U.S. patent application number 14/047342 was filed with the patent office on 2014-04-10 for thermoplastic elastomer compositions having biorenewable content.
This patent application is currently assigned to CERESTECH, INC.. The applicant listed for this patent is CERESTECH, INC., TEKNOR APEX COMPANY. Invention is credited to Prashant A. Bhadane, Ryszard Brzoskowski, Kevin Cai, Basil D. Favis, Alain Perreault, Yundong Wang.
Application Number | 20140100311 14/047342 |
Document ID | / |
Family ID | 50433188 |
Filed Date | 2014-04-10 |
United States Patent
Application |
20140100311 |
Kind Code |
A1 |
Cai; Kevin ; et al. |
April 10, 2014 |
THERMOPLASTIC ELASTOMER COMPOSITIONS HAVING BIORENEWABLE
CONTENT
Abstract
Thermoplastic elastomer compositions, in particular derived from
one or more styrenic block copolymers wherein at least one styrenic
block copolymer comprises a controlled distribution copolymer block
including a conjugated diene and a mono alkenyl arene, a plurality
of biorenewable materials, preferably a softener and one or more
synergistic additives such as a polar polymer; a synergistic block
copolymer such as a relatively high molecular weight styrenic block
copolymer; and/or filler. Numerous desirable articles can be formed
from the compositions. Processes for preparing the compositions and
articles are disclosed.
Inventors: |
Cai; Kevin; (Cumberland,
RI) ; Wang; Yundong; (Lancaster, MA) ;
Brzoskowski; Ryszard; (Village of Nagog Woods, MA) ;
Bhadane; Prashant A.; (Montreal, CA) ; Favis; Basil
D.; (Kirkland, CA) ; Perreault; Alain;
(Outremont, CA) |
|
Applicant: |
Name |
City |
State |
Country |
Type |
CERESTECH, INC.
TEKNOR APEX COMPANY |
MONTREAL
PAWTUCKET |
RI |
CA
US |
|
|
Assignee: |
CERESTECH, INC.
MONTREAL
RI
TEKNOR APEX COMPANY
PAWTUCKET
|
Family ID: |
50433188 |
Appl. No.: |
14/047342 |
Filed: |
October 7, 2013 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
|
|
61710864 |
Oct 8, 2012 |
|
|
|
Current U.S.
Class: |
524/52 ;
524/313 |
Current CPC
Class: |
C08L 3/00 20130101; C08L
53/00 20130101; C08L 51/006 20130101; C08L 3/02 20130101; C08L
25/08 20130101; C08L 25/04 20130101; C08L 53/025 20130101; C08L
3/02 20130101; C08L 67/04 20130101 |
Class at
Publication: |
524/52 ;
524/313 |
International
Class: |
C08L 53/00 20060101
C08L053/00; C08L 3/00 20060101 C08L003/00 |
Claims
1. A thermoplastic elastomer composition, comprising: a styrenic
block copolymer comprising at least one controlled distribution
copolymer block having a conjugated diene and a mono alkenyl arena;
a biorenewable softener comprising a natural ester; and at least
one synergistic additive comprising one or more of starch,
thermoplastic starch, a biorenewable polar polymer, and a high
molecular weight styrenic block copolymer.
2. The composition according to claim 1, wherein the styrenic block
copolymer having the controlled distribution copolymer block is
present in an amount from 5 to 90 parts by weight, wherein the
natural ester is an ester-containing oil which is present in an
amount from 1 to 85 parts by weight, and wherein the composition
further includes a polyolefin, wherein all said parts are based on
100 parts by weight of the composition.
3. The composition according to claim 2, wherein the biorenewable
polar polymer is present in an amount from about 2 to about 60
parts by weight, and wherein the composition is free of mineral
oil.
4. The composition according to claim 2, wherein the composition
further includes a functionalized styrenic block copolymer.
5. The composition according to claim 2, wherein the composition
includes one or more of the starch and the thermoplastic starch in
an amount from 2 parts to 80 parts by weight.
6. The composition according to claim 2, wherein the biorenewable
polar polymer is present in an amount from about 2 parts to about
60 parts by weight, wherein the ester-containing oil is present in
an amount from about 10 parts to about 65 parts by weight, and
wherein the composition is free of a mineral oil.
7. The composition according to claim 1, wherein the composition
includes the high molecular weight styrenic block copolymer in an
amount from about 1 parts to about 30 parts by weight per 100 parts
by weight of the composition, and wherein the composition further
includes a polyolefin.
8. The composition according to claim 1, wherein the biorenewable
polar polymer is present in an amount from 1 to 80 parts by weight,
wherein the natural ester is an ester-containing oil which is
present in an amount from 1 to 85 parts by weight, wherein the
styrenic block copolymer having the controlled distribution
copolymer block is present in an amount from 10 to 70 parts by
weight, wherein all said parts are based on 100 parts by the weight
of the composition.
9. The composition according to claim 8, wherein the biorenewable
polar polymer is one or more of a polylactic acid, polylactide,
poly(glycolic acid), polyglycolide, poly(lactic-co-glycolic),
poly(lactide-co-glycolide), polyglyconate, poly(hydroxyalkanoate),
polyorthoester, polycaprolactone, polydioxanone, polyanhydride, and
polyether-block-amide.
10. The composition according to claim 9, wherein the composition
further includes a polyolefin, and wherein the composition further
includes the high molecular weight styrenic block copolymer.
11. The composition according to claim 2, wherein the
ester-containing oil comprises hydrogenated oil.
12. The composition according to claim 3, wherein the high
molecular weight styrenic block copolymer is present in an amount
from about 2 to about 20 parts by weight, wherein the styrenic
block copolymer having the controlled distribution copolymer block
is present in an amount from 20 to 35 parts by weight, wherein the
biorenewable polymer is present in an amount from 2 to 20 parts by
weight, and wherein the ester-containing oil is present in an
amount from 10 to 65 parts by weight.
13. The composition according to claim 5, wherein the one or more
of the starch and thermoplastic starch are present in an amount
from 2 to 40 parts by weight, wherein a dispersion aid is present
wherein the styrenic block copolymer having the controlled
distribution copolymer block is present in an amount from 15 to 70
parts by weight, wherein the ester-containing oil is present in an
amount from 10 to 65 parts by weight, and wherein the composition
further includes a functionalized styrenic block copolymer.
14. A thermoplastic elastomer composition, comprising: a styrenic
block copolymer comprising at least one controlled distribution
copolymer block having a conjugated diene and a mono alkenyl arene;
a biorenewable softener comprising an ester-containing oil; and one
or more of starch and thermoplastic starch in an amount from about
2 parts to about 80 parts by weight, wherein all parts are based on
100 parts by weight of the composition.
15. The composition according to claim 14, wherein a dispersion aid
is present in an amount from about 1 to about 80 parts by weight
based on 100 total parts by weight of starch and thermoplastic
starch, and wherein a polyolefin is also present.
16. The composition according to claim 14, wherein the styrenic
block copolymer having the controlled distribution copolymer block
is present in an amount from 5 to 90 parts by weight, wherein the
ester-containing oil is present in an amount from about 5 to about
75 parts by weight and wherein the composition further includes a
functionalized styrenic block copolymer.
17. The composition according to claim 14, wherein the styrenic
block copolymer having the controlled distribution copolymer block
is present in an amount from 20 to 35 parts by weight, wherein the
ester-containing oil is present in an amount from 10 to 65 parts by
weight, and wherein the one or more of starch and thermoplastic
starch is present in an amount from 2 to 40 parts by weight.
18. The composition according to claim 17, wherein the composition
further includes a functionalized styrenic block copolymer.
19. An article comprising the composition according to claim 1.
20. A process for preparing a thermoplastic elastomer composition,
comprising the step of combining the components set forth in claim
14, utilizing a one step compounding process.
Description
CROSS REFERENCE
[0001] This application claims the benefit of priority under 35
U.S.C. .sctn.119 of U.S. Provisional Application Ser. No.
61/710,864, filed Oct. 8, 2012 herein fully incorporated by
reference.
FIELD OF THE INVENTION
[0002] The present invention relates to thermoplastic elastomer
compositions, in particular derived from one or more styrenic block
copolymers wherein at least one styrenic block copolymer comprises
a controlled distribution copolymer block including a conjugated
diene and a mono alkenyl arene, a plurality of biorenewable
materials, preferably a softener; and one or more synergistic
additives such as a polar polymer; a synergistic block copolymer
such as a relatively high molecular weight styrenic block
copolymer; and/or filler. Numerous desirable articles can be formed
from the compositions. Processes for preparing the compositions and
articles are disclosed.
BACKGROUND OF THE INVENTION
[0003] Thermoplastic elastomer compositions are versatile as they
exhibit beneficial elastomeric properties and yet may be processed
using standard thermoplastic processing equipment. Numerous
different thermoplastic elastomer compositions, some with
biorenewable components, have been proposed.
[0004] U.S. Patent Application Publication No. 2011/0184082 relates
to a composition that includes a hydrogenated styrenic block
copolymer that has at least one block A and at least one block B,
and about 10 to about 90 percent by weight of an
styrene-isobutylene-styrene block copolymer. Each A is an
monoalkenyl arene and each B block is a controlled distribution
copolymer of at least one mono alkenyl arene and at least one
conjugated diene, having the general formula A-EB/A-A and
(A-EB/A)nX. Each B block comprises terminal regions adjacent to the
A blocks that are rich in conjugated diene units and one or more
regions not adjacent to the A blocks that are rich in mono alkenyl
arena units. Oil-free compositions that reportedly result in the
combination of low gaseous permeability, low thermal conductivity,
strong vibration and sound attenuation, and optionally high levels
of light transmission with relatively low haze values while
maintaining melt flow rates suitable for easy processibility are
preferred.
[0005] U.S. Patent Application Publication No. 2010/00630008
relates to gelatinous elastomer compositions. In certain
embodiments, a gelatinous elastomer composition is disclosed
comprising about 1.0% to 50.0% block copolymer, about 0% to 98%
mineral and/or synthetic oil, and about 0.0% to 98% triglyceride
oil, about 0-15.0% free fatty acids, about 0-30% of a tack
modification agent, about 0-20.0% of a biologically active agent
and, optionally a phytosterol, ceramide and/or bisabolol. The
gelatinous elastomer compositions are reportedly useful for
applying a biologically active agent to a mammal. In certain
embodiments, the gelatinous elastomer composition is formed into a
molded article.
[0006] U.S. Patent Application Publication No. 2008/0171007 relates
to a method of making up keratinous substrates involving applying
onto the keratinous substrates a composition containing a) a block
copolymer, b) a tackifier, c) a wax, d) a liquid fatty phase, e) a
high viscosity ester, and f) optionally, a colorant.
[0007] U.S. Patent Application Publication No. 2008/0171006 relates
to a method of making up keratinous substrates involving applying
onto the keratinous substrate a composition containing a) a block
copolymer, b) a tackifier, c) an alkyl silsesquioxane wax, d) a
liquid fatty phase, and e) optionally, a colorant.
[0008] U.S. Patent Application Publication No. 2006/0121170 relates
to a nonflowable gel composition including a vegetable oil and a
thermoplastic elastomer. The nonflowable gel composition is
characterized by its inability to flow when subjected to pressure.
In another embodiment, the invention is a resilient gel composition
which includes a vegetable oil and a thermoplastic elastomer. The
resilient gel composition is characterized by its ability to
recover its size and form following deformation. In another
embodiment, a support surface for supporting the human body is
disclosed, including the composition and a holding structure for
holding the composition.
[0009] U.S. Pat. No. 7,884,158 relates to a cosmetic composition
containing at least one block copolymer having a hard segment and a
soft segment, at least one tackifier component, at least one
phenylated silicone, at least one solvent, and optionally, at least
one colorant.
[0010] U.S. Pat. No. 7,625,967 relates to oil gel compositions that
include at least one non-aromatic ester oil and an anionic block
copolymer of a mono alkenyl arena and a conjugated diene. The block
copolymer is selectively hydrogenated and has mono alkenyl arena
end blocks and a controlled distribution block of a mono alkenyl
arene and a conjugated diene midblock. The ester oil is a
non-aromatic, ester compound such as soybean oil, rapeseed oil, and
other like compounds.
[0011] U.S. Pat. No. 7,267,855 relates to articles prepared from
anionic block copolymers of mono alkenyl arenas and conjugated
dienes, and to blends of such block copolymers with other polymers.
The block copolymers are selectively hydrogenated and have mono
alkenyl arene end blocks and controlled distribution blocks of mono
alkenyl arenas and conjugated dienes. The block copolymer may be
blended with at least one other polymer selected from the group
consisting of olefin polymers, styrene polymers, amorphous resins
and engineering thermoplastic resins.
[0012] U.S. Pat. No. 7,169,848 relates to a block copolymer
containing a controlled distribution copolymer block of a
conjugated diene and a mono alkenyl arena, where the controlled
distribution copolymer block has terminal regions that are rich in
conjugated diene units and a center region that is rich in mono
alkenyl arene units. Also disclosed is a method for manufacture of
the block copolymer.
[0013] U.S. Pat. No. 6,984,688 relates to a plasticized HSBC
blended with polypropylene and free of a filler material which
adversely affects clarity, provides an injection-moldable
composition for an article required to have specific properties,
namely, tensile strength in the range from about 4.13 to 8.96 MPa
(600 to 1300 psi); tear strength in the range from about 21 to 52.6
N/mm (120 to 300 lbs/in); softness in the range from about 45 but
less than 65 Shore A; and haze less than 20%, measured by ASTM
D1003 using a DYK Gardner Micro Tri-gloss 4525 meter; and it is
essential that all of these properties, along with the physical
dimensions of the molded article, remain substantially unchanged
after immersion of the article in boiling water for 1 hour. Such a
composition reportedly may be injection molded to form a nipple for
feeding an infant, or a teething ring, or goggles for a diver, and
the articles are reportedly sterilizable and recyclable.
