U.S. patent application number 11/773576 was filed with the patent office on 2009-01-08 for resin composition for use in forming a polyurethane article with increased comfort.
Invention is credited to Berend Eling, stephan Goettke, Mark J. Hughes, Juergen Mertes, Raymond A. Neff, Jon P. Pavlinac.
Application Number | 20090012195 11/773576 |
Document ID | / |
Family ID | 39743827 |
Filed Date | 2009-01-08 |
United States Patent
Application |
20090012195 |
Kind Code |
A1 |
Neff; Raymond A. ; et
al. |
January 8, 2009 |
RESIN COMPOSITION FOR USE IN FORMING A POLYURETHANE ARTICLE WITH
INCREASED COMFORT
Abstract
A unique combination of a hydrophilic polyol (A) and a
hydrophobic polyol (B) having a terminal ethylene oxide cap are
used in a resin composition and a polyurethane system, and are used
to form a polyurethane article, such as a polyurethane foam. The
hydrophilic polyol (A) is ethylene oxide (EO) rich and the
hydrophobic polyol (B) is propylene oxide (PO) rich. The
hydrophilic polyol (A) and the hydrophobic polyol (B) are present
in the resin composition and the polyurethane system in a weight
ratio (A:B) of from 1.5:1 to 20:1. The polyurethane article
exhibits excellent comfort for use in vehicle applications, such as
automotive and motorcycle seating, due to reduced resonance
frequency and reduced peak vibration transmissivity relative to
previous polyurethane articles.
Inventors: |
Neff; Raymond A.;
(Northville, MI) ; Pavlinac; Jon P.; (South Lyon,
MI) ; Hughes; Mark J.; (Newport, MI) ; Eling;
Berend; (Lemfoerde, DE) ; Mertes; Juergen;
(Ludwigshafen, DE) ; Goettke; stephan; (Vechta,
DE) |
Correspondence
Address: |
BASF AKTIENGESELLSCHAFT
CARL-BOSCH STRASSE 38, 67056 LUDWIGSHAFEN
LUDWIGSHAFEN
69056
DE
|
Family ID: |
39743827 |
Appl. No.: |
11/773576 |
Filed: |
July 5, 2007 |
Current U.S.
Class: |
521/149 ;
524/548; 525/117 |
Current CPC
Class: |
C08G 18/4837 20130101;
C08G 2110/0083 20210101; C08G 18/4841 20130101; C08G 2110/0058
20210101; C08G 18/632 20130101; C08G 18/7664 20130101; C08G 18/7671
20130101; C08G 2110/0008 20210101; C08G 18/4072 20130101; C08G
18/10 20130101; C08G 2350/00 20130101; C08G 18/10 20130101; C08G
18/40 20130101 |
Class at
Publication: |
521/149 ;
524/548; 525/117 |
International
Class: |
C08G 71/04 20060101
C08G071/04; C08F 8/00 20060101 C08F008/00 |
Claims
1. A resin composition for use in forming a polyurethane article,
said resin composition comprising: (A) a hydrophilic polyol
containing alkylene oxides and having; (i) a nominal functionality
of at least 2, (ii) a hydroxyl number of from 20 to 200 mg KOH/g,
and (iii) at least 50 parts by weight ethylene oxide based on 100
parts by weight of said alkylene oxides; and (B) a hydrophobic
polyol containing alkylene oxides and having; (i) a terminal
ethylene oxide cap, (ii) a nominal functionality of at least 2,
(iii) a hydroxyl number of from 20 to 100 mg KOH/g, and (iv) at
least 60 parts by weight propylene oxide based on 100 parts by
weight of said alkylene oxides; wherein said hydrophilic polyol (A)
and said hydrophobic polyol (B) are present in a weight ratio (A:B)
of from 1.5:1 to 20:1.
2. A resin composition as set forth in claim 1 wherein said
hydrophilic polyol (A) and said hydrophobic polyol (B) are present
in a weight ratio (A:B) of from 1.5:1 to 10:1.
3. A resin composition as set forth in claim 2 wherein said
hydrophilic polyol (A) and said hydrophobic polyol (B) are present
in a weight ratio (A:B) of from 1.5:1 to 6:1.
