyl
where an alkylene is bonded to a phenyl group).
[0081] In some embodiments, in some repeat units of Formula I (I-a
or I-b), at least 40 percent, and preferably at least 50.percent,
of the R.sup.1 groups are phenyl, methyl, or combinations thereof.
For example, at least 60 percent, at least 70 percent, at least 80
percent, at least 90 percent, at least 95 percent, at least 98
percent, or at least 99 percent of the R.sup.1 groups can be
phenyl, methyl, or combinations thereof. In some embodiments, in
some repeat units of Formula I (I-a or I-b), at least 40 percent,
and preferably at least 50 percent, of the R.sup.1 groups are
methyl. For example, at least 60 percent, at least 70 percent, at
least 80 percent, at least 90 percent, at least 95 percent, at
least 98 percent, or at least 99 percent of the R.sup.1 groups can
be methyl. The remaining R.sup.1 groups can be selected from an
alkyl having at least two carbon atoms, haloalkyl, aralkyl,
alkenyl, aryl, or aryl substituted with an alkyl, alkoxy, or
halo.
[0082] Each Y in Formula I (I-a or I-b) is independently an
alkylene, aralkylene, or a combination thereof. Suitable alkylene
groups typically have up to 10 carbon atoms, up to 8 carbon atoms,
up to 6 carbon atoms, or up to 4 carbon atoms. Exemplary alkylene
groups include methylene, ethylene, propylene, butylene, and the
like. Suitable aralkylene groups usually have an arylene group with
6 to 12 carbon atoms bonded to an alkylene group with 1 to 10
carbon atoms. In some exemplary aralkylene groups, the arylene
portion is phenylene. That is, the divalent aralkylene group is
phenylene-alkylene where the phenylene is bonded to an alkylene
having 1 to 10, 1 to 8, 1 to 6, or 1 to 4 carbon atoms. As used
herein with reference to group Y, "a combination thereof" refers to
a combination of two or more groups selected from an alkylene and
aralkylene group. A combination can be, for example, a single
aralkylene bonded to a single alkylene (e.g.,
alkylene-arylene-alkylene). In one exemplary
alkylene-arylene-alkylene combination, the arylene is phenylene and
each alkylene has 1 to 10, 1 to 6, or 1 to 4 carbon atoms.
[0083] Each subscript n in Formula I (I-a or I-b) is independently
an integer of 0 to 1500. For example, subscript n can be an integer
up to 1000, up to 500, up to 400, up to 300, up to 200, up to 100,
up to 80, up to 60, up to 40, up to 20, or up to 10. The value of n
is often at least I, at least 2, at least 3, at least 5, at least
10, at least 20, or at least 40. For example, subscript n can be in
the range of 40 to 1500, 0 to 1000, 40 to 1000, 0 to 500, 1 to 500,
40 to 500, 1 to 400, 1 to 300, 1 to 200, 1 to 100, 1 to 80, 1 to
40, or 1 to 20.
[0084] The subscript p is an integer of 1 to 10. For example, the
value of p is often an integer up to 9, up to 8, up to 7, up to 6,
up to 5, up to 4, up to 3, or up to 2. The value of p can be in the
range of 1 to 8,1 to 6, or 1 to 4.
[0085] Group G in Formula I (I-a or I-b) is a residual unit that is
equal to a diamine compound of formula R.sup.3HN-G-NHR.sup.3 minus
the two amino groups (i.e., --NHR.sup.3 groups). The diamine can
have primary or secondary amino groups. Group R.sup.3 is hydrogen
or alkyl (e.g., an alkyl having 1 to 10, 1 to 6, or 1 to 4 carbon
atoms) or R.sup.3 taken together with G and with the nitrogen to
which they are both attached forms a heterocyclic group (e.g.,
R.sup.3HN-G-NHR.sup.3 is piperazine). In most embodiments, R.sup.3
is hydrogen or an alkyl. In many embodiments, both of the amino
groups of the diamine are primary amino groups (i.e., both R.sup.3
groups are hydrogen) and the diamine is of formula
H.sub.2N-G-NH.sub.2.
[0086] In some embodiments, G is an alkylene, heteroalkylene,
polydiorganosiloxane, arylene, aralkylene, or a combination
thereof. Suitable alkylenes often have 2 to 10, 2 to 6, or 2 to 4
carbon atoms. Exemplary alkylene groups include ethylene,
propylene, butylene, and the like. Suitable heteroalkylenes are
often polyoxyalkylenes such as polyoxyethylene having at least 2
ethylene units, polyoxypropylene having at least 2 propylene units,
or copolymers thereof. Suitable polydiorganosiloxanes include the
polydiorganosiloxane diamines of Formula III, which are described
below, minus the two amino groups. Exemplary polydiorganosiloxanes
include, but are not limited to, polydimethylsiloxanes with
alkylene Y groups. Suitable aralkylene groups usually contain an
arylene group having 6 to 12 carbon atoms bonded to an alkylene
group having 1 to 10 carbon atoms. Some exemplary aralkylene groups
are phenylene-alkylene where the phenylene is bonded to an alkylene
having 1 to 10 carbon atoms, 1 to 8 carbon atoms, 1 to 6 carbon
atoms, or 1 to 4 carbon atoms. As used herein with reference to
group G, "a combination thereof" refers to a combination of two or
more groups selected from an alkylene, heteroalkylene,
polydiorganosiloxane, arylene, and aralkylene. A combination can
be, for example, an aralkylene bonded to an alkylene (e.g.,
alkylene-arylene-alkylene). In one exemplary
alkylene-arylene-alkylene combination, the arylene is phenylene and
each alkylene has 1 to 10, 1 to 6, or 1 to 4 carbon atoms.
[0087] In preferred embodiments, the polydiorganosiloxane polyamide
is a polydiorganosiloxane polyoxamide. The polydiorganosiloxane
polyamide tends to be free of groups having a formula
--R.sup.a--(CO)--NH-- where R.sup.a is an alkylene. All of the
carbonylamino groups along the backbone of the copolymeric material
are part of an oxalylamino group (i.e., the --(CO)--(CO)--NH--
group). That is, any carbonyl group along the backbone of the
copolyineric material is bonded to another carbonyl group and is
part of an oxalyl group. More specifically, the
polydiorganosiloxane polyamide has a plurality of aminoxalylamino
groups.
[0088] The polydiorganosiloxane polyamide is a linear, block
copolymer and can be an elastomeric material. Unlike many of the
known polydiorganosiloxane polyamides that are generally formulated
as brittle solids or hard plastics, the polydiorganosiloxane
polyamides can be formulated to include greater than 50 weight
percent polydiorganosiloxane segments based on the weight of the
copolymer. The weight percent of the diorganosiloxane in the
polydiorganosiloxane polyamides can be increased by using higher
molecular weight polydiorganosiloxanes segments to provide greater
than 60 weight percent, greater than 70 weight percent, greater
than 80 weight percent, greater than 90 weight percent, greater
than 95 weight percent, or greater than 98 weight percent of the
polydiorganosiloxane segments in the polydiorganosiloxane
polyamides. Higher amounts of the polydiorganosiloxane can be used
to prepare elastomeric materials with lower modulus while
maintaining reasonable strength.
[0089] Some of the polydiorganosiloxane polyamides can be heated to
a temperature up to 200.degree. C., up to 225.degree. C., up to
250.degree. C., up to 275.degree. C., or up to 300.degree. C.
without noticeable degradation of the material. For example, when
heated in a thermogravimetric analyzer in the presence of air, the
copolymers often have less than a 10 percent weight loss when
scanned at a rate 50.degree. C. per minute in the range of
20.degree. C. to 350.degree. C. Additionally, the copolymers can
often be heated at a temperature such as 250.degree. C. for 1 hour
in air without apparent degradation as determined by no detectable
loss of mechanical strength upon cooling.
[0090] Certain embodiments of the copolymeric material of Formula I
(I-a or I-b) can be optically clear. As used herein, the term
"optically clear" refers to a material that is clear to the human
eye. An optically clear copolymeric material often has a luminous
transmission of at least 90 percent, a haze of less than 2 percent,
and opacity of less than about 1 percent in the 400 to 700 min
wavelength range. Both the luminous transmission and the haze can
be determined using, for example, the method of ASTM-D 1003-95.
[0091] Additionally, certain embodiments of the copolyineric
material of Formula I (I-a or I-b) can have a low refractive index.
As used herein, the term "refractive index" refers to the absolute
refractive index of a material (e.g., copolymeric material) and is
the ratio of the speed of electromagnetic radiation in free space
to the speed of the electromagnetic radiation in the material of
interest. The electromagnetic radiation is white light. The index
of refraction is measured using an Abbe refractometer, available
commercially, for example, from Fisher Instruments of Pittsburgh,
Pa. The measurement of the refractive index can depend, to some
extent, on the particular refractometer used. The copolymeric
material usually has a refractive index in the range of 1.41 to
1.50.
[0092] The polydiorganosiloxane polyamides are soluble in many
common organic solvents such as, for example, toluene,
tetrahydrofuran, dichloromethane, aliphatic hydrocarbons (e.g.,
alkanes such as hexane), or mixtures thereof.
Optional Additives
[0093] Functional components, tackifiers, plasticizers, and other
property modifiers may be incorporated in the organic polymer, the
polydiorganosiloxane polyamide segmented organic polymer, or both
of the components of the mixtures of the present invention.
Preferred optional additives are not hot melt processable. That is,
they do not melt and flow at the temperatures at which the hot melt
processable organic polymer and the polydiorganosiloxane polyamide
segmented organic polymer melt and flow.
[0094] Functional components include, for example, antistatic
additives, ultraviolet light absorbers (UVAs), hindered amine light
stabilizers (HALS), dyes, colorants, pigments, antioxidants, slip
agents, low adhesion materials, conductive materials, abrasion
resistant materials, optical elements, dimensional stabilizers,
adhesives, tackifiers, flame retardants, phosphorescent materials,
fluorescent materials, nanoparticles, anti-graffiti agents,
dew-resistant agents, load bearing agents, silicate resins, fumed
silica, glass beads, glass bubbles, glass fibers, mineral fibers,
clay particles, organic fibers, e.g., nylon, KEVLAR, metal
particles, and the like. Such optional additives can be added in
amounts up to 100 parts per 100 parts of the sum of the organic
polymer and the polydiorganosiloxane polyamide segmented polymeric
component, provided that if and when incorporated, such additives
are not detrimental to the function and functionality of the final
polymer product. Other additives such as light diffusing materials,
light absorptive materials and optical brighteners, flame
retardants, stabilizers, antioxidants, compatibilizers,
antimicrobial agents such as zinc oxide, electrical conductors,
thermal conductors such as aluminum oxide, boron nitride, aluminum
nitride, and nickel particles, including organic and/or inorganic
particles, or any number or combination thereof, can be blended
into these systems. The functional components listed above may also
be incorporated into polydiorganosiloxane polyamide block copolymer
provided such incorporation does not adversely affect any of the
resulting product to an undesirable extent.
[0095] Tackifying materials or plasticizers useful with the
polymeric materials are preferably miscible at the molecular level,
e.g., soluble in, any or all of the polymeric segments of the
elastomeric material or the thermoplastic elastomeric material.
These tackifying materials or plasticizers are generally immiscible
with the polydiorganosiloxane polyamide-containing component. When
the tackifying material is present it generally comprises 5 to 300
parts by weight, more typically up to 200 parts by weight, based on
100 parts by weight of the polymeric material.
[0096] Examples of tackifiers suitable for the invention include
but are not limited to liquid rubbers, hydrocarbon resins, rosin,
natural resins such as dimerized or hydrogenated balsams and
esterified abietic acids, polyterpenes, terpene phenolics,
phenol-formaldehyde resins, and rosin esters. Examples of
plasticizers include but are not limited to polybutene, paraffinic
oils, petrolatum, and certain phthalates with long aliphatic side
chains such as ditridecyl phthalate.
[0097] Other suitable tackifiers include silicate tackifying
resins. Suitable silicate tackifying resins include those resins
composed of the following structural units M (i.e., monovalent
R3SiO1/2 units), D (i.e., divalent R2SiO2/2 units), T (i.e.,
trivalent RSiO3/2 units), and Q (i.e., quaternary SiO4/2 units),
and combinations thereof. Typical exemplary silicate resins include
MQ silicate tackifying resins, MQD silicate tackifying resins, and
MQT silicate tackifying resins. These silicate tackifying resins
usually have a number average molecular weight in the range of 100
to 50,000 or in the range of 500 to 15,000 and generally have
methyl R groups.
[0098] MQ silicate tackifying resins are copolymeric resins having
R3SiO1/2 units ("M" units) and SiO4/2 units ("Q" units), where the
M units are bonded to the Q units, each of which is bonded to at
least one other Q unit. Some of the SiO4/2 units ("Q" units) are
bonded to hydroxyl radicals resulting in HOSiO3/2 units ("TOH"
units), thereby accounting for the silicon-bonded hydroxyl content
of the silicate tackifying resin, and some are bonded only to other
SiO4/2 units.
[0099] Such resins are described in, for example, Encyclopedia of
Polymer Science and Engineering, vol. 15, John Wiley & Sons,
New York, (1989), pp. 265-270, and U.S. Pat. No. 2,676,182 (Daudt
et al.), U.S. Pat. No. 3,627,851 (Brady), U.S. Pat. No. 3,772,247
(Flannigan), and U.S. Pat. No. 5,248,739 (Schmidt et al.). Other
examples are disclosed in U.S. Pat. No. 5,082,706 (Tangney). The
above-described resins are generally prepared in solvent. Dried or
solventless, M silicone tackifying resins can be prepared, as
described in U.S. Pat. No. 5,319,040 (Wengrovius et al.), U.S. Pat.
No. 5,302,685 (Tsumura et al.), and U.S. Pat. No. 4,935,484
(Wolfgruber et al.).
[0100] Certain MQ silicate tackifying resins can be prepared by the
silica hydrosol capping process described in U.S. Pat. No.