[0014] U.S. Pat. No. 6,673,857 relates to a thermoplastic elastomer
composition comprising a) from 5 to 99% by weight of a block
copolymer which is composed of hard blocks S made from vinyl
aromatic monomers and of one or more random soft blocks B/S made
from dienes and from vinyl aromatic monomers, b) from 1 to 95% by
weight of a plasticizer with a higher polarity than white oil and
with a lower polarity than diisooctyl phthalate, c) from 0 to 50%
by weight of a polyolefin, and d) from 0 to 60% by weight of
additives, where the total of a) to d) is 100% by weight. The use
of the molding compositions to produce flexible or elastic moldings
is described, as are the resultant moldings.
[0015] U.S. Pat. No. 6,031,053 relates to an elastomeric block
copolymer comprising at least one block A having polymerized units
of a vinylaromatic monomer and forming a rigid phase and at least
one elastomeric block EVA having polymerized units of both
vinylaromatic monomers and of a diene and forming a flexible phase,
and glass transition temperature Tg of the block A being above
25.degree. C. and that of the block B/A being below 25.degree. C.
and the phase volume ratio of block A to block B/A being chosen so
that the amount of the rigid phase in the total block copolymer is
1 to 40% by volume and the amount of the diene is less than 50% by
weight.
[0016] WO 2009/152870 relates to a group of thermoplastic
elastomers reportedly with high environmental compatibility and
biodegradability. The compositions include styrenic block
copolymers, vegetal oils, solid vegetal oil products and at least
one styrenic block copolymer modified with maleic anhydride, see
claim 1.
[0017] WO 2008/087675 relates to a plastification process of
thermoplastic elastomers derived from styrenic block copolymers, in
which vegetal oils are used as plastifying substances, and
thermoplastic elastomers obtained with the said process.
[0018] In view of the above it would be desirable to provide a high
performance thermoplastic elastomer composition having biorenewable
components, in particular at least a softener and/or at least one
additional synergistic additive, preferably in a relatively high
percentage by total weight in order to improve oil stability, and
achieve desirable properties including low gloss, high physical
strength, improved melt strength, and suitable melt viscosity range
for both molding and extrusion. In reality, the solution is not
simple as numerous issues exist that must be addressed, including,
but not limited to, providing a relatively low hardness material
without sacrificing tensile strength, recoverable high elongations,
component compatibility, processibility, heat stability,
weatherability, and substantially low or no softener or plasticizer
bleed-out. Desirably, the properties should be met not only at the
room temperature but from -30.degree. C. to 135.degree. C., more
typically from -10.degree. C. to 70.degree. C., for about 168 hrs
(1 week) for most of the applications. In spite of many disclosures
reporting thermoplastic elastomer compositions including
biorenewable content, the applicants have discovered oil bleed-out
problems and poor heat resistance with many proposed formulations
at various temperatures, which limit the commercialization and
application of the bio-based thermoplastic elastomer compositions
containing vegetable oils and the like.
SUMMARY OF THE INVENTION
[0019] In view of the above, it would be desirable to provide a
thermoplastic elastomer composition having relatively high
biorenewable content yet additionally exhibits sought-after
properties, especially excellent elasticity, high physical strength
and desirable oil stability, that is, little or no oil bleed-out at
various temperatures, depending on article requirements.
[0020] Therefore, it is an object of the present invention to
provide a composition comprising at least one styrenic block
copolymer having a controlled distribution block of a conjugated
diene and a mono alkenyl arene, and further one or more and
preferably a plurality of biorenewable components comprising a
softener, for example an ester group-containing oil, generally a
triglyceride; a wax; an ester; an alcohol; an amine, a starch, a
thermoplastic starch, and a polar polymer such as polylactic acid
(PLA), polyhydroxyalkanoates (PHAs), polyhydroxybutyrate (PHB),
polyether-block-amide (PEBA) etc. When starch is included, the
mixture may also contain a plasticizer or dispersion aid dedicated
for the starch phase for its effective gelatinization and
dispersion. The effective plasticizer or dispersion aid can be from
a family of polyols, polyglycols, carboxylic acid derivatives, or
polyesters.
[0021] Yet another object of the present invention is to provide
the controlled distribution block with terminal regions that are
rich in conjugated diene units and one or more regions that are
rich in mono alkenyl arene units, wherein said block surprisingly
provides high compatibility and low oil bleeding or leaching with
both a biorenewable ester, preferably glyceride-containing
component and a biorenewable additive.
[0022] Still another object of the present invention is to provide
the composition with a fatty-triglyceride, wax, an ester, alcohol,
or amine, or a mixture thereof-containing component derived from a
vegetable product, wherein vegetable oils or their derivatives,
such as partially or fully hydrogenated vegetable oil, are
particularly preferred in some embodiments, and a synergistic
biorenewable additive comprising one or more of a starch,
thermoplastic starch, and polar polymer.
[0023] A further object of the present invention is to provide the
composition with biorenewable components comprising triglycerides
of saturated and unsaturated fatty acids.
[0024] An additional object of the present invention is to provide
the compositions with relatively low hardness without sacrificing
tensile strength low modulus and desirable elongation.
[0025] Yet another object of the present invention is to provide a
thermoplastic elastomer composition with enhanced biodegradability,
due at least in part to the presence of a plurality of biorenewable
components. When a composition includes one or more of an ester and
a starch, their hydrophilic natures are keys to
biodegradability.
[0026] Still another object of the present invention is to provide
compositions with a relatively high biorenewable component content
that can be formed into articles having a soft-grip feel, have a
smooth appearance, are dry, and are substantially free of oil
leaching.
[0027] A further object of the present invention is to provide a
thermoplastic elastomer composition that can be processed utilizing
standard processing equipment, such as injection molders and
extruders.
[0028] Another object of the present invention is to provide a
thermoplastic elastomer composition including a styrenic block
copolymer having a controlled distribution midblock including a
mono alkenyl arene and a conjugated diene, wherein the mono alkenyl
arene is present in an amount of less than 30% by weight based on
the total weight of the block.
[0029] An additional object of the present invention includes
providing the thermoplastic elastomer composition having the
styrenic block copolymer with a controlled distribution polymer
block and biorenewable components with other compounds that enhance
the properties of the composition, for example, a softener such as
mineral oil, a polyolefin, other styrenic block copolymer or a
polar polymer such as PLA.
[0030] Yet another object of the invention is to provide a
thermoplastic elastomer composition including a styrenic block
copolymer having a controlled distribution polymer block, a
softener, preferably an ester group-containing oil, a functional
group containing styrenic block copolymer, one or more of starch
and a thermoplastic starch, and glycerin or a glycerin-like
component.
[0031] Still another object of the invention is to provide a
thermoplastic elastomer composition including a styrenic block
copolymer having a controlled distribution polymer block, a
softener, preferably an ester group-containing oil, and a polar
polymer comprising one or more of polylactic acid (PLA),
polyhydroxyalkanoates (PHAs), polyhydroxybutyrate (PHB), ethylene
vinyl acetate copolymer, polyether-block-amide (PEBA) etc.
[0032] Yet another object of the invention is to provide a
thermoplastic elastomer composition including a styrenic block
copolymer having a controlled distribution polymer block, a
softener, preferably an ester group-containing oil, and a
relatively high molecular weight styrenic block copolymer such as
ultra-high molecular weight SEBS.
[0033] Still another object of the invention is to provide a
thermoplastic elastomer composition including a styrenic block
copolymer having a controlled distribution polymer block, a
softener, preferably an ester group-containing oil, a polyolefin,
such as polypropylene, and a polar polymer such as described
herein.
[0034] Still another object of the present invention is to provide
a composition including a styrenic block copolymer, and one or more
of a starch and a thermoplastic starch with glycerin or a glycerin
like component, a natural wax, a fatty ester, a fatty alcohol, a
fatty amine, and a polar polymer.
[0035] Accordingly, in one aspect, a thermoplastic elastomer
composition is disclosed, comprising a styrenic block copolymer
comprising at least one controlled distribution copolymer block
having a conjugated diene and a mono alkenyl arena; a biorenewable
softener comprising a natural ester; at least one synergistic
additive comprising one or more of starch, thermoplastic starch, a
biorenewable polar polymer, and a high molecular weight styrenic
block copolymer.
[0036] In a further aspect of the present invention a thermoplastic
elastomer composition is disclosed, comprising a styrenic block
copolymer comprising at least one controlled distribution copolymer
block having a conjugated diene and a mono alkenyl arena; a
biorenewable softener comprising an ester-containing oil; one or
more of starch and thermoplastic starch in an amount from about 2
parts to about 8 parts by weight, wherein all parts are based on
100 parts by weight of the composition.
BRIEF DESCRIPTION OF THE DRAWINGS
[0037] FIG. 1 illustrates a cross-sectional side view of one
embodiment of a composite of the present invention including a
layer comprising a thermoplastic elastomer composition having
biorenewable content; and
[0038] FIG. 2 illustrates one embodiment of an article, in
particular a grip, of a thermoplastic elastomer composition having
biorenewable content connected to a substrate, in particular a
writing utensil.
DETAILED DESCRIPTION OF THE INVENTION
[0039] The thermoplastic elastomer compositions of the present
invention include a styrenic block copolymer having a controlled
distribution copolymer block having a conjugated diene and a mono
alkenyl arena, wherein said block comprises terminal regions
adjacent relatively harder blocks, with the controlled distribution
block being rich in conjugated dienes adjacent to the relatively
hard blocks and one or more regions not adjacent to the relatively
hard blocks that are rich in mono alkenyl arena units, and
biorenewable components comprising a softener and an additive.
Surprisingly, the inventive compositions exhibit lower hardness
without sacrificing much tensile strength when compared to
combining the styrenic block copolymer having the controlled
distribution copolymer block with a mineral oil. Polar components
such as starch, PLAs, etc. have also found to help better retain
the softener in various formulations. The compositions of the
present invention can also include other compounds, for example as
described herein.
[0040] General Styrenic Block Copolymers
[0041] In various embodiments, the compositions of the present
invention include one or more styrenic block copolymers, in
addition to the styrenic block copolymer having a controlled
distribution copolymer block having a conjugated diene and a mono
alkenyl arena. In a preferred embodiment, the styrenic block
copolymers have a hard block (A) including aromatic vinyl or
mono-alkenyl arena repeat units and at least one soft polymer bock
(B) containing two or more repeat units, that are the same or
different, and independently derived from olefin monomers. The
styrenic block copolymer can be, for example, a triblock copolymer
(A-B-A); or a tetrablock or higher multiblock copolymer. In a
preferred embodiment, the styrenic block copolymer is a triblock
copolymer (A-B-A) having two hard blocks.
[0042] The number average molecular weight and distribution of any
type of styrenic block copolymer (SBC) described in this
application are measured by gel permeation chromatography (GPO).
The SBC is dissolved in a suitable solvent, such as THF, (typically
00001-0.010 wt %), and an appropriate quantity is injected into a
GPO device. One suitable GPO device is available from Waters of
Milford, Mass. as a Waters Breeze Dual Pump LC. The GPO analysis is
performed at an appropriate elution rate (1 to 10 mL/min). The
molecular weight distribution is characterized by the signals from
UV and refractive index detectors, and number average molecular
weights are calculated using a calibration curve generated from a
series of narrow molecular weight distribution polystyrenes with
peak molecular weights of 500 to 1,000,000 as standard.
[0043] Each hard polymer block (A) can have two or more same or
different aromatic vinyl repeat units. For example, the block
copolymer may contain (A) blocks which are
styrene/alpha-methylstyrene copolymer blocks or styrene/butadiene
random or tapered copolymer blocks so long as a majority of the
repeat units of each hard block are aromatic vinyl repeat units.
The (A) blocks are aromatic vinyl compound homopolymer blocks in
one embodiment. The term "aromatic vinyl" is to include those of
the benzene series, such as styrene and its analogs and homologs
including o-methylstyrene, p-methylstyrene, p-tert-butylstyrene,
1,3-dimethylstyrene, alpha-methylstyrene and other ring alkylated
styrenes, particularly ring-methylated styrenes, and other
monoalkenyl polycyclic aromatic compounds such as vinyl
naphthalene, vinyl anthracene and the like. The preferred aromatic
vinyl compounds are monovinyl monocyclic aromatics, such as styrene
and alpha-methylstyrene, with styrene being most preferred. When
three or more different repeat units are present in hard polymer
block (A), the units can be combined in any form, such as random
form, block form and tapered form.
[0044] Optionally, the hard polymer block (A) can comprise small
amounts of structural units derived from other copolymerizable
monomers in addition to the structural units derived from the
aromatic vinyl compounds. The proportion of the structural units
derived from other copolymerizable monomers is desirably 30% by
weight or less and preferably 10% by weight or less based on the
total weight of the hard polymer block (A). Examples of other
copolymerizable monomers include, but are not limited to, 1-butene,
pentene, hexene, conjugated dienes such as butadiene or isoprene,
methyl vinyl ether, and other monomers.
[0045] The soft polymer block (B) of the styrenic block copolymer
includes two or more same or different structural units. Soft
polymer block (B) can be derived from olefin monomers generally
having from 2 to about 12 carbon atoms and can include, for
example, ethylene, propylene, butylene, isobutylene, etc. When the
soft polymer block (B) has structural units derived from three or
more repeat units, the structural units may be combined in any form
such as random, tapered, block or any combination thereof. In one
embodiment, the soft polymer block does not contain any unsaturated
bonds.
[0046] In additional embodiments of the present invention, the
styrenic block copolymer can have at least one soft polymer block
(B) including two or more repeat units that are the same or
different, independently derived from one or more of an olefin
monomer and a diene monomer. When the diene monomer is present, the
styrenic block copolymer is preferably hydrogenated or
substantially hydrogenated. The conjugated diene monomers
preferably contain from 4 to about 8 carbon atoms with examples
including, but not limited to, 1,3-butadiene (butadiene),
2-methyl-1,3-butadiene (isoprene), 2,3-dimethyl-1,3-butadiene,
1,3-pentadiene (piperylene), 1,3-hexadiene, and the like.