4. A resin composition as set forth in claim 1 wherein said
hydrophilic polyol (A) has at least 70 parts by weight ethylene
oxide based on 100 parts by weight of said alkylene oxides.
5. A resin composition as set forth in claim 4 wherein said
hydrophobic polyol (B) has at least 80 parts by weight propylene
oxide based on 100 parts by weight of said alkylene oxides.
6. A resin composition as set forth in claim 5 wherein said
hydrophobic polyol (B) has from 5 to 25 parts by weight ethylene
oxide based on 100 parts by weight of said hydrophobic polyol
(B).
7. A resin composition as set forth in claim 1 further comprising a
filler component in an amount of from about 0.1 to about 30 parts
by weight based on 100 parts by weight of said resin
composition.
8. A resin composition as set forth in claim 7 wherein said filler
component comprises the reaction product of a monomer selected from
the group of styrenes, acrylonitriles, esters of acrylic and
methacrylic acids, ethylenically unsaturated nitrites, amines,
amides, and combinations thereof.
9. A resin composition as set forth in claim 1 wherein said
alkylene oxides of said hydrophilic polyol (A) comprises a mixture
of ethylene oxide and propylene oxide.
10. A resin composition as set forth in claim 1 wherein said
hydrophilic polyol (A) has a number-average molecular weight of
from 3150 to 4150 and said hydrophobic polyol (B) has a
number-average molecular weight of from 4300 to 5300.
11. A resin composition as set forth in claim 1 wherein said
hydrophilic polyol (A) and said hydrophobic polyol (B) are present
in said resin composition in a combined amount of from about 70 to
about 97 parts by weight based on 100 parts by weight of said resin
composition.
12. A polyurethane system for use in forming a polyurethane
article, said polyurethane system comprising: (A) a hydrophilic
polyol containing alkylene oxides and having; (i) a nominal
functionality of at least 2, (ii) a hydroxyl number of from 20 to
200 mg KOH/g, and (iii) at least 50 parts by weight ethylene oxide
based on 100 parts by weight of said alkylene oxides; and (B) a
hydrophobic polyol containing alkylene oxides and having; (i) a
terminal ethylene oxide cap, (ii) a nominal functionality of at
least 2, (iii) a hydroxyl number of from 20 to 100 mg KOH/g, and
(iv) at least 60 parts by weight propylene oxide based on 100 parts
by weight of said alkylene oxides; and (C) an isocyanate component;
wherein said hydrophilic polyol (A) and said hydrophobic polyol (B)
are present in a weight ratio (A:B) of from 1.5:1 to 20:1.
13. A polyurethane system as set forth in claim 12 wherein said
hydrophilic polyol (A) and said hydrophobic polyol (B) are present
in a weight ratio (A:B) of from 1.5:1 to 10:1.
14. A polyurethane system as set forth in claim 13 wherein said
hydrophilic polyol (A) and said hydrophobic polyol (B) are present
in a weight ratio (A:B) of from 1.5:1 to 6:1.
15. A polyurethane system as set forth in claim 12 wherein said
hydrophilic polyol (A) has at least 70 parts by weight ethylene
oxide based on 100 parts by weight of said alkylene oxides.
16. A polyurethane system as set forth in claim 15 wherein said
hydrophobic polyol (B) has at least 80 parts by weight propylene
oxide based on 100 parts by weight of said alkylene oxides.
17. A polyurethane system as set forth in claim 16 wherein said
hydrophobic polyol (B) has from 5 to 25 parts by weight ethylene
oxide based on 100 parts by weight of said hydrophobic polyol
(B).
18. A polyurethane system as set forth in claim 12 further
comprising a filler component in an amount of from about 0.1 to
about 30 parts by weight based on 100 parts by weight of said
hydrophilic polyol (A) and said hydrophobic polyol (B)
combined.
19. A resin composition as set forth in claim 18 wherein said
filler component comprises the reaction product of a monomer
selected from the group of styrenes, acrylonitriles, esters of
acrylic and methacrylic acids, ethylenically unsaturated nitrites,
amines, amides, and combinations thereof.