2,676,182 (Daudt et al.) as modified according to U.S. Pat. No.
3,627,851 (Brady), and U.S. Pat. No. 3,772,247 (Flannigan). These
modified processes often include limiting the concentration of the
sodium silicate solution, and/or the silicon-to-sodium ratio in the
sodium silicate, and/or the time before capping the neutralized
sodium silicate solution to generally lower values than those
disclosed by Daudt et al. The neutralized silica hydrosol is often
stabilized with an alcohol, such as 2-propanol, and capped with
R3SiO1/2 siloxane units as soon as possible after being
neutralized. The level of silicon bonded hydroxyl groups (i.e.,
silanol) on the MQ resin may be reduced to no greater than 1.5
weight percent, no greater than 1.2 weight percent, no greater than
1.0 weight percent, or no greater than 0.8 weight percent based on
the weight of the silicate tackifying resin. This may be
accomplished, for example, by reacting hexamethyidisilazane with
the silicate tackifying resin. Such a reaction may be catalyzed,
for example, with trifluoroacetic acid. Alternatively,
trimethylchlorosilane or trimethylsilylacetamide may be reacted
with the silicate tackifying resin, a catalyst not being necessary
in this case.
[0101] MQD silicone tackifying resins are terpolymers having
R3SiO1/2 units ("M" units), SiO4/2 units("Q" units), and R2SiO2/2
units ("D" units) such as are taught in U.S. Pat. No. 2,736,721
(Dexter). In MQD silicone tackifying resins, some of the methyl R
groups of the R2SiO2/2 units ("D" units) can be replaced with vinyl
(CH2.dbd.CH--) groups ("DVi" units).
[0102] MQT silicate tackifying resins are terpolymers having
R3SiO1/2 units, SiO4/2 units and RSiO3/2 units ("T" units) such as
are taught in U.S. Pat. No. 5,110,890 (Butler) and Japanese Kokai
HE 2-36234.
[0103] Suitable silicate tackifying resins are commercially
available from sources such as Dow Corning, Midland, Mich., General
Electric Silicones Waterford, N.Y. and Rhodia Silicones, Rock Hill,
S.C. Examples of particularly useful MQ silicate tackifying resins
include those available under the trade designations SR-545 and
SR-1000, both of which are commercially available from GE
Silicones, Waterford, N.Y. Such resins are generally supplied in
organic solvent and may be employed in the formulations of the
adhesives of the present invention as received. Blends of two or
more silicate resins can be included in the adhesive
compositions.
Methods of Making Polydiorganosiloxane Polyamide Copolymers
[0104] The linear block copolymers having repeat units of Formula I
(I-a or I-b) can be prepared, for example, as represented in
Reaction Scheme A.
##STR00006##
[0105] In this reaction scheme, a precursor of Formula II is
combined under reaction conditions with a diamine having two
primary or secondary amino groups, two secondary amino groups, or
one primary amino group and one secondary amino group. The diamine
is usually of formula R.sup.3HN-G-NHR.sup.3. The R.sup.2OH
by-product is typically removed from the resulting
polydiorganosiloxane polyamide.
[0106] The diamine R.sup.3HN-G-NHR.sup.3 in Reaction Scheme A has
two amino groups (i.e., --NHR.sup.3). Group R.sup.3 is hydrogen or
alkyl (e.g., an alkyl having 1 to 10, 1 to 6, or 1 to 4 carbon
atoms) or R.sup.3 taken together with G and with the nitrogen to
which they are both attached forms a heterocyclic group (e.g., the
diamine is piperazine or the like). In most embodiments, R.sup.3 is
hydrogen or alkyl. In many embodiments, the diamine has two primary
amino groups (i.e., each R.sup.3 group is hydrogen) and the diamine
is of formula H.sub.2N-G-NH.sub.2. The portion of the diamine
exclusive of the two amino groups is referred to as group G in
Formula I (I-a or I-b).
[0107] The diamines are sometimes classified as organic diamines or
polydiorganosiloxane diamines with the organic diamines including,
for example, those selected from alkylene diamines, heteroalkylene
diamines, arylene diamines, aralkylene diamines, or
alkylene-aralkylene diamines. The diamine has only two amino groups
so that the resulting polydiorganosiloxane polyamides are linear
block copolymers that are often elastomeric, molten at elevated
temperatures, and soluble in some common organic solvents. The
diamine is free of a polyamine having more than two primary or
secondary amino groups. Tertiary amines that do not react with the
precursor of Formula II can be present. Additionally, the diamine
is free of any carbonylamino group. That is, the diamine is not an
amide.
[0108] Exemplary polyoxyalkylene diamines (i.e., G is a
heteroalkylene with the heteroatom being oxygen) include, but are
not limited to, those commercially available from Huntsman, The
Woodlands, Tex. under the trade designation JEFFAMINE D-230 (i.e.,
polyoxypropropylene diamine having an average molecular weight of
230 g/mole), JEFFAMINE D-400 (i.e., polyoxypropylene diamine having
an average molecular weight of 400 g/mole), JEFFAMINE D-2000 (i.e.,
polyoxypropylene diamine having an average molecular weight of
2,000 g/mole), JEFFAMINE HK-511 (i.e., polyetherdiamine with both
oxyethylene and oxypropylene groups and having an average molecular
weight of 220 g/mole), JEFFAMINE ED-2003 (i.e., polypropylene oxide
capped polyethylene glycol having an average molecular weight of
2,000 g/mole), and JEFFAMINE EDR-148 (i.e., triethyleneglycol
diamine).
[0109] Exemplary alkylene diamines (i.e., G is a alkylene) include,
but are not limited to, ethylene diamine, propylene diamine,
butylene diamine, hexamethylene diamine, 2-methylpentamethylene
1,5-diamine (i.e., commercially available from DuPont, Wilmington,
Del. under the trade designation DYTEK A), 1,3-pentane diamine
(commercially available from DuPont under the trade designation
DYTEK EP), 1,4-cyclohexane diamine, 1,2-cyclohexane diamine
(commercially available from DuPont under the trade designation
DHC-99), 4,4'-bis(aminocyclohexyl)methane, and
3-aminoinethyl-3,5,5-trimethylcyclohexylamine.
[0110] Exemplary arylene diamines (i.e., G is an arylene such as
phenylene) include, but are not limited to, m-phenylene diamine,
o-phenylene diamine, and p-phenylene diamine. Exemplary aralkylene
diamines (i.e., G is an aralkylene such as alkylene-phenyl)
include, but are not limited to 4-aminomethyl-phenylamine,
3-aminomethyl-phenylamine, and 2- aminomethyl-phenylamine.
Exemplary alkylene-aralkylene diamines (i.e., G is an
alkylene-aralkylene such as alkylene-phenylene-alkylene) include,
but are not limited to, 4-aminomethyl-benzylamine,
3-aminomethyl-benzylamine, and 2-aminomethyl-benzylamine.
[0111] The precursor of Formula II in Reaction Scheme A has at
least one polydiorganosiloxane segment and at least two oxalylamino
groups. Group R.sup.1, group Y, subscript n, and subscript p are
the same as described for Formula I (I-a or I-b). Each group
R.sup.2 is independently an alkyl, haloalkyl, aryl, or aryl
substituted with an alkyl, alkoxy, halo, or alkoxycarbonyl. The
precursor of Formula II can include a single compound (i.e., all
the compounds have the same value of p and n) or can include a
plurality of compounds (i.e., the compounds have different values
for p, different values for n, or different values for both p and
n). Precursors with different n values have siloxane chains of
different length. Precursors having a p value of at least 2 are
chain extended.
[0112] In some embodiments, the precursor is a mixture of a first
compound of Formula II with subscript p equal to 1 and a second
compound of Formula II with subscript p equal to at least 2. The
first compound can include a plurality of different compounds with
different values of n. The second compound can include a plurality
of compounds with different values of p, different values of n, or
different values of both p and n. Mixtures can include at least 50
weight percent of the first compound of Formula II (i.e., p is
equal to 1) and no greater than 50 weight percent of the second
compound of Formula II (i.e., p is equal to at least 2) based on
the sum of the weight of the first and second compounds in the
mixture. In some mixtures, the first compound is present in an
amount of at least 55 weight percent, at least 60 weight percent,
at least 65 weight percent, at least 70 weight percent, at least 75
weight percent, at least 80 weight percent, at least 85 weight
percent, at least 90 weight percent, at least 95 weight percent, or
at least 98 weight percent based on the total amount of the
compounds of Formula II. The mixtures often contain no greater than
50 weight percent, no greater than 45 weight percent, no greater
than 40 weight percent, no greater than 35 weight percent, no
greater than 30 weight percent, no greater than 25 weight percent,
no greater than 20 weight percent, no greater than 15 weight
percent, no greater than 10 weight percent, no greater than 5
weight percent, or no greater than 2 weight percent of the second
compound.
[0113] Different amounts of the chain-extended precursor of Formula
II in the mixture can affect the final properties of the
elastomeric material of Formula I (I-a or I-b). That is, the amount
of the second compound of Formula II (i.e., p equal to at least 2)
can be varied advantageously to provide elastomeric materials with
a range of properties. For example, a higher amount of the second
compound of Formula II can alter the melt rheology (e.g., the
elastomeric material can flow easier when present as a melt), alter
the softness of the elastomeric material, lower the modulus of the
elastomeric material, or a combination thereof.
[0114] Reaction Scheme A can be conducted using a plurality of
precursors of Formula II, a plurality of diamines, or a combination
thereof. A plurality of precursors having different average
molecular weights can be combined under reaction conditions with a
single diamine or with multiple diamines. For example, the
precursor of Formula II may include a mixture of materials with
different values of n, different values of p, or different values
of both n and p. The multiple diamines can include, for example, a
first diamine that is an organic diamine and a second diamine that
is a polydiorganosiloxane diamine. Likewise, a single precursor can
be combined under reaction conditions with multiple diamines.
[0115] For certain embodiments, the molar ratio of the precursor of
Formula II to the diamine is often 1:1. For example, the molar
ratio is often less than or equal to 1:0.80, less than or equal to
1:0.85, less than or equal to 1:0.90, less than or equal to 1:0.95,
or less than or equal to 1:1. The molar ratio is often greater than
or equal to 1:1.05, greater than or equal to 1:1. 10, or greater
than or equal to 1:1.15. For example, the molar ratio can be in the
range of 1:0.80 to 1:1.20, in the range of 1:0.80 to 1:1.15, in the
range of 1:0.80 to 1:1.10, in the range of 1:0.80 to 1:1.05, in the
range of 1:0.90 to 1:1.10, or in the range of 1:0.95 to 1:1.05.
[0116] For certain embodiments, the molar ratio of the precursor of
Formula II to the diamine is less than 1:1.20 or greater than
1:0.80. For example, it can be 1:0.50, 1:0.55, 1:0.60, 1:0.65,
1:0.70, or 1:0.75, or it can be 1:1.25, 1:1.30, or 1:1.35. For
example, the molar ratio can be in the range of less than 1:1.20
down to and including 1:2.00. Alternatively, it can be in the range
of greater than 1:0.80 up to and including 1:0.50.
[0117] Varying the molar ratio can be used, for example, to alter
the overall molecular weight, which can effect the rheology of the
resulting copolymers. Additionally, varying the molar ratio can be
used to provide oxalylamino-containing end groups or amino end
groups, depending upon which reactant is present in molar
excess.
[0118] The condensation reaction of the precursor of Formula II
with the diamine (i.e., Reaction Scheme A) is often conducted at
room temperature or at elevated temperatures such as at
temperatures up to 250.degree. C. For example, the reaction often
can be conducted at room temperature or at temperatures LIP to
100.degree. C. In other examples, the reaction can be conducted at
a temperature of at least 100.degree. C., at least 120.degree. C.,
or at least 150.degree. C. For example, the reaction temperature is
often in the range of 100.degree. C. to 220.degree. C., in the
range of 120.degree. C. to 220.degree. C., or in the range of
150.degree. C. to 200.degree. C. The condensation reaction is often
complete in less than 1 hour, in less than 2 hours, in less than 4
hours, in less than 8 hours, or in less than 12 hours.
[0119] Reaction Scheme A can occur in the presence or absence of a
solvent. Suitable solvents usually do not react with any of the
reactants or products of the reactions. Additionally, suitable
solvents are usually capable of maintaining all the reactants and
all of the products in solution throughout the polymerization
process. Exemplary solvents include, but are not limited to,
toluene, tetrahydrofuran, dichloromethane, aliphatic hydrocarbons
(e.g., alkanes such as hexane), or mixtures thereof.
[0120] Any solvent that is present can be stripped from the
resulting polydiorganosiloxane polyamide at the completion of the
reaction. Solvents that can be removed under the same conditions
used to remove the alcohol by-product are often preferred. The
stripping process is often conducted at a temperature of at least
100.degree. C., at least 125.degree. C., or at least 150.degree. C.
The stripping process is typically at a temperature less than
300.degree. C., less than 250.degree. C., or less than 225.degree.
C.
[0121] Conducting Reaction Scheme A in the absence of a solvent can
be desirable because only the volatile by-product, R.sup.2OH, needs
to be removed at the conclusion of the reaction. Additionally, a
solvent that is not compatible with both reactants and the product
can result in incomplete reaction and a low degree of
polymerization.
[0122] Any suitable reactor or process can be used to prepare the
copolymeric material according to Reaction Scheme A. The reaction
can be conducted using a batch process, semi-batch process, or a
continuous process. Exemplary batch processes can be conducted in a
reaction vessel equipped with a mechanical stirrer such as a
Brabender mixer, provided the product of the reaction is in a
molten state has a sufficiently low viscosity to be drained from
the reactor. Exemplary semi-batch process can be conducted in a
continuously stirred tube, tank, or fluidized bed. Exemplary
continuous processes can be conducted in a single screw or twin
screw extruder such as a wiped surface counter-rotating or
co-rotating twin screw extruder.