Therefore, in one embodiment, the soft polymer block (B) can have
structural units derived from one or more of an olefin monomer(s)
and diene monomer(s). As indicated hereinabove, when the soft
polymer block (B) has structural units derived from three or more
repeat units, the structural units may be combined in any form.
[0047] The styrenic block copolymers may be prepared utilizing
bulk, solution or emulsion or other techniques as known in the
art.
[0048] Optionally, the soft polymer block (B) can include small
amounts of structural units derived from other copolymerizable
monomers in addition to the structural units described. In this
case, the proportion of the other copolymerizable monomers is
generally 30% by weight or less, and preferably 10% by weight or
less based on the total weight of the soft polymer block (B) of the
styrenic block copolymer. Examples of other copolymerizable
monomers include, for example, styrene, p-methylstyrene,
.alpha.-methylstyrene, and other monomers that can undergo ionic
polymerization.
[0049] Optionally, the styrenic block copolymer can be a
functionalized styrenic block copolymer such as an acid or
anhydride functionalized block copolymer, such as prepared by graft
reacting an acid moiety or its derivative into the styrenic block
copolymer via a free radically initiated reaction. Examples of
suitable monomers which may be grafted include unsaturated mono and
polycarboxylic acids and anhydrides containing from about 3 to
about 10 carbon atoms. Examples of such monomers are fumaric acid,
itaconic acid, citraconic acid, acrylic acid, maleic anhydride,
itaconic anhydride, and citraconic anhydride, or the like. Suitable
functionalized styrenic block copolymers generally contain from
about 0.1 to about 10 percent by weight, preferably from about 0.2
to about 5 percent by weight of the grafted monomer, based on the
total weight of the styrenic block copolymer. Grafting reactions
can be carried out in solution or by melt mixing the base block
copolymer and the acid/anhydride monomer in the presence of a free
radial initiator, such as known in the art, see for example U.S.
Pat. No. 6,653,408, herein fully incorporated by reference.
Suitable functionalized block copolymers are available from KRATON
Polymers, Kuraray, Asahi-Kasei, BASF and the like.
[0050] In various embodiments, the styrenic block copolymers
include, but are not limited to, styrene-butadiene-styrene (SBS),
styrene-butadiene/butylene-styrene (SBBS), styrene-isoprene-styrene
(SIS), styrene-ethylene/propylene-styrene (SEPS),
styrene-ethylene/propylene (SEP), styrene-ethylene/butylene-styrene
(SBBS), styrene-ethylene/ethylene/propylene-styrene (SEEPS) and
styrene-isobutylene-styrene (SIBS).
[0051] Styrenic block copolymers are available in the art from
sources such as Kraton Polymers of Houston, Tex., as Kraton;
Kuraray Co., Ltd. of Tokyo, Japan as SEPTON.TM. styrenic block
copolymers, LCY Chemical Industry Corp, as Globalprene.RTM., and
TSRC Corporation of Taiwan as Taipol.
[0052] When present, the amount of the one or more styrenic block
copolymers utilized in the compositions of the present invention
ranges generally from about 1 to about 40 or 45 parts, desirably
from about 10 to about 35 parts and preferably from about 10 or 15
to about 30 parts based on 100 parts by weight of the
composition.
[0053] Controlled Distribution Copolymer Block-Containing Styrenic
Block Copolymers
[0054] The controlled distribution block-containing styrenic block
copolymers utilized in the invention have at least a first block of
a mono alkenyl arene, such as styrene, and a second block of a
controlled distribution copolymer of diene and mono alkenyl arene.
Thus, the block copolymers can be any di-or higher block
copolymers. In the case of a di-block copolymer composition
copolymer, one block is an alkenyl arene-based block and
polymerized therewith is a second block of the controlled
distribution copolymer comprising diene and alkenyl arene.
Tri-block or higher multi-block copolymers include at least one
alkenyl arene-based block and at least one controlled distribution
copolymer block comprising diene and alkenyl arene. In one
preferred embodiment, the triblock-composition comprises, as end
blocks, alkenyl arene-based blocks and a midblock of a controlled
distribution copolymer comprising diene and alkenyl arene. Where a
tri-block copolymer composition is prepared, the controlled
distribution copolymer block can be designated as "B" and the
alkenyl arene-based block designated as "A". The A-B-A tri-block
compositions can be made by either sequential polymerization or
coupling. In one embodiment, in the sequential solution
polymerization technique, the mono alkenyl arene is first
introduced to produce a relatively hard aromatic-containing block,
followed by introduction of the controlled distribution diene and
alkenyl arene-containing mixture to form the midblock, and then
followed by introduction of the mono alkenyl arena to form the
terminal block.
[0055] In one embodiment, a method for making a controlled
distribution copolymer block-containing styrenic block copolymer is
set forth in U.S. Pat. No. 7,169,848 herein incorporated by
reference. As utilized herein, "controlled distribution" is defined
as referring to a molecular structure having the following
attributes: (1) terminal regions adjacent to the mono alkenyl arene
homopolymer ("A") blocks that are rich in (i.e., having a greater
than average amount of) conjugated diene units; (2) one or more
regions not adjacent to the A blocks that are rich in (i.e., having
a greater than average amount of) mono alkenyl arena units; and (3)
an overall structure having relatively low blockiness. For the
purposes hereof, "rich in" is defined as greater than the average
amount, preferably greater than 5% the average amount. Prior to
hydrogenation the styrene in the rubber block portion is
copolymerized and incorporated in a controlled distribution having
terminal regions that are rich in diene units (e.g. butadiene,
isoprene, or a mixture thereof) and a center region that is rich in
styrene units. Such polymers were hydrogenated under standard
conditions such that greater than 95% of the diene double bonds in
the rubbery block have been reduced. The process for producing a
selectively hydrogenated styrene block copolymer is described in
U.S. Pat. No. 7,169,848 to Bening at al.
[0056] The styrene blockiness is simply the percentage of blocky
styrene to total styrene units:
Blocky %=100 times (Blocky Styrene Units/Total Styrene Units)
[0057] Expressed thus, Polymer-Bd-S--(S)n-S-Bd-Polymer where n is
greater than zero is defined to be blocky styrene. For example, if
n equals 8 in the example above, then the blockiness index would be
80%. It is preferred that the blockiness index be less than about
40. For some polymers, having styrene contents of ten weight
percent to forty weight percent, it is preferred that the
blockiness index be less than about 10. In a preferred embodiment
of the present invention, the subject controlled distribution
copolymer block has two distinct types of regions--conjugated diene
rich regions on the end of the block and a mono alkenyl arene rich
region near the middle or center of the block. What is desired is a
mono alkenyl arene-conjugated diene controlled distribution
copolymer block, wherein the proportion of mono alkenyl arene units
increases gradually to a maximum near the middle or center of the
block and then decreases gradually until the polymer block is fully
polymerized.
[0058] The alkenyl arena can be styrene, alpha-methylstryene,
para-methylstyrene, vinyl toluene, vinylnaphthalene, or para-butyl
styrene or mixtures thereof. Of these, styrene is most preferred
and is commercially available, and relatively inexpensive, from a
variety of manufacturers. The conjugated dienes for use herein
comprise 1,3-butadiene and substituted butadienes such as isoprene,
piperylene, 2,3-dimethyl-1,3-butadiene and 1-phenyl-1,3-butadiene,
or mixtures thereof. Of these, 1,3-butadiene is most preferred.
[0059] For the controlled distribution or B block the weight
percent of mono alkenyl arena in each B block is between about 10
weight percent and about 75 weight percent, preferably between
about 25 weight percent and about 50 weight percent for selectively
hydrogenated polymers.
[0060] It is preferred that, to ensure significantly elastomeric
performance while maintaining desirably high Tg and strength
properties, as well as desirable transparency, the tri block and
multi-block polymer's alkenyl arene content is greater than about
20% weight, preferably from about 20% to about 80% weight. This
means that essentially all of the remaining content, which is part
of the diene/alkenyl arena block, is diene. It is also important to
control the molecular weight of the various blocks. For an AB
diblock, desired block weights are 3,000 to about 60,000 for the
monoalkenyl arene A block, and 30,000 to about 300,000 for the
controlled distribution conjugated diene/mono alkenyl arena B
block. Preferred ranges are 5,000 to 45,000 for the A block and
50,000 to about 250,000 for the B block. For the triblock, which
may be a sequential ABA or coupled (AB).sub.2 X block copolymer,
the A blocks should be 3,000 to about 60,000 preferably 5,000 to
about 45,000, while the B block for the sequential block should be
about 30,000 to about 300,000 and the B blocks (two) for the
coupled polymer half that amount. The total average molecular
weight for the triblock copolymer should be from about 40,000 to
about 400,000 and for the radial copolymer from about 60,000 to
about 600,000. For the tetrablock copolymer ABAB the block size for
the terminal B block should be about 2,000 to about 40,000, and the
other blocks may be similar to that of the sequential triblock
copolymer. These molecular weights are most accurately determined
by light scattering measurements, and are expressed as number
average molecular weight.
[0061] The controlled distribution block copolymer can be
hydrogenated in various embodiments. One preferred hydrogenation is
selective hydrogenation of the diene portions of the final block
copolymer alternatively both the "B" blocks and the "A" blocks may
be hydrogenated, or merely a portion of the "B" blocks may be
hydrogenated.
[0062] Hydrogenation can be carried out via any of the several
hydrogenation or selective hydrogenation processes known in the
prior art. For example, such hydrogenation has been accomplished
using methods such as those taught in, for example, U.S. Pat. Nos.
3,595,942; 3,634,549; 3,670,054; 3,700,633; and Re. No. 27,145, the
disclosures of which are incorporated herein by reference. These
methods operate to hydrogenate polymers containing aromatic or
ethylenic unsaturation and are based upon operation of a suitable
catalyst. Such catalyst, or catalyst precursor, preferably
comprises a Group VIII metal such as nickel or cobalt which is
combined with a suitable reducing agent such as an aluminum alkyl
or hydride of a metal selected from Groups I-A, II-A, AND III-B of
the Periodic Table of the Elements, particularly lithium, magnesium
or aluminum. This preparation can be accomplished in a suitable
solvent or diluent at a temperature from about 20.degree. C. to
about 80.degree. C. Other catalysts that are useful include
titanium based catalyst systems. Hydrogenation can be carded out
under such conditions that at least about 90 percent of the
conjugated diene double bonds have been reduced, and between zero
and 10 percent of the arena double bonds have been reduced.
Preferred ranges are at least about 95 percent of the conjugated
diene double bonds reduced, and more preferably about 98 percent of
the conjugated diene double bonds are reduced. Alternatively, it is
possible to hydrogenate the polymer such that aromatic unsaturation
is also reduced beyond the 10 percent level mentioned above. Such
exhaustive hydrogenation is usually achieved at higher
temperatures. In that case, the double bonds of both the conjugated
diene and arene may be reduced by 90 percent or more.
[0063] In an alternative, the block copolymer of the present
invention may be functionalized in a number of ways. One way is by
treatment with an unsaturated monomer having one or more functional
groups or theft derivatives, such as carboxylic acid groups and
their salts, anhydrides, esters, imide groups, amide groups, and
acid chlorides. The preferred monomers to be grafted onto the block
copolymers are maleic anhydride, maleic acid, fumaric acid, and
their derivatives. A further description of functionalizing such
block copolymers can be found in Gergen et al, U.S. Pat. No.
4,578,429 and in U.S. Pat. No. 5,506,299. In another manner, the
selectively hydrogenated block copolymer of the present invention
may be functionalized by grafting silicon or boron containing
compounds to the polymer as taught in U.S. Pat. No. 4,882,384. In
still another manner, the block copolymer of the present invention
may be contacted with an alkoxy-silane compound to form
silane-modified block copolymer. In yet another manner, the block
copolymer of the present invention may be functionalized by
grafting at least one ethylene oxide molecule to the polymer as
taught in U.S. Pat. No. 4,898,914, or by reacting the polymer with
carbon dioxide as taught in U.S. Pat. No. 4,970,265. Still further,
the block copolymers of the present invention may be metallated as
taught in U.S. Pat. Nos. 5,208,300 and 5,276,101, wherein the
polymer is contacted with an alkali metal alkyl, such as a lithium
alkyl. And still further, the block copolymers of the present
invention may be functionalized by grafting sulfonic groups to the
polymer as taught in U.S. Pat. No. 5,516,831. All of the patents
mentioned in this paragraph are incorporated by reference into this
application.
[0064] In various embodiments of the invention, the mono alkenyl
arene is present in a total weight in an amount of greater than 20%
and preferably greater than 35% based on the total weight of the
controlled distribution block copolymer. In various embodiments the
soft or B block of the controlled distribution copolymer block has
a mono alkenyl arena content of less than 30%, desirably less than
29% by weight. The controlled distribution block copolymer of the
present invention may include the copolymers sold under the trade
name Kraton A.RTM. by Kraton Polymers, Kraton A1536 and A1535 are
examples.
[0065] In various embodiments of the invention, the controlled
distribution block-containing styrenic block copolymers are
utilized in compositions of the present invention in an amount from
about 5 to about 90 parts, desirably from about 10 or about 15 to
about 70 or 80 parts, and preferably from about 20 to about 30 or
35 parts based on 100 parts by weight of the composition.
[0066] High Molecular weight Styrenic Block Copolymers.
[0067] In some embodiments of the present invention, the
compositions include one or more relatively high molecular weight
styrenic block copolymers. High molecular weight as utilized herein
refers to those block copolymers having a number average molecular
weight generally greater than 300,000 g/mol. The high molecular
weight styrenic block copolymers have been found to reduce gloss,
improve physical strength and elasticity, increase melt strength,
improve processibility, especially in extrusion applications, and
to reduce softener or vegetable oil bleeding in various
compositions of the present invention including biorenewable
content.
[0068] in one embodiment, tri-block styrenic block copolymers are
preferred with the copolymers having styrene end blocks with
average block length greater than 50,000 and a butadiene mid-block
greater than 200,000. Such copolymers can be made from sequential
anionic living polymerization. In one embodiment, the high
molecular weight styrenic block copolymers are substantially fully
hydrogenated. High molecular weight styrenic block copolymers are
available from Kraton as Kraton 1633, Kuraray as Septon 4099 and
TSRC as Taipol 6159.