20. A resin composition as set forth in claim 12 wherein said
alkylene oxides of said hydrophilic polyol (A) comprises a mixture
of ethylene oxide and propylene oxide.
21. A polyurethane system as set forth in claim 12 wherein said
hydrophilic polyol (A) has a number-average molecular weight of
from 3150 to 4150 and said hydrophobic polyol (B) has a
number-average molecular weight of from 4300 to 5300.
22. A polyurethane system as set forth in claim 12 wherein said
isocyanate component (C) is selected from the group of polymeric
diphenylmethane diisocyanates, diphenylmethane diisocyanates,
toluene diisocyanates, hexamethylene diisocyanates, isophorone
diisocyanates, and combinations thereof.
23. A polyurethane article comprising the reaction product of: (A)
a hydrophilic polyol containing alkylene oxides and having; (i) a
nominal functionality of at least 2, (ii) a hydroxyl number of from
20 to 200 mg KOH/g, and (iii) at least 50 parts by weight ethylene
oxide based on 100 parts by weight of said alkylene oxides; (B) a
hydrophobic polyol containing alkylene oxides and having; (i) a
terminal ethylene oxide cap, (ii) a nominal functionality of at
least 2, (iii) a hydroxyl number of from 20 to 100 mg KOH/g, and
(iv) at least 60 parts by weight propylene oxide based on 100 parts
by weight of said alkylene oxides; and (C) an isocyanate component;
in the presence of (D) a blowing agent component; wherein said
hydrophilic polyol (A) and said hydrophobic polyol (B) are present
in a weight ratio (A:B) of from 1.5:1 to 20:1 prior to reaction to
make said polyurethane article.
24. A polyurethane article as set forth in claim 23 wherein said
hydrophilic polyol (A) and said hydrophobic polyol (B) are present
in a weight ratio (A:B) of from 1.5:1 to 10:1 prior to reaction to
make said polyurethane article.
25. A polyurethane article as set forth in claim 24 wherein said
hydrophilic polyol (A) and said hydrophobic polyol (B) are present
in a weight ratio (A:B) of from 1.5:1 to 6:1 prior to reaction to
make said polyurethane article.
26. A polyurethane article as set forth in claim 23 wherein said
hydrophilic polyol (A) has at least 70 parts by weight ethylene
oxide based on 100 parts by weight of said alkylene oxides.
27. A polyurethane article as set forth in claim 26 wherein said
hydrophobic polyol (B) has at least 80 parts by weight propylene
oxide based on 100 parts by weight of said alkylene oxides.
28. A polyurethane article as set forth in claim 27 wherein said
hydrophobic polyol (B) has from 5 to 25 parts by weight ethylene
oxide based on 100 parts by weight of said hydrophobic polyol
(B).
29. A polyurethane article as set forth in claim 23 further
comprising a filler component in an amount of from about 0.1 to
about 30 parts by weight based on 100 parts by weight of said
hydrophilic polyol (A) and said hydrophobic polyol (B) combined
prior to reaction to make said polyurethane article.
30. A resin composition as set forth in claim 29 wherein said
filler component comprises the reaction product of a monomer
selected from the group of styrenes, acrylonitriles, esters of
acrylic and methacrylic acids, ethylenically unsaturated nitrites,
amines, amides, and combinations thereof.
31. A resin composition as set forth in claim 23 wherein said
alkylene oxides of said hydrophilic polyol (A) comprises a mixture
of ethylene oxide and propylene oxide.
32. A polyurethane article as set forth in claim 23 wherein said
hydrophilic polyol (A) has a number-average molecular weight of
from 3150 to 4150 and said hydrophobic polyol (B) has a
number-average molecular weight of from 4300 to 5300.
33. A polyurethane article as set forth in claim 23 wherein said
isocyanate component is selected from the group of polymeric
diphenylmethane diisocyanates, diphenylmethane diisocyanates,
toluene diisocyanates, hexamethylene diisocyanates, isophorone
diisocyanates, and combinations thereof.