[0123] In many processes, the components are metered and then mixed
together to form a reaction mixture. The components can be metered
volumetrically or gravimetrically using, for example, a gear,
piston or progressing cavity pump. The components can be mixed
using any known static or dynamic method such as, for example,
static mixers, or compounding mixers such as single or multiple
screw extruders. The reaction mixture can then be formed, poured,
pumped, coated, injection molded, sprayed, sputtered, atomized,
stranded or sheeted, and partially or completely polymerized. The
partially or completely polymerized material can then optionally be
converted to a particle, droplet, pellet, sphere, strand, ribbon,
rod, tube, film, sheet, coextruded film, web, non-woven,
microreplicated structure, or other continuous or discrete shape,
prior to the transformation to solid polymer. Any of these steps
can be conducted in the presence or absence of applied heat. In one
exemplary process, the components can be metered using a gear pump,
mixed using a static mixer, and injected into a mold prior to
solidification of the polymerizing material.
[0124] The polydiorganosiloxane-containing precursor of Formula II
in Reaction Scheme A can be prepared by any known method. In some
embodiments, this precursor is prepared according to Reaction
Scheme B.
##STR00007##
[0125] A polydiorganosiloxane diamine of Formula III (p moles) is
reacted with a molar excess of an oxalate of Formula IV (greater
than p+1 moles) under an inert atmosphere to produce the
polydiorganosiloxane-containing precursor of Formula II and
R.sup.2--OH by-product. In this reaction, R.sup.1, Y, n, and p are
the same as previously described for Formula I (I-a or I-b). Each
R.sup.2 in Formula IV is independently an alkyl, haloalkyl, aryl,
or aryl substituted with an alkyl, alkoxy, halo, or alkoxycarbonyl.
The preparation of the precursor of Formula II according to
Reaction Scheme B is further described in Applicant's Assignee's
copending U.S. patent application Ser. No. 11/317,616, filed on
Dec. 23, 2005.
[0126] The polydiorganosiloxane diamine of Formula III in Reaction
Scheme B can be prepared by any known method and can have any
suitable molecular weight, such as an average molecular weight in
the range of 700 to 150,000 g/mole. Suitable polydiorganosiloxane
diamines and methods of making the polydiorganosiloxane diamines
are described, for example, in U.S. Pat. No. 3,890,269 (Martin),
U.S. Pat. No. 4,661,577 (Jo Lane et al.), U.S. Pat. No. 5,026,890
(Webb et al.), U.S. Pat. No. 5,276,122 (Aoki et al.), U.S. Pat. No.
5,214,119 (Leir et al.), U.S. Pat. No. 5,461,134 (Leir et al.), U.S
Pat. No. 5,512,650 (Leir et al.), and U.S. Pat. No. 6,355,759
(Sherman et al.), incorporated herein by reference in their
entirety. Some polydiorganosiloxane diamines are commercially
available, for example, from Shin Etsu Silicones of America, Inc.,
Torrance, Calif. and from Gelest Inc., Morrisville, Pa.
[0127] A polydiorganosiloxane diamine having a molecular weight
greater than 2,000 g/mole or greater than 5,000 g/mole can be
prepared using the methods described in U.S. Pat. No. 5,214,119
(Leir et al.), U.S. Pat. No. 5,461,134 (Leir et al.), and U.S. Pat.
No. 5,512,650 (Leir et al.). One of the described methods involves
combining under reaction conditions and under an inert atmosphere
(a) an amine functional end blocker of the following formula
##STR00008##
where Y and R.sup.1 are the same as defined for Formula I (I-a or
I-b); (b) sufficient cyclic siloxane to react with the amine
functional end blocker to form a polydiorganosiloxane diamine
having a molecular weight less than 2,000 g/mole; and (c) an
anhydrous aminoalkyl silanolate catalyst of the following
formula
##STR00009##
where Y and R.sup.1 are the same as defined in Formula I (I-a or
I-b) and M+is a sodium ion, potassium ion, cesium ion, rubidium
ion, or tetramethylammonium ion. The reaction is continued until
substantially all of the amine functional end blocker is consumed
and then additional cyclic siloxane is added to increase the
molecular weight. The additional cyclic siloxane is often added
slowly (e.g., drop wise). The reaction temperature is often
conducted in the range of 80.degree. C. to 90.degree. C. with a
reaction time of 5 to 7 hours. The resulting polydiorganosiloxane
diamine can be of high purity (e.g., less than 2 weight percent,
less than 1.5 weight percent, less than 1 weight percent, less than
0.5 weight percent, less than 0.1 weight percent, less than 0.05
weight percent, or less than 0.01 weight percent silanol
impurities). Altering the ratio of the amine end functional blocker
to the cyclic siloxane can be used to vary the molecular weight of
the resulting polydiorganosiloxane diamine of Formula Another
method of preparing the polydiorganosiloxane diamine of Formula III
includes combining under reaction conditions and under an inert
environment (a) an amine functional end blocker of the following
formula
##STR00010##
where R.sup.1 and Y are the same as described for Formula I (I-a or
I-b) and where the subscript x is equal to an integer of 1 to 150;
(b) sufficient cyclic siloxane to obtain a polydiorganosiloxane
diamine having an average molecular weight greater than the average
molecular weight of the amine functional end blocker; and (c) a
catalyst selected from cesium hydroxide, cesium silanolate,
rubidiulIl silanolate, cesium polysiloxanolate, rubidium
polysiloxanolate, and mixtures thereof. The reaction is continued
until substantially all of the amine functional end blocker is
consumed. This method is further described in U.S. Pat. No.
6,355,759 B1 (Shernan et al.). This procedure can be used to
prepare any molecular weight of the polydiorganosiloxane
diamine.
[0128] Yet another method of preparing the polydiorganosiloxane
diamine of Formula III is described in U.S. Pat. No. 6,531,620 B2
(Brader et al.). In this method, a cyclic silazane is reacted with
a siloxane material having hydroxy end groups as shown in the
following reaction.
##STR00011##
The groups R.sup.1 and Y are the same as described for Formula I
(I-a or I-b). The subscript m is an integer greater than 1.
[0129] Examples of polydiorganosiloxane diamines include, but are
not limited to, polydimethylsiloxane diamine, polydiphenylsiloxane
diamine, polytrifluoropropylmethylsiloxane diamine,
polyphenylmethylsiloxane diamine, polydiethylsiloxane diamine,
polydivinylsiloxane diamine, polyvinylmethylsiloxane diamine,
poly(5-hexenyl)methylsiloxane diamine, and mixtures thereof.
[0130] In Reaction Scheme B, an oxalate of Formula IV is reacted
with the polydiorganosiloxane diamine of Formula III under an inert
atmosphere. The two R.sup.2 groups in the oxalate of Formula IV can
be the same or different. In some methods, the two R.sup.2 groups
are different and have different reactivity with the
polydiorganosiloxane diamine of Formula III in Reaction Scheme
B.
[0131] Group R can be an alkyl, haloalkyl, aryl, or aryl
substituted with an alkyl, alkoxy, halo, or alkoxycarbonyl.
Suitable alkyl and haloalkyl groups for R.sup.2 often have 1 to 10,
1 to 6, or 1 to 4 carbon atoms. Although tertiary alkyl (e.g.,
tert-butyl) and haloalkyl groups can be used, there is often a
primary or secondary carbon atom attached directly (i.e., bonded)
to the adjacent oxy group. Exemplary alkyl groups include methyl,
ethyl, n-propyl, iso-propyl, n-butyl, and iso-butyl. Exemplary
haloalkyl groups include chloroalkyl groups and fluoroalkyl groups
in which some, but not all, of the hydrogen atoms on the
corresponding alkyl group are replaced with halo atoms. For
example, the chloroalkyl or a fluoroalkyl groups can be
chloromethyl, 2-chloroethyl, 2,2,2-trichloroethyl, 3-chloropropyl,
4-chlorobutyl, fluoromethyl, 2-fluoroethyl, 2,2,2-trifluoroethyl,
3-fluoropropyl, 4-fluorobutyl, and the like. Suitable aryl groups
for R.sup.2 include those having 6 to 12 carbon atoms such as, for
example, phenyl. An aryl group can be unsubstitited or substituted
with an alkyl (e.g., an alkyl having 1 to 4 carbon atoms such as
methyl, ethyl, or n-propyl), an alkoxy (e.g., an alkoxy having 1 to
4 carbon atoms such as methoxy, ethoxy, or propoxy), halo (e.g.,
chloro, bromo, or fluoro), or alkoxycarbonyl (e.g., an
alkoxycarbonyl having 2 to 5 carbon atoms such as methoxycarbonyl,
ethoxycarbonyl, or propoxycarbonyl).
[0132] The oxalates of Formula IV in Reaction Scheme B can be
prepared, for example, by reaction of an alcohol of formula
R.sup.2--OH with oxalyl dichloride. Commercially available oxalates
of Formula IV (e.g., from Sigma-Aldrich, Milwaukee, Wis. and from
VWR International, Bristol, Conn.) include, but are not limited to,
dimethyl oxalate, diethyl oxalate, di-n-butyl oxalate,
di-tert-butyl oxalate, bis(phenyl)oxalate, bis(pentafluorophenyl)
oxalate, 1-(2,6-difluorophenyl)-2-(2,3,4,5,6-pentachlorophenyl)
oxalate, and bis (2,4,6-trichlorophenyl)oxalate.
[0133] A molar excess of the oxalate is used in Reaction Scheme B.
That is, the molar ratio of oxalate to polydiorganosiloxane diamine
is greater than the stoichiometric molar ratio, which is (p+1): p.
The molar ratio is often greater than 2:1, greater than 3:1,
greater than 4: 1, or greater than 6:1. The condensation reaction
typically occurs under an inert atmosphere and at room temperature
upon mixing of the components.
[0134] The condensation reaction used to produce the precursor of
Formula II (i.e., Reaction Scheme B) can occur in the presence or
absence of a solvent. In some methods, no solvent or only a small
amount of solvent is included in the reaction mixture. In other
methods, a solvent may be included such as, for example, toluene,
tetrahydrofuran, dichloromethane, or aliphatic hydrocarbons (e.g.,
alkanes such as hexane).
[0135] Removal of excess oxalate from the precursor of Formula II
prior to reaction with the diamine in Reaction Scheme A tends to
favor formation of an optically clear polydiorganosiloxane
polyamide. The excess oxalate can typically be removed from the
precursor using a stripping process. For example, the reacted
mixture (i.e., the product or products of the condensation reaction
according to Reaction Scheme B) can be heated to a temperature up
to 150.degree. C., up to 175.degree. C., up to 200.degree. C., up
to 225.degree. C., or LIP to 250.degree. C. to volatilize the
excess oxalate. A vacuum can be pulled to lower the temperature
that is needed for removal of the excess oxalate. The precursor
compounds of Formula II tend to undergo minimal or no apparent
degradation at temperatures in the range of 200.degree. C. to
250.degree. C. or higher. Any other known methods of removing the
excess oxalate can be used.
[0136] The by-product of the condensation reaction shown in
Reaction Scheme B is an alcohol (i.e., R.sup.2--OH is an alcohol).
Group R.sup.2 is often limited to an alkyl having 1 to 4 carbon
atoms, a haloalkyl having 1 to 4 carbon atoms, or an aryl such as
phenyl that form an alcohol that can be readily removed (e.g.,
vaporized) by heating at temperatures no greater than 250.degree.
C. Such an alcohol can be removed when the reacted mixture is
heated to a temperature sufficient to remove the excess oxalate of
Formula IV.
Processes of Making Compositions and Constructions
[0137] The compositions and constructions of the present invention
can be made by solvent-based processes known to the art, by a
solventless process, or by a combination of the two.
[0138] One skilled in the art can expect the optimum material for a
particular application to be a function of the architecture and
ratios of the polydiorganosiloxane polyamide-containing component,
the architecture and ratios of organic polymer, optional initiator
architecture, and whether any functional components, additives, or
property modifiers are added.
[0139] The organic polymer is generally added as a molten stream to
the polydiorganosiloxane polyamide-containing component or to one
of the reactants of the polydiorganosiloxane polyamide-containing
component. Sometimes the polymeric material needs to be melted in a
separate vessel before the polydiorganosiloxane
polyamide-containing component is added (I) as pellets, (2) as
reactants or (3) as a separate molten stream from a second vessel.
Examples when a separate vessel is preferred include, for example,
when (1) additives are preferred to concentrate in the organic
polymer, (2) organic polymers need high processing temperatures,
and (3) organic polymers include elastomeric thermoset
materials.
[0140] The order of adding the various components is important in
forming the mixture. If the organic polymer is substantially
unreactive with the reactants for making the polydiorganositoxane
polyamide (e.g., diamines) as discussed earlier, any order of
addition can be used. The polydiorganosiloxane polyamide-containing
component can be added to the organic polymer, and vice versa, or
the polydiorganosiloxane polyamide-containing component can be made
in the presence of the organic polymer. However, the organic
polymer must be added after the polydiorganosiloxane
polyamide-containing component is formed if the organic polymer is
reactive with the reactants for making such component. Also, the
organic polymer is preferably sufficiently heated to a processable
state in a separate vessel and added to a molten stream of the
polydiorganosiloxane polyamide-containing component if the
temperature needed to process the organic polymer would degrade the
polydiorganosiloxane polyamide-containing component.
[0141] Other additives such as plasticizing materials, tackifying
materials, pigments, fillers, initiators, and the like can
generally be added at any point in the process since they are
usually not reactive with the reactants but are typically added
after a substantial amount of the polydiorganosiloxane
polyamide-containing component is formed.
[0142] When mixing organic polymers that are non-thermoplastic
elastomeric materials with polydiorganosiloxane
polyamide-containing components, the former generally needs special
conditions to be melt processed. Two methods of making
non-thermoplastic elastomeric materials melt processable are (I)
reducing their apparent melt viscosity by swelling them with
tackifying or plasticizing material or (2) masticating the
materials as described in U.S. Pat. No. 5,539,033.