[0069] When present in a composition of the present invention, the
high molecular weight styrenic block copolymer is utilized in an
amount generally from about 1 to about 30, desirably from about 2
to about 20 and preferably from about 3 to about 15 parts by weight
based on 100 total parts by weight of the composition.
[0070] Biorenewable Components
[0071] The composition of the present invention includes at least
one or at least two biorenewable components, preferably at least
one biorenewable softener and at least one biorenewable additive in
various embodiments.
[0072] A) Softener
[0073] As indicated hereinabove, one of the biorenewable components
is a softener preferably an oil, e.g. natural oil, such as an ester
group-containing oil, such as a monoester, diester, or triester. As
defined in the art, an ester comprises the formula R--COO--R.sup.1,
wherein R is hydrogen or a hydrocarbyl and R.sup.1 is a
hydrocarbyl, e.g. an alkyl, aryl, or alkyl aryl, each optionally
substituted.
[0074] In one preferred embodiment, the biorenewable softener
component comprises a glyceride or acylglycerol, i.e. a
monoglyceride, diglyceride, triglyceride, or combination thereof.
Many naturally occurring fats and oils are the fatty acid esters of
glycerol. Triglycerides are preferred in one embodiment. The
glycerides can be saturated or unsaturated or a combination
thereof. The styrenic block copolymers having a controlled
distribution copolymer block including a conjugated diene and a
mono alkenyl arena are less polar than a styrenic block copolymer
containing a random conjugated diene and mono alkenyl arene block.
Thus, it is expected that such block copolymers are miscible with
standard mineral or white oil. However, it was surprisingly
discovered that such controlled distribution copolymer
block-containing styrenic block copolymers can be formulated with
relatively high amounts of biorenewable softeners.
[0075] One or more esters can be employed in the present invention.
In a preferred embodiment at least one ester utilized is
biorenewable. Suitable esters that can be employed in the present
invention include those of the following formulas:
##STR00001##
[0076] where n has any value from 1 to about 8, and R.sub.1 and
R.sub.2 are the same or different and are hydrogen or a hydrocarbyl
(including substituted hydrocarbyls) provided the ester is
compatible in the compositions of the invention. It is noted that a
suitable group for R.sub.2 depends on the value of n.
[0077] In one embodiment of the present invention, n is 1, and the
ester has the formula R.sub.1C(O)OR.sub.2 where R.sub.1 is a
C.sub.10-C.sub.22, preferably a C.sub.5-C.sub.22, alkyl, and
R.sub.2 is a lower alkyl radical containing from 1 to 22 carbon
atoms. R.sub.1 is preferably C.sub.13 or more when SEEPS is present
in a composition.
[0078] Another class of suitable esters that may be employed in the
present invention is represented by the following formula:
##STR00002##
where R.sub.1 is defined above and R.sub.3 includes alkylene or
substituted alkylene.
[0079] Still another class of suitable esters that may be employed
in the present invention is represented by the following
formula:
##STR00003##
where R.sub.4, R.sub.5, and R.sub.6 individually include alkylene
or substituted alkylene; and R.sub.7, R.sub.8, and R.sub.9
individually include hydrogen or a hydrocarbyl.
[0080] Suitable esters of the type mentioned above are eicosyl
erucate ester or a C.sub.12-15 alkyl octanoate. Examples of other
suitable esters include, but are not limited to: acetylline
methylsilanol mannuronate; acetaminosalol; acetylated cetyl
hydroxyprolinate; acetylated glycol stearate; acetylated sucrose
distearate; acetylmethionyl methylsilanol elastinate; acetyl
tributyl citrate; acetyl triethyl citrate; acetyl trihexyl citrate;
aleurites moluccana ethyl ester; allethrins; allyl caproate; amyl
acetate; arachidyl behenate; arachidyl glycol isostearate;
arachidyl propionate; ascorbyl dipalmitate; ascorbyl palmitate;
ascorbyl stearate; aspartame; butyl isostearate; butyl stearate;
bean palmitate; behenyl beeswax; behenyl behenate; behenyl erucate;
behenyi isostearate; behenyl/isostearyl beeswax; borago officinalis
ethyl ester; butoxyethyl acetate; butoxyethyl nicotinate;
butoxyethyl stearate; butyl acetate; butyl acetyl ricinoleate;
2-t-butylcyclohexyl acetate; butylene glycol dicaprylate/dicaprate;
butylene glycol montanate; butyl ester of ethylene/MA copolymer;
butyl ester of PVNI copolymer; butylglucoside caprate; butyl
isostearate; butyl lactate; butyl methacrylate; butyl myristate;
butyloctyl beeswax; butyloctyl candelillate; butyloctyl oleate;
butyl oleate; butyl PABA; butylparaben; butyl stearate; butyl
thioglycolate; butyroyl trihexyl citrate; C.sub.18-36 acid glycol
ester; C.sub.12-20 acid PEG-8 ester; calcium stearoyl lactylate;
C.sub.18-28 alkyl acetate; C.sub.18-38 alkyl beeswax; C.sub.30-50
alkyl beeswax; C.sub.20-40 alkyl behenate; C.sub.18-38 alkyl
C.sub.24-54 acid aster; C.sub.8 alkyl ethyl phosphate; C.sub.18-38
alkyl hydroxystearoyl stearate; C.sub.12-13 alkyl lactate;
C.sub.12-15 alkyl lactate; C.sub.12-13 alkyl octanoate; C.sub.12-15
alkyl octanoate; C.sub.18-36 alkyl stearate; C.sub.20-40 alkyl
stearate; C.sub.30-50 alkylstearate; C.sub.40-60 alkyl stearate;
caproyl ethyl glucoside; caprylyl butyrate; C.sub.10-30
cholesterol/lanoster-ol esters; cellulose acetate; cellulose
acetate butyrate; cellulose acetate propionate; cellulose acetate
propionate carboxylate; Ceteareth-7 stearate; cetearyl behenate;
cetearyl candelillate; cetearyl isononanoate; cetearyl octanoate;
cetearyl palmitate; cetearyl stearate; cetyl acetate; acetyl
ricinoleate; cetyl caprylate; cetyl C.sub.12-15Parath-9
carboxylate; cetyl glycol isostearate; cetyl isononanoate; cetyl
lactate; cetyl laurate; cetyl myristate; cetyl octanoate; cetyl
oleate; cetyl palmitalte; cetyl PCA; cetyl PPG-2 isodeceth-7
carboxylate; cetyl ricinoleate; cetyl stearate; C.sub.16-20 glycol
isostearate; C.sub.20-30 glycol isostearate; C.sub.14-16 glycol
palmitate; chimyl isostearate; chimyl stearate; cholesteryl
acetate; cholesteryl/behenyl/octyldodecyl lauroyl glutamate;
cholesteryl butyrate; cinoxate; citronellyl acetate;
coco-caprylate/caprate; coca rapeseedate; cocoyl ethyl glucoside;
corylus avellanna ethyl ester; C.sub.12-15 Pareth-S hydrogenated
tallowate; C.sub.11-15 Pareth-3 oleate; C.sub.12-15 Pareth-12
oleate; C.sub.11-15 Pareth-3 stearate; C.sub.11-15 Pareth-12
stearate; decyl isostearate; decyl myristate; decyl oleate; decyl
succinate; DEDM hydantoin dilaurate; dextrin behenate; dextrin
laurate; dextrin myristate; dextrin palmitate; dextrin stearate;
diacetin; dibutyl adipate; dibutyl oxalate; dibutyl sebacate;
di-C.sub.12-15 alkyl adipate; di-C.sub.12-15 alkyl fumarate;
di-C.sub.12-13 alkyl malate; di-C.sub.12-13 alkyl tartrate;
di-C.sub.14-15 alkyl tartrate; dicapryl adipate; dicaprylyl
maleate; dicetearyl dimer dilinoleate; dicetyl adipate; dicetyl
thiodipropionate; dicocoyl pentaerythrilyl distearyl citrate;
diethoxyethyl succinate; diethyl acetyl aspartate;
diethylaminoethyl cocoate; diethylaminoethyl PEG-5 cocoate;
diethylaminoethyl PEG-5 laurate; diethylaminoethyl stearate;
diethyl aspartate; diethylene glycol diisononanoate; diethylene
glycol dioctanoate; diethylene glycol dioctanoate/diisononanoate;
diethyl glutamate; diethyl oxalate; diethyl palmitoyl aspartate;
diethyl sebacate; diethyl succinate; digalloyl trioleate;
diglyceryl stearate malate; dihexyl adipate; dihexyldecyl lauroyl
glutamate; dihydroabietyl behenate; dihydroabietyl methacrylate;
dihydrocholesteryl butyrate; dihydrocholesteryl isostearate;
dihydrocholesteryl macadamiate; dihydrocholesteryl nonanoate;
dihydrocholesteryl octyldecanoate; dihydrocholesteryl oleate;
dihydrophytosteryl octyldecanoate; dihydroxyethylamino
hydroxypropyl oleate; dihydroxyethyl soyamine dioleate; diisobutyl
adipate; diisobutyl oxalate; diisocetyl adipate; diisodecyl
adipate; diisopropyl adipate; diisopropyl dimer dilinoleate;
diisopropyl oxalate; diisopropyl sebacate; diisostearamidopropyl
epoxypropylmonium chloride; diisostearyl adipate; diisostearyl
dimer dilinoleate; diisostearyl fumarate; diisostearyl glutarate;
diisostearyl matte; dilaureth-7 citrate; dilauryl thiodipropionate;
dimethicone copolyol acetate; dimethicone copolyol adipate;
dimethicone copolyol almondate; dimethicone copolyol beeswax;
dimethicone copolyol behenate; dimethicone copolyol borageate;
dimethicone copolyol cocoa butterate; dimethiccne copolyol dhupa
butterate; dimethicone copolyol hydroxystearate; dimethicone
copolyol isostearate; dimethicone copolyol kokum butterate;
dimethicone copolyol lactate; dimethicone copolyol laurate;
dimethicone copolyol mango butterate; dimethicone copolyol
meadowfoamate; dimethicone copolyol mohwa butterate; dimethicone
copolyol octyldodecyl citrate; dimethicone copolyol olivate;
dimethicone copolyol sal butterate; dimethicone copolyol rhea
butterate; dimethicone copolyol stearate; dimethicone copoly
undecylenate; dimethiconol beeswax; dimethiconol behenate;
dimethiconol borageate; dimethiconol dhupa butterate; dimethiconol
fluoroalcohol dillnoleic acid; dimethiconol hydroxystearate;
dimethiconol illipe butterate; dimethiconol isostearate;
dimethiconol kokum butterate; dimethiconol lactate; di methiconol
mohwa butterate; dimethiconol sal butterate; dimethiconol stearate;
dimethyl adipate; dimethylaminoethyl methacrylate; dimethyl
brassylate; dimethyl cystinate; dimethyl glutarate; dimethyl
maleate; dimethyl oxalate; dimethyl succinate; dimyristyl tartrate;
dimyristyl thiodipropionate; dinonoxynol-9 citrate; dioctyl
adipate; dioctyl butamido triazone; dioctyl dimer dilinoleate;
dioctyldodeceth-2 lauroyl glutamate; dioctyldodecyl adipate;
dioctyldodecyl dimer dilinoleate; dioctyldodecyl dodecanedioate;
dioctyldodecyl fluoroheptyl citrate; dioctyldodecyl lauroyl
glutamate; dioctyldodecyl stearoyl dimer dilinoleate; dioctydodecyl
stearoyl glutamate; diocty fumarate; dioctyl malate; dioctyl
maleate; dactyl sebacate; dioctyl succinate; dioleoyl edetolmonim
methosulfate; dipalmitoyl hydroxyproline; dipentaerythrityl
hexacaprylate/hexacaprate; dipentaerythrityl
hexaheptanoate/hexacaprylate/hexacaprate; dipentaerythrityl
hexahydroxystearate; dipentaerythrityl
hexahydroxystearate/stearate/rosinate; dipentaerythrityl
hexaoctanoate/behenate; dipentaerythrityl
pentahydroxystearate/isostearat-e; dipropyl adipate; dipropylene
glycol caprylate; dipropylene dipropyl oxalate; disodium laureth-7
citrate; disodium PEG-5 laurylcitrate sulfosuccinate; disodium
PEG-8 ricinosuccinate; disodium succinoyl glycyrrhetinate; disodium
2-sulfolaurate; disteareth-2 lauroyl glutamate; disteareth-5
lauroyl glutamate; distearyl thiodipropionate; ditallowoylethyl
hydroxyethylmonium methosulfate; ditridecyl adipate; ditridecyl
dimer dilinoleate; ditridecyl thiodipropionate; dodecyl gallate;
erucyl arachidate; erucyl erucate; erucyl oleate; ethiodized oil;
ethoxydiglycol acetate; ethoxyethanol acetate; ethyl almondate;
ethyl apricot kemelate; ethyl arachidonate; ethyl aspartate; ethyl
avocadate; ethyl biotinate; ethyl butylacetylaminopropionate; ethyl
cyanoacrylate; ethyl cyclolhexyl propionate; ethyl digydroxypropyl
paba; ethylene brassylate; ethylene carbonate; ethy ester of
hydrolyzed animal protein; ethyl ester of hydrolyzed keratin; ethyl
ester of hydrolyzed silk; ethyl ester of pvm/ma copolymer; ethyl
ferulate; ethyl glutamate; ethyl isostearate; ethyl lactate; ethyl
laurate; ethyl linoleate; ethyl linolenate; ethyl niethacrylate;
ethyl methylphenylglycidate; ethyl minkate; ethyl morrhuate; ethyl
myristate; ethyl nicotinate; ethyl oleate; ethyl olivate; ethyl
paba ethyl palmitate; ethylparaben; ethyl pelargonate; ethyl
persate; ethyl phenylacetate; ethyl ricinoleate; ethyl serinate;
ethyl stearate; ethyl thioglycolate; ethyl urocanate; ethyl wheat
germate; ethyl ximenynate; ltocrylene; farnesyl acetate;
galactonolactone; galbanum (ferula galbaniflua) oil;
gamrnma-nonalacione; geranyl acetate; glucarolactone; glucose
glutamate; glucose pentaacetate; glucuronolactone; glycereth-7
diisononanoate; glycereth-8 hydroxystearate; glycereth-5 lactate;
glycereth-25 PCA isostearate; glycereth-7 triacetate; glyceryl
triacetyl hydroxystearate; glyceryl triacetyl ricinoleate;
glycolamide stearate; glycol/butylene glycol montanate; glycol
catearate; glycol dibehenate; glycol dilaurate; glycol dioctanoate;
glycol dioleate; glycol distearate; glycol ditallowate; glycol