34. A polyurethane article as set forth in claim 33 wherein said
isocyanate component, said hydrophilic polyol (A), and said
hydrophobic polyol (B) are reacted in an amount to have an
isocyanate index of from about 90 to about 120.
35. A polyurethane article as set forth in claim 23 having a peak
vibration transmissivity less than 3.
36. A polyurethane article as set forth in claim 35 having a
density of less than 10 pounds per cubic foot according to ASTM D
3574.
37. A polyurethane article as set forth in claim 23 in combination
with an outer layer in contact with said polyurethane article.
38. A polyurethane article as set forth in claim 37 wherein said
outer layer is further defined as an elastomeric layer.
39. A polyurethane article as set forth in claim 38 wherein said
elastomeric layer comprises the reaction product of a sprayable
elastomer composition.
Description
FIELD OF THE INVENTION
[0001] The present invention generally relates to a resin
composition and to a polyurethane system including the resin
composition, and more specifically, to a polyurethane article
exhibiting increased comfort for use in vehicle applications due to
the resin composition that the polyurethane article is formed
from.
DESCRIPTION OF THE RELATED ART
[0002] Improvement of "comfort" in vehicle seating, such as
automotive and motorcycle seating, has received attention in recent
years. Global demands for improved performance from seat makers and
OEMs have forced a reexamination of many aspects of seat design.
This includes seats that use cushions formed from polyurethane
articles, such as a polyurethane foam. In some cases, such demands
are driven by the desire to reduce the thickness of the cushion to
increase space and reduce weight while achieving the same
performance as the original seat. Comfort has no precise definition
in this regard, although it is frequently described in terms of the
absence of discomfort. The body proportions and weight of a rider,
as well as his or her personal preferences can influence one's
perception. This leads to subjectivity and difficulty in
quantifying comfort.
[0003] With respect to the comfort of a car seat cushion, Japanese
Automobile Standards Organization (JASO) B-407 regulates a standard
on vibration transmissibility characteristics. To obtain a
comfortable feeling, it is effective to remarkably dampen the
vibration in a frequency range that makes riders feel uncomfortable
while being exposed to road vibrations, e.g. while riding on a
motorcycle on a highway. Other sources of discomfort with respect
to the seat include points of high pressure at the interface
between the rider and the seat, in addition to inadequate support
and/or hard feel to the seat. Tendency of polyurethane foams in the
seat to creep with an applied load over time can also affect both
the pressure distribution and the vibration transmissivity of the
seat. Creep is defined as the reversible reduction of the cushion
thickness under constant load and vibration over time, typically up
to 3 hours.
[0004] Vibration performance of the seat can be improved by tuning
the resonance frequency and peak transmissivity of components of
the seat, such as the cushion formed from polyurethane foam.
Generally, lower values for resonance frequency and peak
transmissivity are favorable, as this leads to overall less
vibration transmitted to the rider, and leads to vibrations over a
larger range of frequencies isolated. As described above, changes
in the polyurethane foam properties over time such as creep can
adversely affect comfort, as the car seat will feel harder and the
resonance frequency of the car seat will increase. Fatigue is the
irreversible change in properties resulting from constant or cyclic
loading, as is measured using compression set or pounding tests.
Seats must last many years in order to maintain consumer comfort
and loyalty, of which fatigue properties play an important
role.
[0005] Various polyurethane foams have been developed over the
years for use as cushions for seats. However, these polyurethane
foams suffer from one or more inadequacies, such as the use of
expensive raw materials, use of a high number of components, use of
hazardous components, processing and molding difficulties,
undesirable comfort properties such as high resonance frequencies
and high peak transmissivities, and issues with creeping and
fatigue.
[0006] Accordingly, there remains an opportunity to provide a resin
composition for use in forming a polyurethane article, such as a
polyurethane foam, for a seat cushion that has improved comfort and
performance properties including reduced peak vibration
transmissivity and reduced resonance frequency. In addition, there
remains an opportunity to provide a resin composition, a
polyurethane system, and a polyurethane article that overcomes the
remaining inadequacies described above.