[0143] Four process considerations can affect the final properties
of the mixtures made by the solventless process. First, the
properties of polydiorganosiloxane polyamide-containing component
could be affected by whether the polydiorganosiloxane
polyamide-containing component is made in a solvent or an
essentially solventless process. Second, the polydiorganosiloxane
polyamide-containing component can degrade if exposed to too much
heat and shear. Third, the stability of the mixture is affected by
how the polydiorganosiloxane polyamide-containing component is
mixed with the organic polymer. Fourth, the morphology of the
article made with the mixture is determined by the interaction of
the processing parameters and characteristics of the components in
the mixture.
[0144] In a first consideration, the polydiorganosiloxane
polyamide-containing component can be made previously by either a
solvent or solventless process or can be made in the presence of
the organic polymer. Methods of making the polydiorganosiloxane
polyamide-containing component in solvent were disclosed above.
Methods of making the polydiorganosiloxane polyamide-containing
component in substantially solventless conditions can result in
polydiorganosiloxane polyamide-containing component high in
molecular weight.
[0145] In a second consideration, the polydiorganosiloxane
polyamide-containing component can degrade if it is heated too much
under shear conditions, particularly in the presence of oxygen. The
polydiorganosiloxane polyamide-containing component is exposed to
the least amount of heat and shear when made in the presence of the
organic polymer, and in particular, when the mixture is made under
an inert atmosphere.
In a third consideration, the stability of the mixture is affected
by how the polydiorganosiloxane polyamide-containing component is
mixed with the organic polymer. Polydiorganosiloxanes are generally
immiscible with most other polymeric materials. However, the
inventors have found that a wide variety of polymers can be mixed
with a polydiorganosiloxane polyamide-containing component when
both are in the molten state. Care must be taken that the
conditions needed to soften one component does not degrade the
other. Preferably, the mixing temperature should be at a
temperature above the mixing and conveying temperature of the
mixture and below the degradation temperature of the
polydiorganosiloxane polyamide-containing component. The
polydiorganosiloxane polyoxamide copolymer can usually be subjected
to elevated temperatures up to 250.degree. C. or higher without
apparent degradation.
[0146] Any vessel in which the components can be adequately heated
and mixed in the molten state is suitable for making mixtures of
the invention.
[0147] In a fourth consideration, the processing steps influence
the morphology of an article made with the mixtures of the
invention. The mixtures generally have at least two domains, one
discontinuous and the other continuous, because of the general
iminiscibility of the polydiorganosiloxane polyamide-containing
component with the organic polymer. The component comprising the
minor phase typically forms discontinuous domains that range in
shape from spheroidal to ellipsoidal to ribbon-like to fibrous. The
component comprising the major phase typically forms the continuous
domain that surrounds the discontinuous domains. The discontinuous
domains of the mixture generally elongate if the mixture is
subjected to sufficient shear or extensional forces as the mixture
is formed into an article, such as a film or coating. The
discontinuous domains generally remain elongated if at least one of
the components has a sufficient viscosity at use temperature to
prevent the elongated domain from relaxing into a sphere when the
mixture is no longer under extensional or shear forces. The
elongated morphology is usually stable until the mixture is
reheated above the softening point of the components.
[0148] While both a solvent based process and a solventless process
for making the mixtures of the invention can be used, there may be
some situations where a combination of the two is preferred. In the
latter case, a polydiorganosiloxane polyamide-containing component
could be made by the solvent based process and subsequently dried
and melt mixed with the organic polymer.
Types of Articles
[0149] Polymeric mixtures of the present invention and compositions
containing them, depending on specific formulation, can be used to
make a variety of articles. They can be used, for example, as
release films, optical films and filters, diffuse optical articles,
process aids, optical pressure sensitive adhesives, pressure
sensitive adhesive tapes, pressure sensitive adhesive transfer
tapes, pressure sensitive adhesive medical tapes, including, for
example, transdermal drug delivering devices, rubber-toughened
articles, or pressure sensitive adhesive coatings directly onto
desired articles. They can also be used, for example, as hot melt
adhesives, nonwoven webs, water repellant films, anti-graffiti
films, casting liners, vibration dampers, acoustic dampers, medical
backings, tape backings, sealants, relective polarizers, reflectors
including infrared radiation reflectors, and permeable films. They
can be formed into unsupported films, coated on a support
substrate, and/or incorporated into one or more layers of a
multilayer film.
[0150] Polymeric mixtures of the present invention and compositions
containing them can be used in melt process aids. Surface
modification, slip aids, compatibilizers, refractive index
modifiers, impact modifiers, optics modifiers, rheology modifiers,
permeability modifiers, water repellency modifiers, fiber treatment
materials to impart a perfect smoothness modifiers, lubricity
modifiers, tack modifiers (e.g., to reduce tackiness), and
modifiers of tactile sensation.
[0151] Polymeric mixtures of the present invention and compositions
containing them, dependent on specific formulation used, can be
pressure sensitive adhesive materials, heat activated adhesives,
vibration damping materials, and non-adhesive materials. To employ
non-adhesive vibration damping materials requires the use of a
bonding agent, that is, a material to affix the damping material to
either a constraining layer and/or a resonating structure depending
on the particular use geometry desired.
[0152] Polymeric mixtures of the present invention and compositions
containing them can be cast from solvents as film, molded or
embossed in various shapes, or extruded into films. They can be
formed into various articles, for example, one that includes a
layer containing the mixture containing the polydiorganosiloxane
polyamide copolymer and one or more optional substrates. For
example, the polydiorganosiloxane polyamide copolymer-containing
mixture can be in a layer adjacent to a first substrate or
positioned between a first substrate and a second substrate. That
is, the article can be arranged in the following order: a first
substrate, a layer containing the polydiorganosiloxane polyamide
copolymer-containing mixture, and a second substrate. As used
herein, the term "adjacent" refers to a first layer that contacts a
second layer or that is positioned in proximity to the second layer
but separated from the second layer by one or more additional
layers.
[0153] Pressure sensitive adhesive articles are made by applying
the pressure sensitive adhesive by well known hot melt or solvent
coating process. Any suitable substrates that can by used,
including, but not limited to, for example, cloth and fiber-glass
cloth, metallized films and foils, polymeric films, nonwovens,
paper and polymer coated paper, and foam backings. Polymer films
include, but are not limited to, polyolefins such as polypropylene,
polyethylene, low density polyethylene, linear low density
polyethylene and high density polyethylene; polyesters such as
polyethylene terephthalate; polycarbonates; cellulose acetates;
polyimides such as that available under the trade designation
KAPTON. Nonwovens, generally made from randomly oriented fibers,
include, but are not limited by, nylon, polypropylene,
ethylene-vinyl acetate copolymer, polyurethane, rayon and the like.
Foam backings include, but are not limited to, acrylic, silicone,
polyurethane, polyethylene, neoprene rubber, and polypropylene, and
may be filled or unfilled. Backings that are layered, such as
polyethylene-aluminum membrane composites, are also suitable.
[0154] In the case of pressure sensitive tapes, these materials are
typically applied by first making a tape construction which
comprises a layer of the pressure sensitive adhesive material
coated on a backing. The exposed surface of the pressure sensitive
adhesive coating may be subsequently applied to a surface from
which it could be released later or directly to the desired
substrate.
[0155] Some pressure sensitive adhesive articles use release
liners, i.e., transfer tapes that can be made by coating the
composition between two liners both of which are coated with a
release coating. The release liners typically comprise polymeric
material such as polyester, polyethylene, polyolefin and the like,
or release coated paper or polyethylene coated paper. Preferably,
each release liner is first coated or primed with a release
material for the adhesive materials utilized in the invention. When
the mixture contains a significant amount of a tackified
polydiorganosiloxane polyamide-containing component, useful release
liners include those that are suitable for use with silicone
adhesives. One example is the polyfluoropolyether coated liner
described in European Patent Publication No. 433070. Other useful
release liner release coating compositions are described in
European Patent Publication No. 378420, U.S. Pat. No. 4,889,753,
and European Patent Publication No. 311262. Commercially available
liners and compositions include that available under the trade
designation SYL-OFF Q2-7785 fluorosilicone release coating from Dow
Corning Corp., Midland, Mich., X-70-029NS fluorosilicone release
coatings available from Shin-Etsu Silicones of America, Inc.,
Torrance, Calif.; that available under the trade designation S
TAKE-OFF 2402 fluorosilicone release liner from Release
International, Bedford Park, Ill.; and the like.
[0156] Polymeric mixtures of the present invention and compositions
containing them are also useful in medical applications including
transdermal drug delivery devices. Transdermal drug delivery
devices are designed to deliver a therapeutically effective amount
of drug through or to the skin of a patient. Transdermal drug
delivery provides significant advantages; unlike injection, it is
noninvasive; unlike oral administration, it avoids hepatic first
pass metabolism, it minimizes gastrointestinal effects, and it
provides stable blood levels.
[0157] Polymeric mixtures of the present invention and compositions
containing them may also be used in pressure sensitive adhesives
that readily attach to prepared and unprepared surfaces, especially
metals, polyolefin and fluorine containing polymeric films,
providing a highly conformable, continuous interfacial silicone
coating that prevents ingress of environmental contaminants
including those that corrosively attack unprotected surfaces. A
pressure sensitive adhesive patch typically consists of a
protective polydiorganosiloxane polyamide-containing pressure
sensitive adhesive mixture and optionally a barrier or edge
adhesive, layers of conformable barrier or backing materials, or
combinations of these materials. For some applications it is
preferable that the backing does not shield electric field lines,
making an open structure backing more preferable to solid films of,
for example, polyethylene or PVC. A tapered or profiled adhesive
layer to better match surface topology may be preferred when
patching some surfaces.
[0158] Polymeric mixtures of the present invention and compositions
containing them may also be used as pressure sensitive adhesives or
hot melt adhesives for heat shrink tubes. These constructions
provide a single article that can withstand the high temperatures
experienced during the heat shrink operation and provide an
environmental seal after cooling. The rheology, heat stability,
tack, and clarity of these materials make them especially suitable
for this application.
[0159] Polymeric mixtures of the present invention and compositions
containing them can also be coated onto a differential release
liner; i.e., a release liner having a first release coating on one
side of the liner and a second release coating coated on the
opposite side. The two release coatings preferably have different
release values. For example, one release coating may have a release
value of 5 grains/cm (that is, 5 grains of force is needed to
remove a strip of material 1 cm wide from the coating) while the
second release coating may have a release value of 15 grams/cm. The
material can be coated over the release liner coating having the
higher release value. The resulting tape can be wound into a roll.
As the tape is unwound, the pressure sensitive adhesive adheres to
the release coating with the higher release value. After the tape
is applied to a substrate, the release liner can be removed to
expose an adhesive surface for further use.
[0160] Hot melt adhesives are compositions that can be used to bond
nonadhering surfaces together into a composite. During application
to a substrate, hot melt adhesives should be sufficiently fluid to
wet the surface completely and leave no voids, even if the surface
is rough. Consequently, the adhesive must be low in viscosity at
the time of application. However, the bonding adhesive generally
sets into a solid to develop sufficient cohesive strength to remain
adhered to the substrate under stressful conditions.
[0161] For hot melt adhesives, the transition from fluid to solid
may be accomplished in several ways. First, the hot melt adhesive
may be a thermoplastic that softens and melts when heated and
becomes hard again when cooled. Such heating results in
sufficiently high fluidity to achieve successful wetting.
Alternatively, the hot melt adhesive may be dissolved in a solvent
or carrier that lowers the viscosity of the adhesive sufficiently
to permit satisfactory wetting and raises the adhesive viscosity
when the solvent or carrier is removed. Such an adhesive can be
heat activated, if necessary.
[0162] Polymeric mixtures of the present invention and compositions
containing them may also be used as vibration damping materials
alone, that is, free layer treatment, or in conjunction with a
stiff layer, that is, as part of a constrained-layer treatment.
Vibration damping materials are most efficiently used if they are
sandwiched between the structure/device to be damped and a
relatively stiff layer, such as thin sheet metal. This forces the
viscoelastic material to be deformed in shear as the panel
vibrates, dissipating substantially more energy than when the
material deforms in extension and compression, as occurs in a free
layer treatment. Preferably, constrained-layer constructions
consist of a laminate of one or more stiff layers and one or more
layers of the vibration damping material.
[0163] Constrained-layer constructions can be prepared by several
processes. In one process, a layer of the vibration damping
material is coated onto a release liner by conventional solution
coating or hot melt coating techniques known in the art. The layer
of resulting viscoelastic material is transferred to a stiff
backing and adhered thereto, thereby providing a constrained-layer
construction. In another process, a layer of vibration damping
material is coated directly onto a stiff backing by conventional
solution coating or hot melt coating techniques known in the art.
In each case, the constrained-layer construction is then affixed to
the structure requiring damping. The construction may be attached
in any manner provided that the constraining layer is only fixed to
the vibrating structure via the viscoelastic material interface,
i.e. free of mechanical attachment. When the structure subsequently
vibrates under the influence of an internally or externally applied
force, the vibration is damped.
[0164] Another application of the vibration damping materials of
the present invention is in a bidirectional damping unit such as
described in Neilsen, E. J. et al, "Viscoelastic Damper Overview
For Seismic and Wind Applications," Structural Engineering
Association of California, Tahoe Olympiad, October, 1994.
Bi-directional, or large displacement, damping is the transference
of subsonic oscillations of a structure, such as a building, into
the shear deformation of a viscoelastic material for the purpose of
damping the oscillations of the structure. In this application,
materials which have maximum vibration damping capability
preferably have shear storage moduli, G', of 6.9.times.10.sup.3 Pa
to 3.45.times.10.sup.7 Pa, more preferably 3.45.times.10.sup.4 Pa
to 1.4.times.10.sup.7 Pa, most preferably 3.45.times.10.sup.5 Pa to
6.9.times.10.sup.6 Pa at the use temperature, and have a tan
.delta. as high as possible over the use temperature and frequency
range. The materials also preferably have an elongation in tension
of at least 100 percent or a shear strain capability of at least
100 percent within their use range of temperature and
frequency.