hydroxystearate; glycol montanate; glycol octanoate; glycol oleate;
glycol palmitate; glycol ricinoleate; glycol stearate; glycol
stearate SE; glycyrrhetinyl stearate; hexacosyl glycol isostearate;
hexanediol beeswax; hexanediol distearate; hexanetriol beeswax;
hexyldecyl ester of hydrolyzed collagen; hexyldecyl isostearate;
hexyldecyl laurate; hexyldecyl octanoate; hexyldecyl oleate;
hexyldecyl palmitate; hexyldecyl stearate; hexyl isostearate; hexyl
laurate; hexyl nicotinate; homosalate; hydrogenated castor oil
hydroxystearate; hydrogenated castor oil isostearate; hydrogenated
castor oil lauirate; hydrogenated castor oil stearate; hydrogenated
castor oil triisostearate; hydrogenated methyl abietate;
hydrogenated rosin; hydroquinone pca; hydroxycetyl isostearate;
hydroxyoctacosanyl hydroxystearate; inositol hexa-pca; iodopropynyl
butylcarbamate; isoamyl acetate; isoamyl laurate; isobutylated
lanolin oil; isobutyl myristate; isobutyl palmitate;
isobutylparaben; isobutyl pelargonate; isobutyl stearate; isobutyl
tallowate; isoceteareth-8 stearate; isoceteth-10 stearate; isocetyl
behenate; isocetyl isodecanoate; isocetyl isostearate; isocetyl
laurate; isocetyl linoleoyl stearate; isocetyl myristate; isocetyl
octanoate; isocetyl palmitate; isocetyl stearate; isocetyl stearoyl
stearate; isodeceth-2 cocoate; isodecyl citrate; isodecyl cocoate;
isodecyl hydroxystearate; isodecyl isononanoale; isodecyl laurate;
isodecyl myristate; isodecyl neopentanoate; isodecyl octanoate;
isodecyl oleate; isodecyl palmitate; isodecylparaben; isodecyl
stearate; isohexyl laurate; isohexyl neopentanoate; isohexyl
palmitate; isolauryl behenate; isomerized jojoba oil; isononyl
ferulate; isooctyl thioglycolate; isopropyl arachidate; isopropyl
avocadate; isopropyl behenate; isopropyl citrate; isopropyl
C.sub.12-15 pareth-9 carboxylate; isopropyl hydroxystearate;
isopropyl isostearate; isopropyl jojobate; isopropyl lanolate;
isopropyl laurate; isopropyl linoleate; isopropyl myristate;
isopropyl oleate; isopropylparaben; isopropyl PPG-2-isodeceth-7
carboxylate; isopropyl ricinoleate; isopropyl sorbate; isopropyl
stearate; isopropyl tallowate; isopropyl thioglycolate; isosorbide
laurate; isosteareth-10 stearate; isostearyl avocadate; isostearyl
behenate; isostearyl erucate; isostearyl isononanoate; iscstearyl
isostearate; isostearyl isostearoyl stearate; isostearyl lactate;
isostearyl laurate; isostearyl myristate; isostearyl neopentanoate;
isostearyl octanoate; isostearyl palmitate; isostearyl stearoyl
stearate; isotridecyl isononanoate; isotridecyl laurate;
isotridecyl myristate; jojoba (buxus chinensis) oil; jojoba esters;
kojic dipalmitate; laneth-9 acetate; laneth-10 acetate; laneth-4
phosphate; lanolin linoleate; lanolin ricinoleate; laureth-2
acetate; laureth-6 citrate; laureth-7 citrate; laureth-2 octanoate;
laureth-7 tartrate; lauroyl ethyl glucoside; lauroyl lactylic acid;
lauryl behenate; lauryl cocoate; lauryl isostearate; lauryl
lactate; lauryl methacrylate; lauryl myristate; lauryl octanoate;
lauryl oleate; lauryl palmitate; lauryl stearate; linalyl acetate;
linoleyl lactate; madecassicoside; mannitan laurate; mannitan
oleate; menthyl acetate; menthyl anthranilate; menthyl lactate;
menthyl pca; methoxyisopropyl acetate; methoxy-PEG-7 rutinyl
succinate; methyl acetyl ricinoleate; methyl anthranilate; methyl
behenate; methyl caproate; methyl caprylate; methyl
caprylate/caprate; methyl cocoate; 6-methyl coumarin; methyl
dehydroabietate; methyl dihydroabietate; methyldihydrojasmonate;
methyl glucose dioleate; methyl glucose isostearate; methyl glucose
laurale; methyl glucose sesquicaprylate/sesquicaprate; methyl
glucose sesquicocoate; methyl glucose sesquiisostearate; methyl
glucose sesquilaurate; methyl glucose sesquioleate; methyl glucose
sesquistearate; methyl glycyrrhizate; methyl hydrogenated rosinate;
methyl hydroxystearate; methyl isostearate; methyl laurate; methyl
linoleate; methyl 3-methylresorcylate; methyl myristate; methyl
nicotinate; methyl oleate; methyl palmate; methyl palmitate;
methylparaben; methyl pelargonate; methyl ricinoleate; methyl
rosinate; methylsilanol acetylmethionate; methylsilaiaol
carboxymethyl theophylline; methylsilanol carboxymethyl
theophylline alginate; methylsilanol hydroxyproline; methylsilanol
hydroxyproline aspartate; methylsilanol mannuronate; methylsilanol
pca; methyl soyate; methyl stearate; methyl thioglycolate;
monosaccharide lactate condensata; myreth-3 caprate; myreth-3
laurate; myreth-2 myristate; myreth-3 myristate; myreth-3
octanoate; myreth-3 palmitate; myristoyl ethyl glucoside; myristoyl
lactylic acid; myristyl isostearate; myristyl lactate; myristyl
lignocerate; myristyl myristate; myristyl octanoate; myristyl
propionate; myristyl stearate; neopentyl glycol dicaprate;
neopentyl glycol dicaprylate/dicaprate; neopentyl glycol
dicaprylate/dipelargonate/dicaprate; neopentyl glycol diheptanoate;
neopentyl glycol diisostearate; neopentyl glycol dilaurate;
neopentyl glycol dioctanoate; nonyl acetate; nopyl acetate;
octacosanyl glycol isostearate; octocrylene; octyl acetoxystearate;
octyl caprylate/caprate; octyl cocoate; octyldecyl oleate;
octyldodecyl behenate; octyldodecyl erucate; octyldodecyl
hydroxystearate; octyldodecyl isostearate; octyldodecyl lactate;
octyldodecyl lanolate; octyldodecyl meadowfoamate; octyldodecyl
myristate; octyldodecyl neodecanoate; octyldodecyl neopentanoate;
octyldodecyl octanoate; octyldodecyl octyldodecanoate; octyldodecyl
oleate; octyldodecyl olivate; octyldodecyl ricinoleate;
octyldodecyl stearate; octyldodecyl steroyl stearate; octyl
gallate; octyl hydroxystearate; octyl isononanoate; octyl
isopalmitate; octyl isostearate; octyl laurate; octyl linoleayl
stearate; octyl myristate; octyl neopentanoate; octyl octanoate;
octyl oleate; octyl palmitate; octyl PCA; octyl pelagonate; octyl
stearate; oleoyl ethyl glucoside; oleyl acetate; oleyl arachidate;
oleyl erucate; oleyl ethyl phosphate; oleyl lactate; oleyl
lanolate; oleyl linoleate; oleyl myristate; oleyl oleate; oleyl
phosphate; oleyl stearate; oryzanol; ozonized jojoba oil; palmitoyl
carnitine; palmitoyl inulin; palmitoyl myristyl serinate;
pantethine; panthenyl ethyl ester acetate; panthenyl triacetate;
pea glyceryl oleate; pea palmitate; PEG-18 castor oil dioleate;
PEG-5 DMDM hydantoin oleate; PEG-15 dmdm hydantoin stearate; PEG-30
dipolyhydroxystearate; PEG-20 hydrogenated castor oil isostearate;
PEG-50 hydrogenated castor oil isostearate; PEG-20 hydrogenated
castor oil triisostearate; PEG-20 mannitan laurate; PEG-20 methyl
glucose distearate; PEG 80 methyl glucose laurate; PEG-20 methyl
glucose sesquicaprylate/sescquicaprate; PEG-20 methyl glucose
sesguilaurate; PEG-5 oleamide dioleate; PEG-150 pentaerythrityl
tetrastearate; PEG-3/PPG-2 glyceryl/sorbitol
hydroxystearate/isostearate; PEG-4 proline linoleate; PEG-4 proline
linolenate; PEG-8 propylene glycol cocoate; PEG-55 propylene glycol
oleate; PEG-25 propylene glycol stearate; PEG-75 propylene glycol
stearate; PEG-120 propylene glycol stearate; PEG40 sorbitol
hexaoleate; PEG-50 sorbitol hexaoleate; PEG-30 sorbitol tetraoleate
laurate; PEG-60 sorbitol tetrastearate; PEG-5 tricapryl citrate;
PEG-5 tricetyl citrate; PEG-5 trilauryl citrate; PEG-5
trimethylolpropane trimyristate; PEG-5 trimyristyl citrate; PEG-5
tristeaiyl citrate; PEG-6 undecylenate; pentadecalacione;
pentaerythrityl dioleate; pentaerythrityl distearate;
pentaerythrityl hydrogenated rosinate; pentaerythrityl
isostearate/caprate/caprylate/adipate; pentaerythrityl rosinate;
pentaerythrityl stearate; pentaerythrityl
stearate/caprate/caprylate/adipate; pentaerythrityl
stearate/lsostearate/adipate/hydroxystearate; pentaerythrityl
tetraabietate; pentaerythrityl tetraacetate; pentaerityl
tetrabehenate; petaerythrityl tetracaprylate/tetracaprate;
pentaerythrityl tetracocoate; pentaerythrityl tetraisononanoate;
pentaerythrityl tetralaurate; pentaerythrityl tetramyristate;
pentaerythrityl tetraoctanoate;
pentaerythrityl tetraoleate; pentaerythrityl tetrapelargonate;
petaerythrityl tetrastearate; pentaerythrityl trioleate;
phenoxyethylparaben; phylosteryl macadamiate; potassium
butylparaben; potassium deceth-4 phosphate; potassium ethylparaben;
potassiuim methylparaben; potassium propylparaben; PPG-2
isoceleth-20 acetate; PPG-14 laureth-60 alkyl dicarbamate; PPG-20
methyl glucose ether acetate; PPG-20 methyl glucose ether
distearate; PPG-2 myristyl ether propionate; PPG-14 palmeth-80
alkyl dicarbamate; pregnenolone acetate; propylene glycol alginate;
propylene glycol behenate; propylene glycol caprylate; propylene
glycol Ceteth-3 acetate; propylene glycol Ceteth-3 propionate;
propylene glycol citrate; propylene glycol cocoate; propylene
glycol dicaprate; propylene glycol dicaproate; propylene glycol
dicaprylate; propylene glycol dicocoate; propylene glycol
diisononanoate; propylene glycol diisostearate; propylene glycol
dilaurate; propylene glycol dioctanoate; propylene glycol dioleate;
propylene glycol dipelargonate; propylene glycol distearate;
propylene glycol diundecanoate; propylene glycol hydroxystearate;
propylene glycolisoceteth-3 acetate; propylene glycol isostearate;
propylene glycol laurate; propylene glycol linoleate; propylene
glycol linolenate; propylene glycol myristate; propylene glycol
myristyl ether acetate; propylene glycol oleate; propylene glycol
oleate se; propylene glycol ricinoleate; propylene glycol soyate;
propylene glycol stearate; propylene glycol stearate se; propyl
gallate; propylparaben; pyricarbate; pyridoxine dicaprylate;
pyridoxine dilaurate; pyridoxine dioctenoate; pyridoxine
dipalmitate; pyridoxine glycyrrhetinate; pyridoxine tripalmitate;
raffmose myristate; raffinose oleate; resorcinol acetate; retinyl
acetate; retinyl linoleate; retinyl palmitate; retinyl propionate;
riboflavin tetraacetate; ribonolaclone; siloxanetriol phytate;
silybum marianum ethyl ester; sodium behenoyl lactylate; sodium
butylparaben; sodium caproyl lactylate; sodium cocoyl lactylate;
sodium dilaureth-7 citrate; sodium ethylparaben; sodium ethyl
2-sulfolaurate; sodium isostearoyl lactylate; sodium laureth-7
tartrate; sodium lauroyl lectylate; sodium methylparaben; sodium
methyl 2-sulfolaurate; sodium oleoyl lactylate; sodium panteheine
sulfonate; sodium phytate; sodium propylparaben; sodium stearoyl
lactylate; sorbeth-2 cocoate; sorbeth-6 hexastearate; sorbeth-3
isostearate; sorbityl acetate; soybean palmitate; soy sterol
acetate; stearamide dea-distearate; stearamide diba-stearate;
stearamide mea-stearate; steareth-5 stearate; stearoyl lactylic
acid; stearyl acetate; stearyl acetyl glutamate; stearyl beeswax;
stearyl behenate; stearyl caprylate; stearyl citrate; stearyl
erucate; stearyl glycol isostearate; stearyl glycyrrhetinate;
stearyl heptanoate; stearyl lactate; stearyl linoleate; stearyl
octanoate; stearyl stearalte; stearyl stearoyl stearate; sucrose
cocoate; sucrose dilaurate; sucrose distearate; sucrose laurate;
sucrose myristate; sucrose octaacetate; sucrose oleate; sucrose
palmitate; sucrose polybehenate; sucrose polycottonseedate; sucrose
polylaurate; sucrose polylinoleate; sucrose polypalmate; sucrose
polysoyate; sucrose polystearate; sucrose ricinoleate; sucrose
stearate; sucrose tetrastearate triacetate; sucrose tribehenate;
sucrose tristearate; tallowoyl ethyl glucoside; tannic acid;
TEA-lauroyl lactylate; telmesteine; terpineol acetate;
tetradecyleicosyl stearate; tetrahexyldecyl ascorbate;
tetrahydrofurfuryl ricinoleate; tocophersolan; tocopheryl acetate;
tocopheryl linoleate; tocopheryl linoleate/oleate; tocopheryl
nicotinate; tocopheryl succinate; tributyl citrate; tri-C
.sub.12-13 alkyl citrate; tri-C.sub.14-15 alkyl citrate;
tricaprylyl citrate; tridecyl behenate; tridecyl cocoate; tridec),
erucate; tridecyl isononanoate; tridecyl laurate; tridecyl
myristate; tridecyl neopentanoate; tfridecyl octanoate; tridecyl
stearate; tridecyl stearoyl stearate; tridecyl trimellitate;
triethylene glycol hydrogenated rosinate; trihexyldecyl citrate;
triisocetyl citrate; triisopropyl trilinoleate; triisostearyl
citrate; triisostearyl trilinoleate; trilactin; trilauryl citrate;
trimethylolpropane tricaprylate/tricaprate; trimethylolpropane
tricocoate; trimethylolpropane trilaurate; trimethylalpropane
trioctanoate; trimethylolpropane tristearate; trimethyl pentanyl
diisobutyrate; trioctyl citrate; trioctyldodecyl borate; trictyl
trimellitate; trioleyl citrate; tripaba panthenol; tripropylene
glycol citrate; tristearyl citrate; tristearyl phosphate; and yeast
palmitate.