SUMMARY OF THE INVENTION AND ADVANTAGES
[0007] The present invention provides a resin composition for use
in forming a polyurethane article. The resin composition comprises
a hydrophilic polyol (A) containing alkylene oxides and having a
nominal functionality of at least 2, a hydroxyl number of from 20
to 200 mg KOH/g, and at least 50 parts by weight ethylene oxide
based on 100 parts by weight of the alkylene oxides. The resin
composition further comprises a hydrophobic polyol (B) containing
alkylene oxides and having a terminal ethylene oxide cap, a nominal
functionality of at least 2, a hydroxyl number of from 20 to 100 mg
KOH/g, and at least 60 parts by weight propylene oxide based on 100
parts by weight of the alkylene oxides. The hydrophilic polyol (A)
and the hydrophobic polyol (B) are present in the resin composition
in a weight ratio (A:B) of from 1.5:1 to 20:1. The present
invention further provides a polyurethane system comprising the
hydrophilic polyol (A), the hydrophobic polyol (B), and an
isocyanate component (C).
[0008] The present invention provides a unique combination of the
hydrophilic polyol (A) and the hydrophobic polyol (B) used in the
resin composition and the polyurethane system, and used to form the
polyurethane article. The polyurethane article exhibits excellent
comfort for use in vehicle applications due to the resin
composition that the polyurethane article is formed from. The
polyurethane article shows reduced resonance frequency and reduced
peak vibration transmissivity relative to previous polyurethane
articles. Other properties such as creep, hysteresis, and fatigue
are also excellent.
BRIEF DESCRIPTION OF THE DRAWINGS
[0009] Other advantages of the present invention will be readily
appreciated, as the same becomes better understood by reference to
the following detailed description when considered in connection
with the accompanying drawings wherein:
[0010] FIG. 1 is a line graph illustrating vibration transmissivity
as a function of a change in frequency of Comparative (Comp.)
Example 1 and Example 6 of the present invention;
[0011] FIG. 2 is a line graph illustrating percent deflection as a
function of a change in time of Comp. Example 1 and Example 6 of
the present invention;
[0012] FIG. 3 is a line graph illustrating dynamic creep,
specifically DMA (dynamic storage modulus) as a function of a
change in time of Comp. Example 1 and Example 6 of the present
invention;
[0013] FIG. 4 is a line graph illustrating vibration transmissivity
as a function of a change in frequency of Comp. Example 3 and
Example 10 of the present invention; and
[0014] FIG. 5 is a line graph illustrating dynamic creep,
specifically a change in thickness as a function of a change in
time of Comp. Example 3 and Example 10 of the present
invention.
DETAILED DESCRIPTION OF THE INVENTION
[0015] The present invention provides a resin composition for use
in forming a polyurethane article. The resin composition comprises
a hydrophilic polyol (A). The hydrophilic polyol (A) typically has
a nominal functionality of at least 2, more typically from 2 to 6,
and most typically from 2 to 4. By "nominal functionality", it is
meant that the functionality is based upon the functionality of an
initiator molecule, rather than the actual functionality of the
polyol after manufacture. The hydrophilic polyol (A) typically has
a hydroxyl number of from 20 to 200, more typically from 20 to 100,
and most typically from 25 to 55, mg KOH/g. In one embodiment, the
hydrophilic polyol (A) has a hydroxyl number of from about 44 to
about 47 mg KOH/g.
[0016] The hydrophilic polyol (A) contains alkylene oxides. The
hydrophilic polyol (A) typically has at least 50, more typically at
least 70, parts by weight ethylene oxide, each based on 100 parts
by weight of the alkylene oxides. Accordingly, the hydrophilic
polyol (A) is an ethylene oxide rich polyol, which imparts the
hydrophilic polyol (A) with hydrophilicity. In one embodiment, the
hydrophilic polyol (A) is formed from the reaction of one or more
types of alkylene oxides, e.g. oxyalkylene monomers such as
ethylene oxide (EO) monomers, propylene oxide (PO) monomers,
butylene oxide (BO) monomers, etc. It is to be appreciated that the
present invention is not limited to any particular method of making
the hydrophilic polyol (A).