[0165] When the vibration damping material has pressure sensitive
adhesive properties, the material can usually be adhered to a stiff
layer without the use of an additional bonding agent. However, it
is sometimes necessary to use a thin layer, for example, 20-50
.mu.m in thickness, of a high strength adhesive, such as, for
example, an acrylic adhesive, an epoxy adhesive, or a silicone
adhesive, all of which are well-known to those skilled in the art,
to bond the vibration damping composition of the invention to a
structure.
[0166] For most applications, the layer of vibration damping
material has a thickness of at least 0.01 mm up to 100 mm, more
preferably 0.05 to 100 mm. The damping material can be applied by
any of the techniques known in the art such as by spraying,
dipping, knife, or curtain coating, or molding, laminating,
casting, or extruding.
[0167] As mentioned above, a stiff layer is an essential part of
constrained-layer vibration-damping constructions of the present
invention. A suitable material for a stiff layer preferably has a
stiffness of at least 100 times the stiffness, i.e., storage
modulus, of the vibration damping material, the stiffness of the
stiff layer being measured in extension. The desired stiffness of
the stiff layer can be varied by adjusting the thickness of this
layer, for example, from 25 micrometers to 5 centimeters, depending
on the modulus of the stiff layer. Examples of suitable stiff
materials for use in a constrained-layer construction include, for
example, metals such as iron, steel, nickel, aluminum, chromium,
cobalt, and copper, and alloys thereof and stiff polymeric
materials such as polystyrene; polyester; polyvinyl chloride;
polyurethane; polycarbonate; polyimide; and polyepoxide;
fiber-reinforced plastics such as glass fiber-reinforced, ceramic
fiber-reinforced, and metal fiber-reinforced polyester; glasses;
and ceramics.
[0168] The vibration damping compositions of the present invention
are useful in a variety of applications that demand effective
damping over a broad range of temperature and frequency, with the
additional requirement that minimum and/or maximum modulus
requirements, over a specified range of temperatures, also be
satisfied. It is often desirable that the region of maximum
damping, that is, the point at which the loss factor is near a
maximum occurs in the center of the desired damping temperature and
frequency range. Designing the optimum damping material for a
specific application requires understanding the effect the
polydiorganosiloxane polyamide segmented copolymer, the organic
polymer, the silicate resin, optional polydiorganosiloxane
oligopolyamide segmented copolymer and filler, and concentration of
each have on damping performance.
[0169] In the case of vibration damping materials providing
pressure sensitive adhesive properties, these materials are
typically applied by first making a tape construction which
comprises a layer of the vibration damping material coated between
two liners at least one of which is coated with a release material.
The vibration damping materials of the invention having pressure
sensitive adhesive qualities and adhere well to polyesters,
polycarbonates, polyolefins such as polyethylene and polypropylene,
and TEFLON of which the latter two classes of materials are
traditionally known to be difficult materials to bond with
adhesives.
[0170] The present invention provides the following
embodiments:
1 . A mixture comprising:
[0171] at least one copolymer comprising at least two repeat units
of Formula I-a:
##STR00012##
wherein:
[0172] each R.sup.1 is independently an alkyl, haloalkyl, aralkyl,
alkenyl, aryl, or aryl substituted with an alkyl, alkoxy, or
halo;
[0173] each Y is independently an alkylene, aralkylene, or a
combination thereof;
[0174] G is a divalent residue equal to a diamine of formula
R.sup.3HN-G-NHR.sup.3 minus the two -NHR.sup.3 groups;
[0175] R.sup.3 is hydrogen or alkyl or R.sup.3 taken together with
G and to the nitrogen to which they are both attached form a
heterocyclic group;
[0176] each group B is independently a covalent bond, an alkylene
of 4-20 carbons, an aralkylene, an arylene, or a combination
thereof;
[0177] n is independently an integer of 0 to 1500; and
[0178] p is an integer of 1 to 10; and
[0179] at least one hot organic polymer selected from the group of
a hot melt processable thermoplastic, a hot melt processable
elastomeric thermoset, a silicone polymer and mixtures thereof;
[0180] wherein the at least one organic polymer is not a copolymer
comprising at least two repeat units of Formula I-a, is not a
tackifying resin, and is not nylon in the form of fibers; and
[0181] wherein the mixture does not occur at the interface between
two layers.
2. The mixture of embodiment 1, wherein the copolymer comprises at
least two repeat units of Formula I-b:
##STR00013##
and wherein the at least one organic polymer is not a copolymer
comprising at least two repeat units of Formula I-b. 3. The mixture
of embodiment 1 or embodiment 2, wherein each R.sup.1 of the
copolymer is methyl. 4. The mixture of embodiment 1 or embodiment
2, wherein at least 50 percent of the R.sup.1 groups of the
copolymer are phenyl, methyl, or combinations thereof. 5. The
mixture of any one of embodiments 1 through 4, wherein each Y of
the copolyiner is an alkylene having 1 to 10 carbon atoms,
phenylene bonded to an alkylene having 1 to 10 carbon atoms, or
phenylene bonded to a first alkylene having 1 to 10 carbon atoms
and to a second alkylene having 1 to 10 carbon atoms. 6. The
mixture of embodiment 5, wherein Y is an alkylene having 1 to 4
carbon atoms. 7. The mixture of any one of embodiments 1 through 6,
wherein the copolymer has a first repeat unit where p is equal to 1
and a second repeat unit where p is at least 2. 8. The mixture of
any one of embodiments 1 through 7, wherein G of the copolymer is
an alkylene, heteroalkylene, arylene, aralkylene,
polydiorganosiloxane, or a combination thereof. 9. The mixture of
any one of embodiments 1 through 8, wherein n of the copolymer is
at least 40. 10. The mixture of any one of embodiments 1 through 9,
wherein R.sup.3 of the copolymer is hydrogen. 11. A composition
comprising a mixture of any one of embodiments 1 through 10 and at
least one tackifying material. 12. The composition of embodiment 11
wherein the tackifying material is a silicate resin or an organic
tackifier. 13. A mixture or composition of any one of embodiments 1
through 12 further comprising one or more additives that are not
hot melt processable. 14. A vibration damping constrained layer
construction comprising at least one substrate having a stiffness
and at least one layer comprising a tackified composition of
embodiment 11, wherein the tackified composition is fixed to the
substrate. 15. A vibration damping composite comprising a flexible
substrate coated thereon a composition of any one of embodiments 11
through 13 or a mixture of any one of embodiments 1 through 10. 16.
A bi-directional vibration damping constrained layer construction
comprising at least two rigid members, each rigid member having a
broad surface proximate to a broad surface of another rigid member
and closely spaced therefrom and a tackified composition of any one
of embodiments 11 through 13, wherein the tackified composition is
contained between the closely spaced rigid members and adhered to
the members. 17. A pressure sensitive adhesive article comprising a
flexible substrate and coated thereon a tackified composition of
any one of embodiments 11 through 13. 18. A pressure sensitive
adhesive article comprising a layer comprising a mixture of any one
of embodiments 1 through 10 or a composition of any one of
embodiments 11 through 13 having a surface that is non-tacky and a
surface that is tacky. 19. A release coated article comprising a
flexible substrate and coated thereon a mixture of any one of
embodiments 1 through 10 or a composition of any one of embodiments
11 through 13. 20. An article comprising a mixture of any one of
embodiments 1 through 10 or a composition of any one of embodiments
11 through 13. 21. The article of embodiment 20, further comprising
a substrate, wherein the mixture or composition comprising the
copolyiner is in a layer adjacent to the substrate. 22. The article
of embodiment 21, further comprising a first substrate and a second
substrate, wherein the mixture or composition comprising the
copolymer is in a layer positioned between the first substrate and
the second substrate. 23. A multilayer film comprising one or more
layers comprising a mixture of any one of embodiments 1 through 10
or a composition of any one of embodiments I through 13. 24. A
process for producing the mixture of any one of embodiments 1
through 10 or composition of any one of embodiments 1 through 13,
wherein the process comprises: continuously providing at least one
polydiorganosiloxane polyamide-containing component and at least
one organic polymer to a vessel; mixing the components to form a
mixture; and conveying the mixture from the vessel. 25. The process
of embodiment 24 wherein the mixing is under substantially
solventless conditions. 26. A process for producing the mixture of
any one of embodiments 1 through 10 or a composition of any one of
embodiments 11 through 13, wherein the process comprises:
continuously providing reactant components for making at least one
polydiroganosiloxane polyamide and at least one organic polymer
that is not reactive with the reactant components; mixing the
components; allowing the reactant components to react to form a
polydiorganosiloxane amide segmented copolymer, and conveying the
mixture from the reactor.
[0182] The foregoing describes the invention in terms of
embodiments foreseen by the inventor for which an enabling
description was available, notwithstanding that insubstantial
modifications of the invention, not presently foreseen, may
nonetheless represent equivalents thereto.
EXAMPLES
[0183] These examples are merely for illustrative purposes only and
are not meant to be limiting on the scope of the appended claims.
All parts, percentages, ratios, and the like in the examples are by
weight, unless noted otherwise. Solvents and other reagents used
were obtained from Sigma-Aldrich Chemical Company; Milwaukee, Wis.
unless otherwise noted.
TABLE-US-00001 Table of Abbreviations Abbreviation or Trade
Designation Description 14K PDMS A polydimethylsiloxane diamine
with an average molecular diamine weight of about 14,000 g/mole
that was prepared as described in U.S. Pat. No. 5,214,119 THF
Tetrahydrofuran DEO Diethyl oxalate Siliconized A siliconized
polycoated kraft paper liner that is Sn catalyzed polycoated with
an easy release on one side and a medium release on the kraft paper
other side commercially available from Loparex Inc., liner
Willowbrook, IL. MORTHANE Thermoplastic elastomeric polyurethane
available from Morton International, Inc., Chicago, IL CRYSTAR PC
Amorphous PET-CPET resins include those such as Crystar.RTM. 5005
from E. I. du Pont de Nemours and Company (DuPont) PEN Polymer
produced by 3M Company comprising the reaction product ethylene
glycol and dimethyl 2,6-naphthalene dicarboxylate CoPEN Polymer
produced by 3M Company comprising the reaction product ethylene
glycol and dimethyl 2,6-naphthalene dicarboxylate and dimethyl
terephthalate SPS-Questra SPS homopolymer, syndiotactic polystyrene
from Dow MA405 Chemical Co. MAKROLON A polycarbonate from Bayer
MaterialScience PC3158 Exxon 129.24 Low density polyethylene resin
available from ExxonMobil Chemical Company, Houston, TX Exxon
Linear low density polyethylene resin available from EXACT 5181
ExxonMobil Chemical Company, Houston, TX mLDPE Medium linear
low-density polyethylene available from ExxonMobil Chemical
Company, Houston, TX ENGAGE A poly-alpha-olefins based
thermoplastic elastomeric material 8200 such as an
ethylene/poly-alpha-olefin copolymer available from Dow Plastics
Co. of Midland, MI KRATON Linear styrene-(ethylene-propylene) block
copolymers available G1657 from Shell Chemical Co. PRIMACOR
PRIMACOR 1410 Copolymer is an ethylene acrylic acid 1410 copolymer
from Dow Plastics PVC PVC white resin from, Alphagary Corp.,
Leonminster, MA PLA Natureworks LLC 3051D resin available from
Natureworks LLC., in Blair, Nebraska, USA SURLYN An ionomer resin,
marketed by the manufacturer, the E. I. DuPont 1705-1 and
Company
Titration Method to Determine Equivalent Weight
[0184] Ten (10) grains (precisely weighed) of the compound of
Preparative Example 1 was added to ajar. Approximately 50 grains
THF solvent (not precisely weighed) was added. The contents were
mixed using a magnetic stir bar mix until the mixture was
homogeneous. The theoretical equivalent weight of precursor was
calculated and then an amount of N-hexylamine (precisely weighed)
in the range of 3 to 4 times this number of equivalents was added.
The reaction mixture was stirred for a minimum of 4 hours.
Bromophenol blue (10-20 drops) was added and the contents were
mixed until homogeneous. The mixture was titrated to a yellow
endpoint with 1.0N (or 0.1N) hydrochloric acid. The number of
equivalents of precursor was equal to the number of equivalents of
N-hexylainine added to the sample minus the number of equivalents
of hydrochloric acid added during titration. The equivalent weight
(grams/equivalent) was equal to the sample weight of the precursor
divided by the number of equivalents of the precursor.
Inherent Viscosity (IV) for Polydiorganosiloxane Polyoxamide Block
Copolymer
[0185] Average inherent viscosities (IV) were measured at
30.degree. C. using a Canon-Fenske viscometer (Model No.50 P296) in
a tetrahydrofuran (THF) solution at 30.degree. C. at a
concentration of 0.2 grams per deciliter (g/dL). Inherent
viscosities of the materials of the invention were found to be
essentially independent of concentration in the range of 0.1 to 0.4
g/dL. The average inherent viscosities were averaged over 3 or more
runs. Any variations for determining average inherent viscosities
are set forth in specific Examples.
Preparative Example 1
[0186] A sample of 14K PDMS diamine (830.00 grams) was placed in a
2-liter, 3-neck resin flask equipped with a mechanical stirrer,
heating mantle, nitrogen inlet tube (with stopcock), and an outlet
tube. The flask was purged with nitrogen for 15 minutes and then,
with vigorous stirring, diethyl oxalate (33.56 grams) was added
dropwise. This reaction mixture was stirred for approximately one
hour at room temperature and then for 75 minutes at 80.degree. C.