[0081] In a preferred embodiment, the ester-containing oils are
natural product oils that are typically found in animal or plant
tissues, including those which have been hydrogenated to eliminate
or reduce unsaturation. These natural product oils that can be
employed in the present invention include compounds that have the
following formula:
##STR00004##
where R.sub.10 R.sub.11 and R.sub.12 may be the same or different
fatty acid radicals containing from 8 to 22 carbon atoms.
[0082] Suitable natural product oils of the above formula that can
be employed in the present invention include, but are not limited
to: Kernel Oil; Argania Spinosa Oil; Argemone Mexicana Oil; Avocado
(Persea Gratissima) Oil; Babassu (Orbignya Olelfera) Oil; Balm Mint
(Melissa Officinalis) Seed Oil; Bitter Almond (Prunus Amygdalus
Amara) Oil; Bitter Cherry (Prunus Cerasus) Oil; Back Currant (Ribes
Nigrum) Oil; Borage (Borago Officinalis) Seed Oil; Brazil
(Bertholletia Excelsa) Nut Oil; Burdock (Arctium Lappa) Seed Oil;
Butter; C.sub.12-16 Acid Triglyceride; Calophyllurn Tacamahaca Oil;
Camellia Kissi Oil; Camellia Oleifera Seed Oil; Canola Oil;
Caprylic/Capric/Liuric Triglyceride; Caprylic/Capric/Linoleic
Triglyceride; Caprylic/Capric/Myristic/Stearic Triglyceride;
Caprylic/Capric/Stearic Triglyceride; Caprylic/Capric Triglyceride;
Caraway (Carum Carvi) Seed Oil; Carrot (Daucus Carota Sativa) Oil;
Cashew (Anacardium Occidentale) Nut Oil; Castor (Ricinus Communis)
Oil; Cephalins; Chaulmoogra (Taraktogenos Kurzii) Oil, Chia (Salvia
Hispanica) Oil; Cocoa (Theobrama Cacao) Butter; Coconut (Cocos
Nucifera) Oil; Cod Liver Oil; Coffee (Coffee Arabica) Oil; Corn
(Zea Mays) Germ Oil; Corn (Zea Mays) Oil; Cottonseed (Gossypium)
Oil; C.sub.10-18 Triglycerides; Cucumber (Cucumis Sativus) Oil; Dog
Rose (Rosa Canina) Hips Oil; Egg Oil; Emu Oil; Epoxidized Soybean
Oil; Evening Primrose (Oenothera Biennis) Oil; Fish Liver Oil;
Gevuina Avellana Oil; Glyceryl Triacetyl Hydroxystearate; Glyceryl
Triacetyl Ricinoleate; Glycolipids; Glycosphingolipids; Goat
Butter; Grape (Vitis Vinifera) Seed Oil; Hazel (Croylus Americana)
Nut Oil; Hazel (Corylus Aveilana) Nut Oil; Human Placental Lipids;
Hybrid Safflower (Ceathamus Tinctorius) Oil; Hybrid Sunflower
(Helianthus Annuus) Seed Oil; Hydrogenated Canala Oil; Hydrogenated
Castor Oil; Hydrogenated Castor Oil Laurate; Hydrogenated Castor
Oil Triisostearate; Hydrogenated Coconut Oil; Hydrogenated
Cottonseed Oil; Hydrogenated C.sub.12-18 Triglycerides;
Hydrogenated Fish Oil; Hydrogenated Lard; Hydrogenated Menhaden
Oil; Hydrogenated Milk Lipids; Hydrogenated Mink Oil; Hydrogenated
Olive Oil; Hydrogenated Orange Roughy Oil; Hydrogenated Palm Kernel
Oil; Hydrogenated Palm Oil; Hydrogenated Peanut Oil; Hydrogenated
Rapeseed Oil; Hydrogenated Shark Liver Oil; Hydrogenated Soybean
Oil; Hydrogenated Tallow; Hydrogenated Vegetable Oil; Isatis
Tinctoria Oil; Job's Tears (Coix Lacryma-Jobi) Oil; Jojoba Oil;
Kiwi (Actinidia Chinensis) Seed Oil; Kukui (Aleurites Moluccana)
Nut Oil; Lard; Lauric/Palmitic/Oleic Triglyceride; Linseed (Linum
Usitatissiumum) Oil; Lupin (Lupines Albus) Oil; Macadamia Nut Oil;
Macadamia Ternifolia Seed Oil; Macadamia integrifolia Seed Oil;
Maleated Soybean Oil; Mango (Mangifera Indica) Seed Oil; Marmot
Oil; Meadowfoam (Limnanthes fragraAlba) Seed Oil; Menhaden Oil;
Milk Lipids; Mink Oil; Moringa Pterygosperma Oil; Mortierella Oil;
Musk Rose (Rosa Moschata) Seed Oil; Neatsfoot Oil; Neem (Melia
Azadirachta) Seed Oil; Oat (Avena Sativa) Kernel Oil;
Oleic/Linoleic Triglyceride;
Oleic/Palmitic/Lauric/Myristic/L-inoleic Triglyceride;
Oleostearine; Olive (Olea Europaea) Husk Oil; Olive (Olea Europaea)
Oil; Omental Lipdis; Orange Roughy Oil; Ostrich Oil; Oxidized Corn
Oil; Palm (Elaeis Guineensis) Kernel Oil; Palm (Elaeis Guineensis)
Oil; Passionflower (Passiflora Edulis) Oil; Peach (Prunus Persica)
Kernel Oil; Peanut (Arachis Hypogaea) Oil; Pecan (Caiya
Illinoensis) Oil; Pengawar Djambi (Cibotium Barometz) Oil;
Phospholipids; Pistachio (Pistacia Vera) Nut Oil; Placental Lipids;
Poppy (Papaver Orientale) Oil; Pumpkin (Cucurbita Pepo) Seed Oil;
Quinoa (Chenopodium Quinoa) Oil; Rapeseed (Brassica Campestris)
Oil; Rice (Oryza Sativa) Bran Oil; Rice (Oryza Sativa) Germ Oil;
Safflower (Carthamus Tinctorius) Oil; Salmon Oil; Sandalwood
(Santalum Album) Seed Oil; Seabuchthom (Hippophae Rhamnoides) Oil;
Sesame (Sesamum Indicum) Oil; Shark Liver Oil; Shea Butter
(Butyrospermum Parkii); Silk Worm Lipids; Skin Lipids; Soybean
(Glycine Soja) Oil; Soybean Lipid; Sphingolipids; Sunflower
(Helianthus Annuus) Seed Oil; Sweet Almond (Prunus Amygdalus
Dulcis) Oil; Sweet Cherry (Prunus Avium) Pit Oil; Tali Oil; Tallow;
Tea Tree (Melaleuca Altemifolia) Oil; Telphairia Pedata Oil; Tomato
(Solanum Lycopersicum) Oil; Triarachidin; Tiibehenin; Tricaprin;
Tricaprylin; Trichodesma Zeylanicum Oil; Trierucin; Triheptanoin;
Triheptylundecanoin; Trihydroxymethoxystearin; Trihydroxystearin;
Triisononanoin; Triisopalmitin; Triisostearin; Trilaurin;
Trilinolein; Trilinolenin; Trimyristin; Trioctanoin; Triolein;
Tripalmitin; Tripalmitolein; Triricinolein; Trisebacin; Tristearin;
Triundecanoin; Tuna Oil; Vegetable Oil; Walnut (Juglans Regia) Oil;
Wheat Bran Lipids; and Wheat (Triticum Vulgare) Germ Oil. In some
preferred embodiments, the natural oil product is one or more of
soybean oil, coconut oil, rapeseed oil, high oleic acid sunflower
oil or olive oil. The oils of the present invention may be
partially or fully hydrogenated.
[0083] The amount of softener or ester, preferably biorenewable
ester-containing oils, present in the thermoplastic elastomer
compositions of the present invention can vary depending upon the
types of polymers utilized and end products desired to be formed
with the compositions. That said, in one embodiment, the amount of
softener, preferably biorenewable, utilized in the thermoplastic
elastomer compositions ranges generally from about 5 to about 400
parts, desirably from about 50 to about 250 parts, and preferably
from about 75 or 100 to about 200 parts by weight based on 100
total parts by weight of totals styrenic block copolymer. In
another embodiment, the softener or ester, preferably biorenewable,
ranges in an amount generally from about 1 to about $5 parts,
desirably from about 5 to about 75 parts, and preferably from about
10 to 65 about parts by weight based on 100 total parts by weight
of the composition.
[0084] Still additional softeners or extenders include fatty
ethers, fatty alcohols and fatty amines. Said components,
individually, can be utilized in amounts set forth for the
softeners or esters hereinabove.
[0085] Fatty Ethers
[0086] Fatty ethers are utilized in some compositions of the
present invention. Fatty ethers having the general formula
R.sub.13--O--R.sub.14, can be utilized wherein R.sub.13 contains
from about 6 to about 34 carbon atoms and preferably from about 10
to about 22 carbon atoms, and R.sub.4 contains from about 1 to
about 22 carbon atoms and preferably from about 4 to about 22
carbon atoms. The fatty ethers can be linear or branched.
[0087] Fatty Alcohols
[0088] Fatty alcohols are utilized in some compositions of the
present invention. Fatty alcohols having the general formula
R.sub.15--OH, can be utilized wherein R.sub.15 contains from about
6 to about 34 carbon atoms and preferably from about 13 to about 34
carbon atoms. Examples of fatty alcohols include, but are not
limited to 1-hexanol, 1-heptanol, 1-octanol, 1-nonanol, 1-decanol,
1-undecanol, 1-dodecanol, 1-tridecanol, 1-tetradecanol
1-pentadecanol, 1-hexadecanol, 1-heptadecanol, 1-octadecanol,
1-nonadecanol, 1-eicosanol, 1-heneicosanol, 1-docosanol,
1-tricosanol, 1-tetracosanol, 1-pentacosanol, 1-hexacosanol,
1-heptacosanol, 1-octasanol, 1-nonacosanol, 1-tricontanol,
1-hentriacontanol, 1-dotriacontanol, 1-tritriacontanol, and
1-tetratriacontanol. In one embodiment, at least one fatty alcohol
utilized includes saturation and branching. The fatty alcohols can
be linear or branched, for example Guerbet alcohols.
[0089] Fatty Amines
[0090] Fatty amines are utilized in some compositions of the
present invention. Fatty amines can be utilized having the general
formula:
##STR00005##
wherein each R.sub.16, R.sub.17 and R.sub.18, independently, is
hydrogen, or contains from about 4 to about 34 carbon atoms and
preferably from about 10 to about 22 carbon atoms, with the proviso
that at least one said R is not hydrogen. Examples of suitable
fatty amines include, but are not limited to, amines derived from
fatty acids, for example, dimethyl stearamine, stearyl amine, and
oleyl amine. In one embodiment at least one fatty amine utilized
includes saturation and branching. The fatty amines can be linear
or branched.
[0091] B) Synergistic Additives, Preferably Biorenewable
[0092] As indicated hereinabove, the compositions of the present
invention also include a synergistic additive that is believed to
create greater stability within the thermoplastic elastomer
compositions. Some biorenewable synergistic additives are polar
components in various embodiments. The polar synergistic additive
can provide one or more of better oil retention at room temperature
and at higher temperatures and in some embodiments, greater tensile
strength, tensile modulus at various percentages, tensile
elongation and tear strength when compared to a corresponding
composition without the additive. The thermoplastic elastomer
compositions of the present invention can be processed in standard
processing equipment such as injection molders and extruders.
[0093] A number of different biorenewable synergistic additives can
be utilized in combination with the biorenewable softeners of the
present invention. For example, additives include, but are not
limited to, starches; thermoplastic starches; and biorenewable
polar polymers such as aliphatic polyesters, e.g. polylactic acids
and polylactides.
[0094] Starch
[0095] In one embodiment, starches and/or starch-containing
components are utilized as a biorenewable synergistic additive.