[0017] In one embodiment, the alkylene oxides of the hydrophilic
polyol (A) comprise a mixture of ethylene oxide and propylene
oxide. In another embodiment, the alkylene oxides of the
hydrophilic polyol (A) include only ethylene oxide. In a further
embodiment, the hydrophilic polyol (A) has about 75 parts by weight
ethylene oxide and about 25 parts by weight propylene oxide, each
based on 100 parts by weight of the alkylene oxides. In certain
embodiments, and as alluded to above, the hydrophilic polyol (A)
comprises other types of alkylene oxides known in the art, e.g.
butylene oxide, in combination with ethylene oxide, and optionally,
in combination with propylene oxide.
[0018] The alkylene oxides of the hydrophilic polyol (A) may be
arranged in various configurations, such as a random (heteric)
configuration, a block configuration, a capped configuration, or a
combination thereof. In one embodiment, the hydrophilic polyol (A)
comprises a heteric mixture of ethylene oxide and propylene oxide.
In certain embodiments, the hydrophilic polyol (A) is terminally
capped, such as with an ethylene oxide cap, a propylene oxide cap,
or a butylene oxide cap. If the hydrophilic polyol (A) is
terminally capped, the hydrophilic polyol (A) typically has a
terminal cap of from about 5 to about 25, more typically from about
5 to about 20, and most typically from about 10 to about 15, parts
by weight terminal cap, e.g. ethylene oxide cap, based on 100 parts
by weight of the hydrophilic polyol (A).
[0019] Suitable hydrophilic polyols (A) for purposes of the present
invention include, but are not limited to, glycerine-initiated,
trimethylolpropane-initiated, and sucrose-initiated polyether
polyols, and combinations thereof. In one embodiment, the
hydrophilic polyol (A) is a glycerine-initiated polyether polyol.
The alkylene oxides of the hydrophilic polyol (A) generally extend
from the respective initiator portion of the hydrophilic polyol
(A), and optionally, are terminally capped, as described above. A
specific example of a suitable hydrophilic polyol (A) is
PLURACOL.RTM. 593 polyol, commercially available from BASF
Corporation of Florham Park, N.J. In one embodiment, the
hydrophilic polyol (A) has a number-average molecular weight of
from 3150 to 4150. It is to be appreciated that the hydrophilic
polyol (A) may include any combination of two or more of the
aforementioned hydrophilic polyols. For example, the hydrophilic
polyol (A) can include a first hydrophilic polyol having a nominal
functionality of 2 and a second hydrophilic polyol having a nominal
functionality of 3.
[0020] The resin composition further comprises a hydrophobic polyol
(B) having a terminal ethylene oxide cap. The hydrophobic polyol
(B) typically has a nominal functionality of at least 2, more
typically from 2 to 6, and most typically from 2 to 4. The
hydrophobic polyol (B) typically has a hydroxyl number of from 20
to 100 mg, more typically from 20 to 80, and most typically from 20
to 60, mg KOH/g. In one embodiment, the hydrophobic polyol (B) has
a hydroxyl number of from about 23 to about 26 mg KOH/g. In another
embodiment, the hydrophobic polyol (B) has a hydroxyl number of
from about 34 to about 36 mg KOH/g.
[0021] The hydrophobic polyol (B) contains alkylene oxides. The
hydrophobic polyol (B) typically has at least 60, more typically at
least 80, parts by weight propylene oxide, each based on 100 parts
by weight of the alkylene oxides. Accordingly, the hydrophobic
polyol (B) is a propylene oxide rich polyol, which imparts the
hydrophobic polyol (B) with hydrophobicity. In one embodiment, the
hydrophobic polyol (B) is formed from the reaction of one or more
types of alkylene oxides. It is to be appreciated that the present
invention is not limited to any particular method of making the
hydrophobic polyol (B).