The reaction flask was fitted with a distillation adaptor and
receiver. The reaction mixture was heated under vacuum (133
Pascals, 1 Torr) for 2 hours at 120.degree. C. and then 30 minutes
at 130.degree. C., until no further distillate was able to be
collected. The reaction mixture was cooled to room temperature to
provide the compound of Formula I product. Gas chroinatographic
analysis of the clear, mobile liquid showed that no detectable
level of diethyl oxalate remained. The ester equivalent weight was
determined using .sup.1H NMR (equivalent weight equal to 7,916
grams/equivalent) and by titration (equivalent weight equal to
8,272 grams/equivalent).
Preparative Example 2
[0187] Into a 20.degree. C. 10-gallon (37.85-Liter) stainless steel
reaction vessel, 18158.4 grams of 14K ethyl oxalylamidopropyl
terminated polydimethyl siloxane (titrated MW=14,890, which was
prepared in a fashion similar to the description in the Preparative
Example 1, with the volumes adjusted accordingly) was placed. The
vessel was subjected to agitation (75 revolutions per minute
(rpm)), and purged with nitrogen flow and vacuum for 15 minutes.
The kettle was then heated to 80.degree. C. over the course of 25
minutes. Ethylene diamine (73.29 grams, GFS Chemicals) was vacuum
charged into the kettle, followed by 73.29 grams of toluene (also
vacuum charged). The kettle was then pressurized to 1 psig (6894
Pa) and heated to a temperature of 120.degree. C. After 30 minutes,
the kettle was heated to 150.degree. C. Once a temperature of
150.degree. C. was reached, the kettle was vented over the course
of 5 minutes. The kettle was subjected to vacuum (approximately 65
mm Hg, 8665Pa) for 40 minutes to remove the ethanol and toluene.
The kettle was then pressured to 2 psig (13789 Pa) and the viscous
molten polymer was then drained into TEFLON coated trays and
allowed to cool. The cooled silicone polyoxamide product,
polydiorganosiloxane polyoxamide block copolymer, was then ground
into fine pellets.
Preparative Example 3
[0188] This example was prepared as in Preparative Example 2 except
1.0 mole % of the ethylene diamine (EDA) was replaced with
Tris(2-aminoethyl)amine. The IV of this material was determined to
be 1.37 g/dL (in THF).
Preparative Example 4
[0189] Diethyl oxalate (241.10 grams) was placed in a 3-liter,
3-neck resin flask equipped with a mechanical stirrer, heating
mantle, nitrogen inlet tube (with stopcock), and an outlet tube.
The flask was purged with nitrogen for 15 minutes and 5K PDMS
diamine (a polydimethylsiloxane diamine with an average molecular
weight of about 5,000 g/mole that was prepared as described in
Example 2 in U.S. Pat. No. 5,214,119) (2,028.40 grams, MW=4,918)
was added slowly with stirring. After 8 hours at room temperature,
the reaction flask was fitted with a distillation adaptor and
receiver, the contents stirred and heated to 150.degree. C. under
vacuum (1 Torr, 133 Pa) for 4 hours, until no further distillate
was able to be collected. The remaining liquid was cooled to room
temperature to provide 2,573 grains of oxamido ester terminated
product. Gas chromatographic analysis of the clear, mobile liquid
showed that no detectable level of diethyl oxalate remained.
Molecular weight was determined by .sup.1H NMR (MW=5,477
grams/mole) and titration (Equivalent weights of 2,573 grams/mole
and 2,578 grams/mole).
Preparative Example 5
[0190] Into a 20.degree. C. 10-gallon (37.85-Liter) stainless steel
reaction vessel, 40 pounds of the material from Preparative Example
4 was placed. The vessel was subjected to agitation (80 rpm) and
purged with Nitrogen flow and vacuum for 15 minutes. The reactor
was then nitrogen pressurized to 5 pounds per square inch and
heated to 90.degree. C. over the course of 25 minutes. Ethylene
diamine (0.44 pound) was added to the reactor. This addition was
followed by 80 grams of toluene. Next the reactor was heated to a
temperature of 105.degree. C. and the pressure on the reactor was
slowly vented over the course of 5 minutes. The reactor was then
subjected to vacuum (approximately 20 mm Hg, 2666 Pa) for one hour
to remove the ethanol and toluene. The reactor was then
repressurized to 2 psig (13789 Pa) and the viscous molten product
was drained into a TEFLON-coated tray and allowed to cool. The
cooled silicone polyoxamide product, was then ground into fine
pellets. The IV of this material was determined to be 1.135 g/dL
(in THF).
Preparative Example 6
[0191] This example was prepared as in Preparative Example 2,
except 3.0 mole % of the ethylene diamine (EDA) was replaced with
Tris(2-aminoethyl)amine.
Preparative Example 7
[0192] Into a 20.degree. C. 10-gallon (37.85-Liter) stainless steel
reaction vessel, 1 8158.4 grams of 5K ethyl oxalylamidopropyl
terminated polydimethyl siloxane (titrated MW=5,146, which was
prepared in a Preparative Example 4) was placed. The vessel was
subjected to agitation (75 rpm), and purged with nitrogen flow and
vacuum for 15 minutes. The kettle was then heated to 80.degree. C.
over the course of 25 minutes. Ethylene diamine (250.3 grains, GFS
Chemicals) was vacuum charged into the kettle, followed by 73.29
grams of toluene (also vacuum charged). The kettle was then
pressurized to 1 psig (6894 Pa) and heated to a temperature of
120.degree. C. After 30 minutes, the kettle was heated to
150.degree. C. Once a temperature of 150.degree. C. was reached,
the kettle was vented over the course of 5 minutes. The kettle was
subjected to vacuum (approximately 65 mm Hg, 8665Pa) for 40 minutes
to remove the ethanol and toluene. The kettle was then pressured to
2 psig (13789 Pa) and the viscous molten polymer was then drained
into TEFLON-coated trays and allowed to cool. The cooled amine
capped silicone polyoxamide oligoiner product, was then ground into
fine crumbs.
Color, Haze, and Luminous Transmittance Measurement
[0193] The luminous transmittance and haze of the samples were
measured according to the American Society for Testing and
Materials (ASTM) Test Method D 1003-95 ("Standard Test for Haze and
Luminous Transmittance of Transparent Plastic") using a TCS Plus
Spectrophotometer from BYK-Gardner Inc., Silver Springs, Md. Color
measurements were made using the same instrument, following the CIE
(French abbreviation for Commission of Lighting) established
international color scale of L*, a*, b*.
Release Test
[0194] Samples were prepared for release testing by attaching
3-layer laminates of backing/adhesive/liner to a 17.8-centimeter
(cm) by 33-centimeter steel panel using double-coated adhesive tape
(commercially available from 3M Company under the trade designation
"410B") via the non-release side of the liner using a 2.3 kg rubber
roller. The backing/adhesive was then peeled from the liner at
180.degree. at a rate of 2.3 meters/minute (90 inches/minute). All
tests were done in a facility at constant temperature (70.degree.
C.) and constant humidity (50% RH), unless noted. In the case of
shocky peel, the minimum, maximum, and average peel values are all
reported to indicate the level of shockiness and a description of
the peel is also included. The peel tester used for all examples
was an IMass model SP2000 peel tester obtained from IMASS, Inc.,
Accord, Mass.. Measurements were obtained in ounces/inch and in
some cases converted to grains per inch.
Release Test for UV Polymerized Adhesive Samples
[0195] A 1-mil thick PET film was laminated to the pressure
sensitive adhesive side of the sample resulting in a 3 layer
construction of 1-mil PET/2-mil pressure sensitive adhesive/liner.
The 3 layer sample was prepared for release testing by cutting a
test sample strip of 2.54-cm wide by nominally 12 cm in length. The
test sample, liner side down, was then attached to the working
platen of a an INSTRUMENTORS, Inc. Slip/Peel tester Model 3M90A
using a 2.54-cm wide double-coated adhesive tape and a 2.54-cm wide
single sided tape (commercially available from 3M Company under the
trade designation "9579" and "8403", respectively). The test sample
was rolled once on the working platen with a 2.3-kg rubber roller.
The backing and pressure sensitive adhesive was then peeled from
the liner at 180.degree. at a rate of 2.3 meters/minute (90
inches/minute) over a five second data collection time. A minimum
of two samples were tested; the reported release force value is an
average of the release force value from each of the test samples.
All tests were done in a facility at constant temperature
(70.degree. C.) and constant humidity (50% RH) unless noted.
Measurements were obtained in ounces/inch and in some cases
converted to grains per inch
Examples 1-4 and Comparative Examples 1-4: Extrusion Blending Film
Making Process
[0196] A 3/4-inch (0.19-dM) Brabender single screw extruder with a
mixing screw was used to produce blended films in the following
examples. After melting and mixing, in the single screw extruder,
the extrudate was forced through a 6-inch (1.524-dM) flat cast
extrusion die to form a molten film. The molten film was then
passed through a chilled roll stack to cool and solidify the resins
into final, finished film form.
[0197] To generate examples for release testing, the adhesive side
of four different adhesive products available from 3M Co., Saint
Paul, Minn. were laminated to the films.
[0198] Four commercial tapes were used: (Red) 3M SCOTCHCAL 7725-13;
(White) 3M SCOTCHCAL 160-30; 845 Book Tape; and 371 Box Tape, all
available from 3M Co., Saint Paul, Minn.
Comparative Example 1
[0199] A film of 100% Exxon 129.24 low density polyethylene was
produced using the above Extrusion Blending Film Making Process.
Extrusion zone temperatures of 185.degree. C., 190.degree. C.,
195.degree. C., 200.degree. C., 200.degree. C. were used in the
extrusion process. The film samples produced had a thickness of
approximately 5 mils (125 microns).
Comparative Example 2
[0200] One hundred percent (100%) of Preparative Example 2 was fed
to the extruder to produce films using the process described above.
Extrusion profile temperatures of 100.degree. C., 115.degree. C.,
120.degree. C., 140.degree. C., 140.degree. C. were used, the
extrusion pressure was 60 pounds (413685 Pa) at 90 rpm. The
resultant extruded film was transparent. The resultant extruded
film was rubbery and elastic and required the use of a PET carrier
liner to carry the material through the chilled nip rolls and
winder. The film samples produced had a thickness of approximately
5 mils (125 microns).
Example 1
[0201] One percent (1%) of Preparative Example 2 was dry blended
with 99% Exxon 129.24 low density polyethylene and fed to the
extruder to produce films using the process described above.
Extrusion profile temperatures of 100.degree. C., 115.degree. C.,
120.degree. C., 140.degree. C., 140.degree. C. were used, extrusion
pressure was 610 pounds (4205802 Pa) at 90 rpm. The resultant film
had physical properties similar to the polyethylene film in
Comparative Example 1. The resultant film was transparent. The film
samples produced had a thickness of approximately 5 mils (125
microns).
Example 2
[0202] Two percent (2%) of Preparative Example 2 was dry blended
with 98% Exxon 129.24 low density polyethylene and fed to the
extruder to produce films using the process described above.
Extrusion profile temperatures of 100.degree. C., 115.degree. C.,
120.degree. C., 140.degree. C., 140.degree. C. were used, extrusion
pressure was 500 pounds (3447379 Pa) at 90 rpm. The resultant
extruded film was transparent. The film samples produced had a
thickness of approximately 5 mils (125 microns).
Example 3
[0203] Three percent (3%) of Preparative Example 2 was dry blended
with 97% Exxon 129.24 low density polyethylene and was fed to the
extruder to produce films using the process described above.
Extrusion profile temperatures of 100.degree. C., 115.degree. C.,
120.degree. C., 140.degree. C., 140.degree. C. were used, extrusion
pressure was 620 pounds(4274750 Pa) at 90 rpm. The resultant
extruded film had a transparent, hazy appearance. The film samples
produced had a thickness of approximately 5 mils (125 microns).
Example 4
[0204] Four percent (4%) of Preparative Example 2 was dry blended
with 95% Exxon 129.24 low density polyethylene and was fed to the
extruder to produce films using the process described above.
Extrusion profile temperatures of 100.degree. C., 115.degree. C.,
120.degree. C., 140.degree. C., 140.degree. C. were used, extrusion
pressure was 580 pounds (3998959 Pa) at 90 rpm. The resultant
extruded film had a transparent, hazy appearance. The film samples
produced had a thickness of approximately 5 mils (125 microns).
Comparative Example 3
[0205] One hundred percent (100%) Exxon 129.24 low density
polyethylene was introduced into the extruder (now at the lower
temperatures used in Examples 1-5) and the extruder shut down due
to excessive torque. Sample film could not be collected at these
extrusion conditions (when the silicone additive of the invention
was not present to form a mixture).
Comparative Example 4
[0206] A film of 100% Exxon EXACT 5181 linear low density
polyethylene was produced using the above steps. Extrusion zone
temperatures of 185.degree. C., 190.degree. C., 195.degree. C.,
200.degree. C., 200.degree. C. were used in the extrusion
process.
Examples 5-14
[0207] These film examples were made with the method described in
Comparative Example 4 and Examples 2 and 4. The table below details
the type and percentage (%) of each polymer used to create the
example films. Extrusion zone temperatures of 1 85.degree. C.,
190.degree. C., 195.degree. C., 200.degree. C., 200.degree. C. were
used in the extrusion process to make these examples. The film
samples produced had a thickness of approximately 5 mils (125
microns).
Examples 15-17 and Comparative Examples 5-7
[0208] The films made in Comparative Examples 1 and 4 and Examples
6-8, were used to make film composites. The PSA/film composite was
prepared by coating an acrylic radiation sensitive syrup (isooctyl
acrylate:acrylic acid at 90:10 (w/w), that was less than 10%
polymerized) using a notched bar coater to form a continuous web of
nominally 2 mils (0.002 inch, 0.051 millimeter) thickness on the
example films of the invention. The coating was then polymerized to
more than 95% by exposing the radiation sensitive syrup to UV
radiation in a inert environment, created with nitrogen environment
or an overlay with a 1 mil (0.001 inch, 0.025 millimeter) thick
polyester terephthalate (PET) film. Upon curing the example films
of the invention and the polymerized syrup formed a pressure
sensitive adhesive similar to that described in Examples 1-7 in
U.S. Pat. No. 4,181,752. (Note the table will explain what the %'s
are of each resin and the manner we used was already described
above for both the films and the composite samples.)