Starch-containing components as utilized herein refer to a
composition comprising at least starch and preferably a dispersion
aid, for example glycerin. For example, in one embodiment of a dry
blend process, if starch is used, a dispersion aid such as glycerin
is added to provide desired dispersion of the starch in the
blend.
[0096] The term "starch" as utilized herein refers to any starch of
natural origin whether processed, chemically modified, or treated.
Suitable starches comprise corn starch, potato starch, amaranth
starch, arrowroot starch, banana starch, barley starch, cassava
starch, millet starch, oat starch, pea starch, rice starch, rye
starch, sago starch, sorghum starch, sweet potato starch, tapioca
starch, wheat starch, and yam starch.
[0097] The effective plasticizer or dispersion aid helps swell and
break the crystalline starch granule, and helps lubricate newly
exfoliated, amorphous crystalline starch segments to obtain the
thermoplastic starch. Heat and shear further aids in the starch
gelatinization process. The plasticizer or dispersion aid can
include polyols, such as glycerol, sorbitol etc., adipic acid
derivatives, such as tridecyl adipate, benzoic acid derivatives,
such as isodecyl benzoate, citric acid derivatives, such as
tributyl citrate, glycerol derivatives, phosphoric acid
derivatives, such as tributyl phosphate, polyesters, sebacic acid
derivatives, dimethyl sebacate, urea. The plasticizer or dispersion
aid can also be selected from one or more of glycerine, ethylene
glycol, propylene glycol, ethylene diglycol, ethylene triglycol,
propylene triglycol, polyethylene glycol, polypropylene glycol,
1,2-propanediol, 1,3-propanediol, 1,2-butanediol, 1,3-butanediol,
1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,5-hexanediol,
1,2,6-hexanetriol, 1,3,5-hexanetriol, neopentyl glycol, trimethylol
propane, pantaerythritol, and the acetate, ethoxylate, and
propoxylate derivatives thereof. Moreover, the plasticizer or
dispersion aid can be selected from one or more of sorbitol
ethoxylate, glycerol ethoxylate, pentaerythritol ethoxylate,
sorbitol acetate, and pentaerythritol acetate.
[0098] Starches and starch-containing components provide improved
softener stability. In various embodiments with other biorenewable
components, for example PLA, compositions having desired hardness
ranges can be achieved. Starches and starch-containing components
further increase bio-renewable content of the compositions in
addition to the biorenewable content of the compositions derived
from the softener or plasticizer, without significant deterioration
of the mechanical properties of the compositions.
[0099] Starch includes modified starches, such as chemically
treated and cross-linked starches, and starches in which the
hydroxyl groups have been substituted with organic acids, to
provide esters or with organic alcohols to provide ethers, with
degrees of substitution in the range 0-3.
[0100] Starch also includes extended starches, such as those
extended with proteins; for example with soya protein.
[0101] Thermoplastic Starch
[0102] The biorenewable additives of the present invention also
include thermoplastic starches. Thermoplastic starches offer the
advantages of the capability of flow and are thus suitable for use
in polymer processing methods and equipment. Thermoplastic starches
are available from various commercial sources in compounded form.
In various embodiments, thermoplastic starches are prepared and
used simultaneously in a compounding process to form compositions
of the present invention. Methods of preparing thermoplastic starch
are disclosed in U.S. Pat. No. 6,605,657, herein incorporated by
reference. In various embodiments of the present invention a dry
blended mixture of elastomer such as styrenic block copolymer,
thermoplastic and softener together with other processing additives
are fed through an extruder. The mixture is then melt mixed with
the thermoplastic starch in the remaining downstream portion of the
extruder. There are two extruders involved in this operation. The
two are connected in a "T" shape.
[0103] When present in compositions of the present invention, the
total starch, one or more of starch and thermoplastic starch, is in
an amount from about 2 to about 40 or 80, desirably from about 2 to
about 60 and preferably from 2 to about 40 parts by weight based on
100 total parts by weight of the composition. When utilized, the
dispersion aid is present in an amount from about 1 to about 80,
desirably from about 2 to about 60 and preferably from 2 to about
50 parts by weight based on 100 parts of the starch.
[0104] Polar Polymer
[0105] The biorenewable synergistic additives also include polar
polymers such as aliphatic polyesters. Examples of suitable
aliphatic polyesters include polylactic acids, and polylactides
[PLAs], poly(glycolic acids) and polyglycolides [PGAs], poly
(lactic-co-glycolic), and poly(lactide-co-glycolide) [PLGA],
polyglyconate, poly(hydroxyalkanoates) [PHAs], polyorthoesters
[POEs], polycaprolactones [PCLs], polydioxanone [PDS],
polyanhydrides [PANs], polyether-block-amide (PEBA), and their
copolymers.
[0106] The polar polymers are provided in amounts which impart
desirable properties to the thermoplastic elastomer compositions of
the invention, and, when present, generally range in an amount from
about 0.1 or 1 to about 80 parts, desirably from about 2 to about
60 parts, and preferably from about 2 or 3 to about 20 or 40 parts
based on 100 total parts by weight of the composition of the
present invention.
[0107] Polyolefins
[0108] In one embodiment, the compositions of the present invention
optionally include one or more polyolefins, which as utilized
herein are defined as one or more of a polyolefin polymer and a
polyolefin copolymer unless otherwise indicated. Polyolefins
suitable for use in the compositions of the present invention
comprise amorphous or crystalline homopolymers or copolymers of two
or more same or different monomers derived from alpha-monoolefins
having from 2 to about 12 carbon atoms, and preferably from 2 to
about 8 carbon atoms. Examples of suitable olefins include
ethylene, propylene, 1-butene, 1-pentene, 1-hexene,
2-methyl-1-propene, 3-methyl-1-pentene, 4-methyl-1-pentene,
5-methyl-1-hexene, and combinations thereof. Polyolefins include,
but are not limited to, low-density polyethylene, high-density
polyethylene, linear-low-density polyethylene, polypropylene
(isotactic and syndiotactic), ethylene/propylene copolymers, and
polybutene. Polyolefin copolymers can also include the greater part
by weight of one or more olefin monomers and a lesser amount of one
or more non-olefin monomers such as vinyl monomers including vinyl
acetate, or a diene monomer, etc. Polar polyolefin polymers include
ethylene acrylate and ethylene vinyl acetate, for example. In a
preferred embodiment, EVA is utilized that has a vinyl acetate
content of greater than 5 percent. Generally, a polyolefin
copolymer includes less than 40 weight percent of a non-olefin
monomer, desirably less than 30 weight percent, and preferably less
than about 10 weight percent of a non-olefin monomer.
[0109] In a further embodiment, the polyolefin can include at least
one functional group per chain or can be a blend of
non-functionalized polyolefins and functionalized polyolefins.
Functional groups can be incorporated into the polyolefin by the
inclusion of for example, one or more non-olefin monomers during
polymerization of the polyolefin. Examples of functional groups
include, but are not limited to, anhydride groups such as maleic
anhydride, itaconic anhydride and citraconic anhydride; acrylates
such as glycidyl methacrylate; acid groups such as fumaric acid,
itaconic acid, citraconic acid and acrylic acid; epoxy functional
groups; and amine functional groups. Functional group-containing
polyolefins and methods for forming the same are well known to
those of ordinary skill in the art. Functionalized polyolefins are
available commercially from sources such as Uniroyal, Atofina, and
DuPont. Epoxy modified polyethylenes are available from Atofina as
LOTADER.RTM.. Acid modified polyethylenes are available from DuPont
as FUSABOND.RTM..
[0110] Polyolefin polymers and copolymers are commercially
available from sources including, but not limited to, Chevron, Dow
Chemical, DuPont, ExxonMobil, Huntsman Polymers, Ticona and
Westlake Polymer under various designations.
[0111] When present, the polyolefins range in an amount generally
from about 0.5 to about 60 parts, desirably from about 0.5 or 2 to
about 30 or 50 parts, and preferably from about 0.5 to about 20 or
40 parts by weight based on 100 total parts by weight of the total
composition.
[0112] Additives
[0113] The compositions of the present invention may include
additional additives including, but not limited to lubricants,
light stabilizers, antioxidant, flame retardant additives,
pigments, peroxides, heat stabilizers, processing aids, mold
release agents, flow enhancing agents, nanoparticles, foam agents,
platelet fillers and non-platelet fillers. Examples of fillers for
use in the compositions include, but are not limited to, one or
more of calcium carbonate, talc, clay, zeolite, silica, titanium
dioxide, carbon black, barium sulfate, mica, glass fibers,
whiskers, carbon fibers, magnesium carbonate, glass powders, metal
powders, kaolin, graphite, and molybdenum disulfide. Suitable
fillers include bio-based fillers, e.g. various fibers, cellulose,
and/or lignin.
[0114] Other Polymers
[0115] In various embodiments, other polymers can be added to the
compositions of the present invention in an assortment of amounts
provided that such polymers do not interfere with the desired
performance of the compositions and constructions formed therewith.
Examples of additional polymers include, but are not limited to,
polyamide such as nylon, acrylonitrile-butadiene-styrene copolymers
(ABS), halogenated polymers such as polyvinyl chloride,
polycarbonates, acrylic polymers, PET, PBT, TPU (including TPU with
a bio based polyester block), polyether-block-amide (PEBA).
[0116] The high biorenewable content thermoplastic elastomer
compositions of the present invention can be formed by blending the
desired components in one or more steps, preferably by mixing. The
composition is preferably heated to obtain a melted composition,
preferably with mixing, to substantially disperse the components
thereof. Melt blending is performed at a temperature generally from
about 150.degree. C. to about 250.degree. C. and preferably from
about 170.degree. C. to about 210.degree. C. The compositions can
be prepared for example in a Banbury, on a two roll mill, in a
continuous mixer such as a single screw or twin screw extruder, a
kneader, or any other mixing machine as known to those of ordinary
skill in the art. The compositions containing thermoplastic starch
are prepared in a one step process using combination of single
screw extruder connected midway to a twin screw extruder. The
process is described in detail in U.S. Pat. No. 6,844,380 herein
fully incorporated by reference. After preparation of the
compositions, they can be pelletized or diced utilizing appropriate
equipment, if desired for future further processing. Alternatively,
the compositions can be directly molded, or shaped as desired for
example using an extruder, injection molder, compression molder,
calender, or the like.
[0117] As described herein, desirable compositions can be formed
utilizing the teachings of the present invention which exhibit high
oil stability; low oil softener or ester leaching; or low oil,
etc., bleeding. Oil stability or the like is defined in one
embodiment according to the present invention utilizing a loop spew
test as defined with the examples section. Desirable compositions
according to the present invention have a loop spew rating of 2 or
less, desirably 1 or less, and preferably 0, that is no visible
evidence of oil on the loop surface.
[0118] The compositions of the present invention can be utilized to
form a variety of articles or parts of articles such as, but not
limited to, shaving razors, toothbrushes, writing utensils such as
pens or pencils, brushes such as paint brushes and her brushes,
hair dryers, tools, for example screwdrivers, hammers, wrenches,
pliers and saws, kitchen appliances, for example handles for
refrigerators, ovens, microwaves, dishwashers, kitchen utensils,
such as spoons, forks, knives, spatulas, can openers, bottle
openers, corkscrews, whisks and vegetable peelers, vacuum cleaner
handles, brooms, mops, rakes, shovels, scissors, sporting
equipment, such as fishing poles, firearms, tennis rackets, and
golf clubs, bracelets for example for absorbing sweat, various
seals including automotive weather seals, window encapsulation. The
thermoplastic elastomer compositions of the invention can also be
coated on fabric, such as making wet grip gloves, non-skid fabrics,
etc.
[0119] The compositions of the present invention may be formed as a
composite with a different substrate for example by connecting the
composition of the present invention to the substrate utilizing any
desired method, for example overmolding, insert molding,
coextrusion, welding or bonding with an adhesive. Overmolding
generally involves bonding the thermoplastic elastomer composition
to a polymeric substrate utilizing a two-shot or multi-shot
injection molding process or a co-injection molding process.
Overmolding generally includes providing two or more different
materials that are injected into the same mold during the same
molding cycle. Insert molding generally comprises inserting
pre-molded or preformed substrate into a mold and the composition
of the present invention is molded directly over or to at least a
portion of the insert.
[0120] FIG. 1 illustrates one embodiment of a composite 10 which
comprises a layer 20 including a thermoplastic elastomer
composition having biorenewable content of the present invention
connected to a substrate 30. The substrate can be, for example, one
or more of a polymer, rubber or other elastomer, glass, metal or
natural substrate, such as wood. FIG. 2 illustrates a writing
utensil 40 having a grip 50 formed comprising a composition of the
present invention including biorenewable content. Grip 50 is
connected to body 60, in particular formed in the shape of a
pen.
[0121] For the avoidance of doubt, the compositions of the present
invention encompass all possible combinations of the components,
including various ranges of said components, disclosed herein.
EXAMPLES
[0122] The examples set forth below are provided to illustrate the
high biorenewable content thermoplastic elastomer compositions of
the present invention. These examples are not intended to limit the
scope of the invention.
[0123] Sample Preparation:
[0124] All formulations were prepared in a Leistriz 30 mm
intermeshing co-rotating twin screw extruder with L/D ratio of
40:1. All ingredients were premixed to a uniform, free-flowing
state and then fed to the main feed throat. The extrusion
temperature was 170-200.degree. C. and the extruder screw speed was
180-350 RPM. Samples from the twin screw extruder were then
injection molded at 170-190.degree. C. into plaques approximately 2
mm thick, 6.0 cm wide by 8.75 cm long.
TABLE-US-00001 Specific Gravity ASTM D-792 Hardness (Inst./5 sec)
Shore A ASTM D-2240 MFR 190.degree. C., 2.16 kg g/10 min ASTM
D-1238 Tensile Strength psi ASTM D-412 50% Modulus psi ASTM D-412
100% Modulus psi ASTM D-412 300% Modulus psi ASTM D-412 Tensile
Elongation % ASTM D-412 Tear Strength pli ASTM D-624 Shear
Viscosity, 5-5000 Pa s ASTM D3835 1/S, 200.degree. C.