[0022] In one embodiment, the alkylene oxides of the hydrophobic
polyol (B) comprise a mixture of ethylene oxide and propylene
oxide. In another embodiment, the alkylene oxides of the
hydrophobic polyol (B) include only propylene oxide. In certain
embodiments, the hydrophobic polyol (B) comprises other types of
alkylene oxides known in the art, e.g. butylene oxide, in
combination with propylene oxide, and optionally, in combination
with ethylene oxide. The alkylene oxides of the hydrophobic polyol
(B) may be arranged in various configurations, such as a random
(heteric) configuration, a block configuration, a capped
configuration, or a combination thereof. In one embodiment, the
hydrophobic polyol (B) comprises a heteric mixture of ethylene
oxide and propylene oxide.
[0023] As described above, the hydrophobic polyol (B) is terminally
capped with ethylene oxide. The hydrophobic polyol (B) typically
has a terminal cap of from about 5 to about 25, more typically from
about 5 to about 20, and most typically from about 10 to about 15,
parts by weight ethylene oxide, based on 100 parts by weight of the
hydrophobic polyol (B). In one embodiment, the hydrophobic polyol
(B) has about 13 parts by weight ethylene oxide cap based on 100
parts by weight of the hydrophobic polyol (B). It is to be
appreciated that in certain embodiments, the ethylene oxide may
only be present in the terminal ethylene oxide cap; however, in
other embodiments, the ethylene oxide may also be present along
with the propylene oxide, and optionally, other alkylene oxides,
e.g. butylene oxide, in the alkylene oxides of the hydrophobic
polyol (B).
[0024] Suitable hydrophobic polyols (B) for purposes of the present
invention include, but are not limited to, glycerine-initiated,
trimethylolpropane-initiated, and sucrose-initiated polyether
polyols, and combinations thereof. In one embodiment, the
hydrophobic polyol (B) is a glycerine-initiated polyether polyol.
The alkylene oxides of the hydrophobic polyol (B) generally extend
from the respective initiator portion of the hydrophobic polyol
(B). In another embodiment, the hydrophilic polyol (A) and the
hydrophobic polyol (B) are both glycerine-initiated polyether
polyols. Specific examples of a suitable hydrophobic polyols (B)
are PLURACOL.RTM. 538 and PLURACOL.RTM. 2097, both commercially
available from BASF Corporation of Florham Park, N.J. In one
embodiment, the hydrophobic polyol (B) has a number-average
molecular weight of from about 4300 to about 5300. It is to be
appreciated that the hydrophobic polyol (B) may include any
combination of two or more of the aforementioned hydrophobic
polyols. For example, the hydrophobic polyol (B) can include a
first hydrophobic polyol having a nominal functionality of 2 and a
second hydrophobic polyol having a nominal functionality of 3.
[0025] In certain embodiments, the resin composition further
comprises a filler component. The filler component typically
comprises the reaction product of a monomer selected from the group
of styrenes, acrylonitriles, esters of acrylic and methacrylic
acids, ethylenically unsaturated nitriles, amines, amides, and
combinations thereof. In one embodiment, the filler component is
styrene-acrylonitrile copolymer (SAN), which is the reaction
product of a styrene monomer and an acrylonitrile monomer. In
another embodiment, the filler component is urea, which is the
reaction product of an amine monomer and an isocyanate (NCO) group,
such as an NCO group of a diisocyanate. If employed in the resin
composition, the filler component can be a distinct component added
to the resin composition and/or can be included with at least one
of the hydrophilic polyol (A) and the hydrophobic polyol (B), which
is described in further detail below.