TABLE-US-00002 TABLE 1 Organic Silicone Percent Polymer Block
Silicone Heat Mixed With Polymer Block Tape Aged Example Silicone
Block Used in Polymer Used for Release Release Number Polymer
Mixture Used Testing in N/dm in N/dm Comp. Exxon EXACT Preparative
0 7725-13 2.54 at 3.20 at 7 Ex. 4 5181 Example 2 adhesive 24 hrs at
days at coated RT 65.degree. C. graphic film Ex. 5 Exxon EXACT
Preparative 2% 7725-13 1.40 at 0.70 at 7 5181 Example 2 adhesive 24
hrs at days at coated RT 65.degree. C. graphic film Ex. 6 Exxon
EXACT Preparative 4% 7725-13 1.05 at 1.57 at 7 5181 Example 2
adhesive 24 hrs at days at coated RT 65.degree. C. graphic film Ex.
7 Exxon 129.24 Preparative 4% 7725-13 7.88 at 6.64 at 7 low density
Example 2 adhesive 24 hrs at days at polyethylene coated RT
65.degree. C. graphic film Comp. 129.24 low Preparative 0 7725-13
3.68 at 7.75 at 7 Ex. 1 density Example 2 adhesive 24 hrs at days
at polyethylene coated RT 65.degree. C. graphic film Ex. 8 Exxon
129.24 Preparative 2% 7725-13 6.65 at 4.52 at 7 low density Example
2 adhesive 24 hrs at days at polyethylene coated RT 65.degree. C.
graphic film Ex. 9 Exxon 129.24 Preparative 2% 7725-13 5.25 at Not
tested low density Example 5 adhesive 24 hrs at polyethylene coated
RT graphic film Ex. 10 Exxon 129.24 Preparative 2% 7725-13 7.88 at
Not tested low density Example 7 adhesive 24 hrs at polyethylene
coated RT graphic film Ex. 11 Exxon 129.24 Preparative 2% 7725-13
4.03 at Not tested low density Example 2 adhesive 24 hrs at
polyethylene coated RT graphic film Ex. 12 Exxon 129.24 Preparative
2% 7725-13 4.38 at Not tested low density Example 6 adhesive 24 hrs
at polyethylene coated RT graphic film Ex. 13 Exxon 129.24
Preparative 2% 7725-13 5.95 at Not tested low density Example 2
adhesive 24 hrs at polyethylene coated RT graphic film Comp. Exxon
129.24 Preparative 0% 160-30 9.28 at 3 Not tested Ex. 1 low density
Example 2 adhesive days at polyethylene coated RT graphic film Ex.
14 PVC Preparative 4% 7725-13 Not 10.78 at 7 Example 2 adhesive
tested days at coated 65.degree. C. graphic film Ex. 9 Exxon 129.24
Preparative 2% 160-30 8.75 at 3 Not tested low density Example 2
adhesive days at polyethylene coated RT graphic film Ex. 13 Exxon
129.24 Preparative 4% 160-30 6.65 at 3 Not tested low density
Example 2 adhesive days at polyethylene coated RT graphic film
Comp. Exxon EXACT Preparative 0 160-30 2.10 at 3 Not tested Ex. 4
5181 Example 2 adhesive days at coated RT graphic film Ex. 5 Exxon
EXACT Preparative 2% 160-30 0.70 at 3 Not tested 5181 Example 2
adhesive days at coated RT graphic film Ex. 6 Exxon EXACT
Preparative 4% 160-30 0.53 at 3 Not tested 5181 Example 2 adhesive
days at coated RT graphic film Comp. Exxon 129.24 Preparative 0% UV
cured 1.74 after 0.90 after 1 Ex. 5 low density Example 2 PSA, 1
week at week at polyethylene cured in RT 65.degree. C. place on
example substrate Ex. 15 Exxon 129.24 Preparative 2% UV cured 1.06
after 0.96 after 1 low density Example 2 PSA, 1 week at week at
polyethylene cured in RT 65.degree. C. place on example substrate
Ex. 16 Exxon 129.24 Preparative 4% UV cured 1.59 after 0.89 after 1
low density Example 2 PSA, 1 week at week at polyethylene cured in
RT 65.degree. C. place on example substrate Ex. 17 Exxon EXACT
Preparative 4% UV cured .46 after 0.61 after 1 5181 Example 2 PSA,
1 week at week at cured in RT 65.degree. C. place on example
substrate Comp. Exxon EXACT Preparative 0 UV cured 4.04 at 2.77 at
19 Ex. 6 5181 Example 2 PSA, 24 hrs at days at RT cured in RT place
on example substrate Comp. Siliconized 0 UV cured 1.00 after 0.89.
after Ex. 7 polycoated PSA, 1 week at 1 week at kraft paper cured
in RT 65.degree. C. liner place on example substrate
Example 18
[0209] Blended films of polyethylene terephthalate (PET) and
Silicone Polyoxamide (Preparative Example 5) were produced as
follows: Invista 8602 PET (approximately 0.60 IV) was loaded into a
K-Tron Model K-SFS-24/6 pellet feeder (feeder #1). Silicone
Polyoxamide was loaded into a similar K-Tron Model K-SFS-24/6
pellet feeder (feeder #2). The outlets of these feeders were placed
over the feed throat of a 25-mm Berstroff twin-screw extruder.
Downstream from the Berstorff was a neck tube, gear pump, neck
tube, feedblock, and 8-inch die. The die was positioned immediately
over and in close proximity to a chilled casting roll and
associated wind-up equipment. This set-up was utilized to produce
cast web samples of film. The die, feedblock, necktubes, and gear
pump were all heated to a temperature of 530.degree. F.
(277.degree. C.). The twin-screw extruder had a progressive heat
profile beginning at 450.degree. F. (232.degree. C.) and increasing
to 530.degree. F. (277.degree. C.) over the course of the heat
zones.
[0210] The Silicone Polyoxamide and Invista 8602 PET resin
(available from Invista of Charlotte, N.C. were fed to the extruder
at various ratios with a series of melt blended samples produced
ranging from 6 to 22 wt % Silicone Polyoxamide dispersed in PET.
These approximate 20-mil thick cast web films exhibited varying
levels of haze, graffiti resistance, and slip properties, all
increasing with the level of Silicone Polyoxamide dispersed in the
film.
Example 19
[0211] Blended films of polyethylene terephthalate (PET) and
Silicone Polyoxamide (Preparative Example 2) were produced as
follows: Invista 8602 PET resin (available from Invista of
Charlotte, N.C. (approximately 0.60 IV) was loaded into a K-Tron
Model K-SFS-24/6 pellet feeder (feeder #1). Silicone Polyoxamide
was loaded into a similar K-Tron Model K-SFS-24/6 pellet feeder
(feeder #2). The outlets of these feeders were placed over the feed
throat of a 25-mm Berstroff twin-screw extruder. Downstream from
the Berstorff was a neck tube, gear pump, neck tube, feedblock, and
8-inch die. The die was positioned immediately over and in close
proximity to a chilled casting roll and associated wind-up
equipment. This set-up was utilized to produce cast web samples of
film. The die, feedblock, necktubes, and gear pump were all heated
to a temperature of 530.degree. F. (277.degree. C.). The twin-screw
extruder had a progressive heat profile beginning at 450.degree. F.
(232.degree. C.) and increasing to 530.degree. F. (277.degree. C.)
over the course of the heat zones.
[0212] The Silicone Polyoxamide and Invista PET were fed to the
extruder at various ratios with a series of melt blended samples
produced ranging from 6 to 22 wt % Silicone Polyoxamide dispersed
in PET. These approximately 20-mil thick cast web films exhibited
varying levels of haze, graffiti resistance, and slip properties,
all increasing with the level of Silicone Polyoxamide dispersed in
the film.
Example 20
[0213] Blended films of Low Melt PEN (an approximately 0.48 IV
polymer produced by 3M company comprising the reaction product of
ethylene glycol and 90 mol % (on esters basis) dimethyl
2,6-naphthalene dicarboxylate and 10 mol % (on esters basis)
Dimethyl Terephthalate)) and Silicone Polyoxamide (Preparative
Example 3) were produced as follows: Low Melt PEN was loaded into a
K-Tron Model K-SFS-24/6 pellet feeder (feeder #1). Silicone
Polyoxamide was loaded into a similar K-Tron Model K-SFS-24/6
pellet feeder (feeder #2). The outlets of these feeders were placed
over the feed throat of a 25-mm Berstroff twin-screw extruder.
Downstream from the Berstorff was a neck tube, gear pump, neck
tube, feedblock, and 8-inch die. The die was positioned immediately
over and in close proximity to a chilled casting roll and
associated wind-up equipment. This set-up was utilized to produce
cast web samples of film. The die, feedblock, necktubes and gear
pump were all heated to a temperature of 530.degree. F.
(277.degree. C.). The twin-screw extruder had a progressive heat
profile beginning at 450.degree. F. (232.degree. C.) and increasing
to 530.degree. F. (277.degree. C.) over the course of the heat
zones.
[0214] The Silicone Polyoxamide and Low Melt PEN were fed to the
extruder at various ratios with a series of melt blended samples
produced ranging from 6 to 22 wt % Silicone Polyoxainide dispersed
in Low Melt PEN. These approximate 20-ml thick cast web films
exhibited varying levels of haze, graffiti resistance, and slip
properties, all increasing with the level of Silicone Polyoxamide
dispersed in the film.
Example 21
[0215] Blended films of polyethylene naphthalate (PEN) (a
approximately 0.48 IV polymer produced by 3M company comprising the
reaction product ethylene glycol and Dimethyl 2,6-Naphthalene
Dicarboxylate) and Silicone Polyoxamide (Preparative Example 2)
were produced as follows: PEN was loaded into a K-Tron Model
K-SFS-24/6 pellet feeder (feeder #1 ). Silicone Polyoxamide was
loaded into a similar K-Tron Model K-SFS-24/6 pellet feeder (feeder
#2). The outlets of these feeders were placed over the feed throat
of a 25-mm Berstroff twin-screw extruder. Downstream from the
Berstorff was a neck tube, gear pump, neck tube, feedblock, and
8-inch die. The die was positioned immediately over and in close
proximity to a chilled casting roll and associated wind-up
equipment. This set-up was utilized to produce cast web samples of
film. The die, feedblock, necktubes, and gear pump were all heated
to a temperature of 540.degree. F. (282.degree. C.). The twin-screw
extruder had a progressive heat profile beginning at 480.degree. F.
(249.degree. C.) and increasing to 540.degree. F. (282.degree. C.)
over the course of the heat zones.
[0216] The Silicone Polyoxamide and PEN were fed to the extruder at
various ratios with a series of melt blended samples produced
ranging from 5 to 70 wt % Silicone Polyoxamide dispersed in PEN.
These approximately 25-mil thick cast web films exhibited varying
levels of haze, graffiti resistance, and slip properties, all
increasing with the level of Silicone Polyoxamide dispersed in the
film.
Examples 22-43 and Comparative Examples 8-13
[0217] Ten-gram (I0-gram) batches were dry blended by hand, in the
percentage shown in Table 2 below, and fed into a DSM micro 15
extruder. Each batch was pushed into the extruder using a plunger.
Each sample was mixed 2-4 minutes at 150 rpm except for Examples
28-31 which were mixed at 100 rpm. The melted mixture came out the
end of the extruder into a small heated cylinder for molding into
bars or onto a heated piece of aluminum for creating pressed
sheets. The cylinder was placed in front of a die and a plunger
forced the material into the die. The material on the sheet of
aluininum had another sheet of aluminum placed on top and was put
into a Carver hydraulic press. The press was set at the same
temperature used for extrusion of the example. The material was
flattened as the platens came together. Each sample used a
different amount of pressure to obtain desired thickness of 5
mils.
[0218] The materials were tested according to the Release Test and
the results reported below in Tables 3 and 4.
TABLE-US-00003 TABLE 2 Percent and Type Organic 10 g batches
Polymer Organic Mixed with Percent Process Preparative Polymer
Preparative Preparative Temperature Example 2 (in Example Number
Example 2 Example 2 Used (.degree. C.) (in grams) grams) Ex. 22
99.5% 0.50% 196 0.05 9.95 MORTHANE PE44-203 Ex. 23 98.25% 1.75% 196
0.175 9.825 MORTHANE PE44-203 Ex. 24 97% 3.00% 196 0.3 9.7 MORTHANE
PE44-203 Ex. 25 75% 25.00% 196 2.5 7.5 MORTHANE PE44-203 Comp. 100%
0.00% 196 10 0 Ex. 8 KRATON G1567 Ex. 26 99.5% 0.50% 196 0.5 9.95
KRATON G1567 Ex. 27 98.25% 1.75% 196 0.175 9.825 KRATON G1567 Ex.