[0125] Loop Spew Test:
[0126] The oil stability in the compounded TPE was tested with a
method modified from ASTM D 3291, which was designed for testing
plasticizer stability in PVC compound. An approximately 2.54
cm.times.815 cm specimen was cut from an approximately 2 mm thick
molded plaque. The test specimen was conditioned for a minimum of
20 hours at 23.degree. C. A line having a width of about 0.5 mm is
drawn in the middle of the specimen along the long direction of the
specimen using a ballpoint pen. The conditioned specimen was placed
in the loop holder so that a 1.27 cm loop was formed from the edge
of the clamp to the inner edge of the loop, with tolerance being
+/-0.159 cm. The clamped specimen was conditioned for 24 hrs at
23.degree. C., or other temperature as specified within a specific
example. The specimen was removed from the clamp, examined, and
rated as follows:
TABLE-US-00002 Loop Spew Amount of Oil Rating Exudation Comment 0
None No visible evidence of oil in the loop surface 1 Very Slight
Very slight sign of oil appears near the crease line, ball-point
line stays sharp, and cannot be rubbed off 2 Slight Slight sign of
oil appears uniformly in the loop, line stays sharp but starts to
widen 3 Moderate Moderate oil uniformly appears in the loop. Line
further widens and can be rubbed off 4 Severe Some areas have oil
drop, some part of the line starts to disappear 5 Heavy/ Heavy oil
dripping, line has mostly disappeared Dripping
[0127] The following raw materials were utilized for the
examples.
TABLE-US-00003 SBC1 Septon 4055 from Kuraray SBC2 Kraton A1535H
SBC3 Kraton 1633 Soybean oil Cargill technical grade soybean oil
HOAS oil High Oleic Acid Sunflower oil, Cargil Agri-pure 80 HS oil
Hydrogenated Soybean oil, Cargil 23765 - Stable Flake S PP1 Braskem
D115A 12 MI PP PP2 Braskem F008F 0.8 MI PP PLA Nature Works
polylactic acid 4032D SEBS-MA Kraton FG1901 GT Pure TPS
Thermoplastic starch containing 24% glycerin and 76% potato starch
was prepared according to U.S. Pat. No. 6,605,657 White Mineral Oil
Kristaol 550 from Petra-Canada CaCO3 Omyacarb 3 from Omya Inc
Potato Starch MSP Potato Starch from Manitoba Starch Products
Glycerin, technical TR-Glycerine from Twin Rivers grade
Technologies Inc. EVA Elvax 460 from DuPont
TABLE-US-00004 TABLE 1 Comparative Comparative Comparative
Experiment Number Units #1 #2 #3 Example #1 SBC1 37.23% SBC2 37.23%
37.23% 25.34% SBC3 6.98% PP1 13.96% 13.96% 13.96% PP2 10.68% PLA
4.65% White Mineral Oil 48.40% 48.40% Soybean Oil 48.40% 48.17%
CaCO3 3.72% Irganox 1010 0.20% 0.20% 0.20% 0.23% Irgafos 168 0.20%
0.20% 0.20% 0.23% Total (Wt. %) 100.00% 100.00% 100.00% 100.00%
Total Bio Content (Wt. %) 0.0% 0.0% 48.4% 52.8% Loop Spew (Room 0,
no oil 3, oil spew, 2, oil spew, 1 Temperature, 1.27 cm spew line
straight, line straight, Very minor oil loop, 24 hrs) easily easily
spew at the rubbed off. rubbed off. crease line. Much improved over
other hard grade bio TPE Specific Gravity 0.884 0.904 0.932 0.939
Stand Hardness (inst.) A 60.0 58.0 56.0 60.0 Stand Hardness (5 sec)
A 54.0 50.0 50.0 53.0 Tensile Strength Psi 1362 759 1144 804
Tensile Modulus at Psi 194 177 199 233 50% Tensile Modulus at Psi
230 223 244 297 100% Tensile Modulus at Psi 326 369 385 452 300%
Tensile Elongation % 798 611 793 713 Tear Strength (Die C) Pli 138
103 136 153
TABLE-US-00005 TABLE 2 Comparative Experiment Number Units #4
Example #2 Example #3 SBC2 29.44% 26.76% 26.76% PP1 8.61% 7.83%
7.83% SOYBEAN OIL 54.45% 49.50% 49.50% CaCO3 4.00% 3.64% 3.64%
SEBS-MA 3.00% 2.73% 2.73% Pure TPS 9.09% Potato Starch 7.27%
Glycerin, technical grade 1.82% Irganox 1010 0.25% 0.23% 0.23%
Irgafos 168 0.25% 0.23% 0.23% Total (Wt. %) 100.00% 100.00% 100.00%
Total Bio Content (Wt. %) 54.5% 58.6% 58.6% Loop Spew (Room 2, line
may 1, No oil 0 Temperature, 1.27 cm be rubbed spew, but line No
oil loop, 24 hrs) off may be spew rubbed off Specific Gravity 0.953
0.979 0.979 Melt Flow Rate g/10 min 41.0 78.9 41.5 (190.degree.
C./2160 kg) Stand Hardness (inst.) A 38.0 38.0 34.0 Stand Hardness
(5 sec) A 33.0 30.0 31.0 Tensile Strength psi 420 466 362 Tensile
Modulus at 50% psi 135 105 108 Tensile Modulus at 100% psi 172 137
139 Tensile Modulus at 300% psi 265 224 221 Tensile Elongation %
601 747 638 Tear Strength (Die C) pli 91 84 88 Shear Viscosity @
232 Pa s 73 81 71 1/s (200.degree. C., L/D = 30)
TABLE-US-00006 TABLE 3 Experiment Number Comparative #5 Example #4
Example #5 Example #6 Example #7 SBC2 24.24% 27.24% 25.34% 25.34%
25.34% SBC3 6.98% 6.98% 6.98% PP1 16.48% PP2 10.68% 10.68% Soybean
Oil 51.78% 51.78% 48.17% 48.17% 48.17% CaCO3 4.00% 4.00% 3.72%
3.72% 3.72% SEBS-MA 3.00% PLA 16.48% 15.33% 4.65% EVA 4.65% Irganox
1010 0.25% 0.25% 0.23% 0.23% 0.23% Irgafos 168 0.25% 0.25% 0.23%
0.23% 0.23% Total (Wt. %) 100.00% 100.00% 100.00% 100.00% 100.00%
Total Bio Content (Wt. %) 51.8% 68.3% 63.5% 52.8% 48.2% Loop Spew
(Room Units 3, oil spew 0 No Oil 0 No Oil 1 Very minor oil 1 Very
minor oil Temperature, visible Spew Spew spew at the crease spew at
the crease 0.5 in loop, line. Much improved line. Much improved 24
hrs) over other hard over other hard grade bio TPE grade bio TPE
Specific Gravity 0.950 1.003 0.995 0.939 0.933 Melt Flow Rate g/10
min 56.1 65.2 14.0 5.1 4.0 (190.degree. C./2160 kg) Stand Hardness
A 57.0 20.0 18.0 60.0 53.0 (inst.) Stand Hardness A 52.0 17.0 17.0
53.0 46.0 (5 sec delayed) Tensile Strength Psi 552 343 417 804 826
Tensile Modulus Psi 222 54 157 233 172 at 50% Tensile Modulus Psi
269 83 219 297 222 at 100% Tensile Modulus Psi 390 173 349 452 358
at 300% Tensile Elongation % 575 683 540 713 769 Tear Strength Pli
129 54 122 153 113 (Die C) Shear Viscosity @ Pa s 59 68 144 171 181
232 1/s (200.degree. C., L/D = 30)
TABLE-US-00007 TABLE 4 Experiment Number Comparative #6 Example #8
Example #9 Example #10 Example #11 Example #12 SBC2 21.19% 21.45%
24.19% 22.50% 22.50% 22.50% SBC3 7.59% 6.98% 6.98% 6.98% PP1 20.71%
15.18% PP2 14.61% 14.61% Soybean Oil 50.60% 51.22% 50.60% 47.07%
47.07% 47.07% CaCO3 4.00% 4.05% 4.00% 3.72% 3.72% 3.72% SEBS-MA
3.00% PLA 20.71% 19.27% 4.65% EVA 4.65% Irganox 1010 0.25% 0.25%
0.25% 0.23% 0.23% 0.23% Irgafos 168 0.25% 0.25% 0.25% 0.23% 0.23%
0.23% Total (Wt. %) 100.00% 100.00% 100.00% 100.00% 100.00% 100.00%
Total Bio Content (Wt. %) 50.6% 51.2% 71.3% 66.3% 51.7% 47.1% Loop
Spew (Room Units 3, oil spew 2 Slight oil 0 No oil 0 No oil 1 Very
minor oil 1 Very minor oil Temperature, visible spew. Line spew
spew spew at the crease spew at the crease 0.5 in loop, stay sharp
line. Much improved line. Much improved 24 hrs) over other hard
over other hard grade bio TPE grade bio TPE Specific Gravity 0.948
0.955 1.013 1.006 0.934 0.930 Melt Flow Rate g/10 min 58.3 26.1
94.7 22.4 4.8 4.9 (190.degree. C./2160 kg) Stand Hardness A 67.0
58.0 19.0 13.0 70.0 63.0 (inst.) Stand Hardness A 63.0 52.0 16.0
12.0 62.0 57.0 (5 sec) Tensile Strength Psi 528 687 215 383 859 873
Tensile Modulus Psi 283 179 36 209 302 264 at 50% Tensile Modulus
Psi 330 220 52 283 368 323 at 100% Tensile Modulus Psi 443 338 117
379 519 470 at 300% Tensile Elongation % 497 750 625 278 686 653
Tear Strength Pli 140 112 69 111 171 147 (Die C) Shear Viscosity @
Pa s 56 91 49 116 160 175 232 1/s (200.degree. C., L/D = 30)
TABLE-US-00008 TABLE 5 Experiment Number Comparative #7 Example #13
Example #14 Example #15 Example #16 SBC2 27.44% 23.84% 23.84%
23.84% 23.84% SBC3 7.15% 7.15% 7.15% 7.15% Soybean Oil 60.33%
52.46% 35.77% HOAS oil 52.45% 35.77% HS Oil 16.69% 16.69% PP2 6.23%
7.15% 7.15% 7.15% 7.15% PLA 5.96% 5.96% 5.96% 5.96% CaCO3 3.29%
2.87% 2.87% 2.87% 2.87% Irganox 1010 .44% .38% .38% .38% .38%
Irgafos 168 .22% .19% .19% .19% .19% Total (Wt. %) 100 100 100 100
100 Total Bio content, (Wt. %) 60.37% 58.42% 58.42% 58.42% 58.42%
Loop Spew (Room Units 3.0 1.5 0.0 1.5 0.0 Temperature, 0.5 in loop,
24 hrs) Specific Gravity 0.940 0.957 0.968 0.952 0.968 Melt Flow
Rate g/10 min 36.9 9.2 5.8 5.8 4.3 (190.degree. C./2160 kg) Stand
Hardness A 30.0 41.0 60.0 42.0 60.0 (inst.) Stand Hardness A 28.0
39.0 58.0 40.0 58.0 (5 sec delayed) Tensile Strength Psi 537 525
834 578 896 Tensile Modulus Psi 101 142 241 161 255 at 50% Tensile
Modulus Psi 138 200 299 224 310 at 100% Tensile Modulus Psi 248 344
465 362 499 at 300% Tensile Elongation % 740 659 666 701 571 Tear
Strength Pli 96 117 169 122 167 (Die C) Shear Viscosity @ 232 84
137 134 134 134 232 1/s (200.degree. C., L/D = 30)
[0128] As shown in Table 1, Comparative #1 is a general purpose TPE
based on regular SBC and white mineral oil, Comparative #2 is based
on a controlled distribution block-containing SEES and mineral oil,
and Comparative #3 on a controlled distribution block-containing
SEES with vegetable oil, and both Comparatives #2 and #3 showed
noticeable oil spew. With the use of high MW SBC, and some polar
polymer, PLA, the oil stability is much improved at equivalent
hardness as illustrated in Example #1.
[0129] In Table 2, Comparative #4 showed substantial oil bleeding.
Examples #2 and #3 with either TPS or starch with glycerin as a
dispersion aid exhibited greatly improved oil stability.
[0130] In Table 3, Comparative #5 showed substantial oil bleeding.
Examples #4 and #5 with a polar polymer, PLA, improved the oil
stability, but reduced hardness/strength. Examples #6 & 7
showed improved oil stability and strength while maintaining
hardness with the use of high MW SBC, high MW PP in addition to PLA
or EVA.
[0131] In Table 4, Comparative #6 showed substantial oil bleeding.
Example #8 showed some oil stability improvement with the use of
relatively high MW SBC. Examples #9 and #10 with the polar polymer
PLA improved the oil stability, but reduced hardness/strength.
Examples #11 and #12 showed improved oil stability and strength
while maintaining hardness with the use of high MW SBC, high MW PP
in addition to PLA or EVA.
[0132] In Table 5, Comparative #7 exhibited substantial oil
bleeding. The addition of a polar biopolymer, namely PLA, and high
MW SBC significantly improved oil stability. Replacing a portion of
the soybean oil with an ester-containing oil having relatively low
polyunsaturation such as high oleic acid sunflower oil improved oil
compatibility and heat stability, see Example 14. Replacing the
soybean oil with an ester-containing oil having
low-polyunsaturation, namely the high oleic acid sunflower oil also
improved the oil compatibility and heat stability, see Example #15,
as compared to Comparative #7. Example #16 including a combination
of ester-containing oils, namely a high oleic acid sunflower oil
and hydrogenated soybean oil exhibited the best bio-compatibility
and heat stability between Examples 13 through 16.
[0133] While in accordance with the patent statutes the best mode
and preferred embodiment have been set forth, the scope of the
invention is not intended to be limited thereto, but only by the
scope of the attached claims.
* * * * *