28 97% KRATON 3.00% 196 0.3 9.7 G1567 Ex. 29 20% KRATON 80.00% 196
8 2 G1567 Ex. 30 75% KRATON 25.00% 196 2.5 7.5 G1567 Comp. 100% SPS
0.00% 274 10 0 Ex. 9 Ex. 31 99.5% SPS 0.50% 274 0.5 9.95 Ex. 32
98.25% SPS 1.75% 274 0.175 9.825 Ex. 33 97% SPS 3.00% 274 0.3 9.7
Comp. 100% 0.00% 274 10 0 Ex. 10 CRYSTAR PC Ex. 34 99.5% 0.50% 274
0.5 9.95 CRYSTAR PC Ex. 35 98.25% 1.75% 274 0.175 9.825 CRYSTAR PC
Ex. 36 97% 3.00% 274 0.3 9.7 CRYSTAR PC Comp. 100% PET 0.00% 274 10
0 Ex. 11 Ex. 37 99.5% PET 0.50% 274 0.5 9.95 Ex. 38 98.25% PET
1.75% 274 0.175 9.825 Ex. 39 97% PET 3.00% 274 0.3 9.7 Comp. 100%
0.00% 196 10 0 Ex. 12 ENGAGE 8200 Ex. 40 99.5% 0.50% 196 0.5 9.95
ENGAGE 8200 Ex. 41 98.25% 1.75% 196 0.175 9.825 ENGAGE 8200 Ex. 42
97% ENGAGE 3.00% 196 0.3 9.7 8200 Ex. 43 0.5% 99.50% 196 10 0
ENGAGE 8200 Comp. None 100.00% 196 0 10 Ex. 13
TABLE-US-00004 TABLE 3 Results of Release Testing the Examples of
22-43 and Comparative Examples 8-13 Using Book Tape 845 Percent of
Heat Aged Percent and Type Silicone Release Release Organic Polymer
Block (N/dm) (N/dm) Example Mixed with Silicone Polymer Room 4 Days
at Number Block Polymer Used Temp. 65.degree. C. Ex. 22 99.5%
MORTHANE 0.50% 38.4 84.2 PE44-203 Ex. 23 98.25% 1.75% 41.0 96.4
MORTHANE PE44- 203 Ex. 24 97% MORTHANE 3.00% 45.0 95.2 PE44-203 Ex.
25 75% MORTHANE 25.00% 35.8 64.1 PE44-203 Comp. 100% KRATON 0.00%
6.3 24.7 Ex. 8 G1567 Ex. 26 99.5% KRATON 0.50% 6.3 17.9 G1567 Ex.
27 98.25% KRATON 1.75% 8.2 22.5 G1567 Ex. 28 97% KRATON 3.00% 7.7
20.5 G1567 Ex. 29 20% KRATON 80.00% 0.5 1.1 G1567 Ex. 30 75% KRATON
25.00% 5.5 24.6 G1567 Comp. 100% SPS 0.00% 21.9 34.8 Ex. 9 Ex. 31
99.5% SPS 0.50% 4.4 36.8 Ex. 32 98.25% SPS 1.75% 9.1 30.5 Ex. 33
97% SPS 3.00% 13.2 22.8 Comp. 100% CRYSTAR PC 0.00% 17.4 20.5 Ex.
10 Ex. 34 99.5% CRYSTAR 0.50% 27.8 36.1 PC Ex. 35 98.25% CRYSTAR
1.75% 12.5 54.3 PC Ex. 36 97% CRYSTAR PC 3.00% 14.0 50.1 Comp. 100%
PEN 0.00% 11.0 64.0 Ex. 11 Ex. 37 99.5% PEN 0.50% 31.9 62.6 Ex. 38
98.25% PEN 1.75% 41.0 59.6 Ex. 39 97% PEN 3.00% 24.1 56.5 Comp.
100% ENGAGE 0.00% 3.3 17.5 Ex. 12 8200 Ex. 40 99.5% ENGAGE 0.50%
3.1 11.2 8200 Ex. 41 98.25% ENGAGE 1.75% 3.4 13.5 8200 Ex. 42 97%
ENGAGE 8200 3.00% 2.8 8.2 Ex. 43 0.5% ENGAGE 8200 99.50% 8.0 24.8
Comp. None 100.00% 0.5 1.3 Ex. 13
TABLE-US-00005 TABLE 4 Results of Release Testing the Examples of
22-43 and Comparative Examples 8-13 Using Box Tape 371 Percent and
Type Heat Aged Organic Polymer Release Release Mixed with Percent
(N/dm) (N/dm) Example Preparative Silicone Block Room 4 Days at
Number Example 2 Polymer Used Temp. 65.degree. C. Ex. 22 99.5%
0.50% 17.6 32.6 MORTHANE PE44-203 Ex. 23 98.25% 1.75% 15.5 31.6
MORTHANE PE44-203 Ex. 24 97% MORTHANE 3.00% 16.5 31.7 PE44-203 Ex.
25 75% MORTHANE 25.00% 11.0 33.1 PE44-203 Comp. 100% KRATON 0.00%
20.2 Not tested Ex. 8 G1567 Ex. 26 99.5% KRATON 0.50% 18.7 Not
tested G1567 Ex. 27 98.25% KRATON 1.75% 18.7 Not tested G1567 Ex.
28 97% KRATON 3.00% 20.1 Not tested G1567 Ex. 29 20% KRATON 80.00%
0.3 0.7 G1567 Ex. 30 75% KRATON 25.00% 12.4 38.2 G1567 Comp. 100%
SPS 0.00% 34.5 46.7 Ex. 9 Ex. 31 99.5% SPS 0.50% 6.3 26.1 Ex. 32
98.25% SPS 1.75% 11.5 55.1 Ex. 33 97% SPS 3.00% 22.3 27.4 Comp.
100% CRYSTAR 0.00% 16.1 59.7 Ex. 10 PC Ex. 34 99.5% CRYSTAR 0.50%
27.6 18.3 PC Ex. 35 98.25% CRYSTAR 1.75% 17.0 42.2 PC Ex. 36 97%
CRYSTAR 3.00% 17.7 38.3 PC Comp. 100% PEN 0.00% 9.0 51.5 Ex. 11 Ex.
37 99.5% PEN 0.50% 31.6 48.2 Ex. 38 98.25% PEN 1.75% 28.4 48.7 Ex.
39 97% PEN 3.00% 25.6 29.6 Comp. 100% ENGAGE 0.00% 21.9 36.4 Ex. 12
8200 Ex. 40 99.5% ENGAGE 0.50% 22.4 37.1 8200 Ex. 41 98.25% ENGAGE
1.75% 26.0 32.8 8200 Ex. 42 97% ENGAGE 3.00% 22.0 20.6 8200 Ex. 43
0.5% ENGAGE 99.50% 22.4 43.8 8200 Comp. None 100.00% 0.4 0.8 Ex.
13
Examples 44-47 and Comparative Example 14
[0219] The compounded blends (compositions of which are reported in
Table 5) were mixed by hand and flood feed into a 1-1/4 Killion
Single Screw extruder, compression ration 2.93:1. The material
melted and mixed in the extruder. The melted material was metered
thru a necktube into a 6-inch (1.524-dM) flat film die. The molten
material came out the die onto a heated chrome roll and was nipped
with a rubber roll. Throat cooling was needed to prevent
surging.
[0220] Extrusion conditions were monitored to record processing
conditions as the percentage of silicone block copolymer varied.
The results are reported in Table 6.
[0221] The materials were tested according to the Release Test and
the results reported below in Table 7.
TABLE-US-00006 TABLE 5 2268 gram batch Percentage Preparative
Example Preparative Percentage Example 2 mLDPE Number Example 2
mLDPE (grams) (grams) Comp. Ex. 14 100% 0 2268 Ex. 44 0.05% 99.95%
1.134 2266.828 Ex. 45 0.10% 99.90% 2.268 2265.694 Ex. 46 0.50%
99.50% 11.340 2154.563 Ex. 47 2.50% 97.50% 56.699 2211.263
TABLE-US-00007 TABLE 6 Single Screw Extrusion Data Example Zone 1
Zone 2 Zone 3 Clamp Necktube Speed Pressure Melt Temp. Number
(.degree. C.) (.degree. C.) (.degree. C.) Ring (.degree. C.)
(.degree. C.) Die (.degree. C.) (rpm) (Pascals) Amps (.degree. C.)
Extruder set 257.22 282.22 279.44 279.44 279.44 279.44 44 points
Comp. Ex. 14 246.11 282.78 279.44 279.44 279.44 279.44 43.9
17236893 17 291.11 Ex. 44 223.33 282.22 279.44 278.89 278.89 279.44
43.2 15168466 14 287.22 Ex. 45 222.78 282.22 279.44 278.89 278.89
279.44 43.2 13789515 13 283.33 Ex. 46 221.11 281.11 277.78 279.44
279.44 279.44 44.1 13789515 10 287.22 Ex. 47 222.78 281.67 280.00
279.44 277.22 279.44 43.2 13100039 9 286.11
TABLE-US-00008 TABLE 7 Release testing Results Percent Release
(N/dm Example Preparative Percent Tape Used for at Room Temp.,
Number Example 2 mLDPE Testing 1 Minute Dwell) Comp. -- 100% Book
tape 845 12.5 Ex. 14 Ex. 44 0.05% 99.95% Book tape 845 13.3 Ex. 45
0.10% 99.90% Book tape 845 12.3 Ex. 46 0.50% 99.50% Book tape 845
11.3 Ex. 47 2.50% 97.50% Book tape 845 9.3 Comp. -- 100% Box tape
371 12.4 Ex. 14 Ex. 44 0.05% 99.95% Box tape 371 10.9 Ex. 45 0.10%
99.90% Box tape 371 10.7 Ex. 46 0.50% 99.50% Box tape 371 9.4 Ex.
47 2.50% 97.50% Box tape 371 10.3
Examples 48-51 and Comparative Example 15
[0222] The compounded blends (compositions of which are reported in
Table 8) were mixed by hand and flood fed into a Berstroff ultra
glide 25-mm twin screw extruder with L/D 36:1 with a K-Tron feeder
KCLK20 at 10 pounds per hour. The extruder melted and mixed the
materials which were metered out a one hole die. This created one
strand which was cooled in a water bath. The molten material came
out the die in a stand and was cooled in a water bath after which
it is dried and chopped into pellets.
[0223] Extrusion conditions were monitored to record processing
conditions as the percentage of silicone block copolyiner varied.
The results are reported in Table 9.
TABLE-US-00009 TABLE 8 4535 gram batch Percent Preparative Example
Preparative Percent Example 2 Number Example 2 mLDPE (grams) mLDPE
(grams) Comp. Ex. 15 -- 100% 0 4536 Ex. 48 0.05% 99.95% 2.268
4533.655 Ex. 49 0.10% 99.90% 4.536 4531.387 Ex. 50 0.50% 99.50%
22.680 4309.127 Ex. 51 2.50% 97.50% 113.398 4422.525
TABLE-US-00010 TABLE 9 Twin Screw Extrusion Data Feed- Zone Zone
Zone Zone Zone Zone Zone Zone Zone Ex- throat 1 2 3 4 5 6 7 8 9
Exam- truder (.degree. C.) (.degree. C.) (.degree. C.) (.degree.
C.) (.degree. C.) (.degree. C.) (.degree. C.) (.degree. C.)
(.degree. C.) (.degree. C.) Zone Melt ple speed Set points 10 Temp.
Pressure Percent Number (rpm) 249 254 254 254 254 254 254 254 254
254 (.degree. C.) (.degree. C.) (Pa) Amps Torque Comp. 325 248 253
256 256 257 257 259 257 257 260 302 301.67 7191231.8 39 72 Ex. 15
Ex. 48 325 247 253 255 256 256 257 257 256 256 260 301 300.56
6853388.7 37 69 Ex. 49 325 248 257 261 252 253 251 252 254 259 258
295 295.00 6563808.9 33 61 Ex. 50 325 247 249 251 252 251 250 251
253 248 249 293 293.33 6363861 30 58 Ex. 51 325 248 253 251 252 251
250 251 253 253 251 290 290.00 5819175.1 28 51
Examples 52-55 and Comparative Examples 16 and 17
[0224] These film examples were made per the method described in
Examples 6-19. Table below details the type and percentage of each
polymer used to create the example films.
TABLE-US-00011 TABLE 10 Percent Heat Aged Organic Silicone Release
Polymer Mixed Block N/dm, 7 Example with Silicone Silicone Block
Polymer Days at Number Block Polymer Polymer Used Used Tape Used
for Testing 65.degree. C. Comp. PRIMACOR Preparative 0 7725-13
20.65 Ex. 16 1410 Example 2 adhesive coated graphic film Ex. 52
PRIMACOR Preparative 2% 7725-13 22.76 1410 Example 2 adhesive
coated graphic film Ex. 53 PRIMACOR Preparative 4% 7725-13 22.23
1410 Example 2 adhesive coated graphic film Comp. SURLYN 1705-1
Preparative 0% 7725-13 33.78 Ex. 17 Example 2 adhesive coated
graphic film Ex. 54 SURLYN 1705-1 Preparative 2% 7725-13 30.28
Example 2 adhesive coated graphic film Ex. 55 SURLYN 1705-1
Preparative 4% 7725-13 30.81 Example 2 adhesive coated graphic
film
Examples 56-58 and Comparative Example 18
[0225] The compounded blends were mixed by hand and flood fed into
a 1-1/4 Killion Single Screw extruder, compression ration 2.93:1.
The material melted and mixed in the extruder. The melted material
was metered thru a necktube into a 6-inch (I .524-dM) flat film
die. The molten material came out the die onto a heated chrome roll
and was nipped with a rubber roll. Throat cooling was needed to
prevent surging. The amounts for each example are in Table 11
below. The cooled film was tested for release properties with Box
tape 371.
TABLE-US-00012 TABLE 11 Percentage Polymer Silicone Release Mixed
With Block (N/dm) Room Example Silicone Block Polymer Tape Used for
Temperature Number Polymer Used Testing for 4 Days Comp. 100% PLA
0% Box Tape 371 63.67 Ex. 18 Ex. 56 99.5% PLA 0.50% Box Tape 371
65.42 Ex. 57 98.25% PLA 1.75% Box Tape 371 58.31 Ex. 58 97.5% PLA
2.50% Box Tape 371 52.07
[0226] The complete disclosures of the patents, patent documents,
and publications cited herein are incorporated by reference in
their entirety as if each were individually incorporated. Various
modifications and alterations to this invention will become
apparent to those skilled in the art without departing from the
scope and spirit of this invention. It should be understood that
this invention is not intended to be unduly limited by the
illustrative embodiments and examples set forth herein and that
such examples and embodiments are presented by way of example only
with the scope of the invention intended to be limited only by the
claims set forth herein as follows.
* * * * *