[0026] In certain embodiments, at least one of the hydrophilic
polyol (A) and hydrophobic polyol (B) includes the filler
component. In these embodiments, the hydrophilic polyol (A) and/or
the hydrophobic polyol (B) is classified as a polymer polyol. The
polymer polyol can be selected from the group of graft polyols,
graft dispersion polyols, PHD (polyharnstoff dispersion) polyols,
PIPA (polyisocyanate polyaddition) polyols, and combinations
thereof. Graft and graft dispersion polyols are well known to those
skilled in the polyurethane art and include products obtained by
the in-situ polymerization, i.e., reaction, of one or more vinyl
monomers, e.g. styrene monomers and/or acrylonitrile monomers, in a
polyol, e.g. a polyether polyol. In one embodiment, the hydrophobic
polyol (B) is a styrene-acrylonitrile graft polyol. Specific
examples of suitable graft polyols include PLURACOL.RTM. 1365,
PLURACOL.RTM. 4600, PLURACOL.RTM. 4800, PLURACOL.RTM. 4815, and
PLURACOL.RTM. 4830, all commercially available from BASF
Corporation of Florham Park, N.J. PHD polyols are typically formed
by in-situ reaction of a diisocyanate with a diamine in a polyol to
give a stable dispersion of polyurea particles. PIPA polyols are
similar to PHD polyols, except that the dispersion is typically
formed by in-situ reaction of a diisocyanate with an alkanoamine
instead of a diamine, to give a polyurethane dispersion in a
polyol. In certain embodiments, the hydrophobic polyol (B) includes
the filler component in an amount of from about 5 to about 50, more
typically from about 15 to about 40, and most typically from about
20 to about 35, parts by weight of the filler component, based on
100 parts by weight of the hydrophobic polyol (B) and the filler
component combined. In other embodiments, the hydrophilic polyol
(A) includes the filler component in the amounts described above.
It is to be appreciated that in certain embodiments, both the
hydrophilic polyol (A) and hydrophobic polyol (B) can include the
filler component. It is also to be appreciated that the present
invention is not limited to any particular method of making the
polymer polyol, if employed.
[0027] The hydrophilic polyol (A) and the hydrophobic polyol (B)
are present in the resin composition in a weight ratio (A:B) of
from 1.5:1 to 20:1, more typically from 1.5:1 to 10:1, and most
typically from 1.5:1 to 6:1. If the filler component is included
with the hydrophilic polyol (A) and/or the hydrophobic polyol (B),
the respective polymer polyol includes the filler component and a
carrier polyol portion. For purposes of the present invention, the
weight ratio (A:B) described above applies to the parts by weight
of the carrier polyol portion and not to the parts by weight
attributed to by the filler component, if included. This concept is
illustrated by the following formula:
weight ratio (A:B)=(A-X.sub.A):(B-X.sub.B)
where A is equal to the combined parts by weight of the carrier
polyol portion and the filler component of hydrophilic polyol (A),
X.sub.A is equal to only the parts by weight of the filler
component present in the hydrophilic polyol (A), B is equal to the
combined parts by weight of the carrier polyol portion and the
filler component of the hydrophobic polyol (B), and X.sub.B is
equal to only the parts by weight of the filler component present
in the hydrophobic polyol (B). For example, if the hydrophilic
polyol (A) does not include the filler component and is included in
the resin composition in an amount of 60 parts by weight, A=60 and
X.sub.A=0. Further, if the hydrophobic polyol (B) is included in
the resin composition in an amount of 40 parts by weight, and the
hydrophobic polyol (B) includes 25 parts by weight of the filler
component and 75 parts by weight of the carrier polyol portion,
based on 100 parts by weight of the hydrophobic polyol (B), B=40
and X.sub.B=10). Accordingly, with exclusion of the parts by weight
attributed to by the filler component, the hydrophilic polyol (A)
and the hydrophobic polyol (B) are present in the resin composition
in a weight ratio (A:B) of 2:1. The weight ratio (A:B) is important
for controlling the total amount of ethylene oxide and propylene
oxide present in the resin composition, which imparts the resin
composition with hydrophilic/phobic end properties. Overall, the
resin composition is considered hydrophilic, due to the excess of
the hydrophilic polyol (A) relative to the hydrophobic polyol
(B).
[0028] The resin composition may further comprise an additive
component. If employed, the additive component is typically
selected from the group of surfactants, catalysts, fillers, flame
retardants, water, plasticizers, stabilizers, cross-linking agents,
chain-extending agents, chain-terminating agents, air releasing
agents, wetting agents, surface modifiers, waxes, foam stabilizing
agents, moisture scavengers, desiccants, viscosity reducers,
cell-size reducing compounds, cell openers, reinforcing agents,
dyes, pigments, colorants, mold release agents, anti-oxidants,
compatibility agents, ultraviolet light stabilizers, thixotropic
agents, anti-aging agents, lubricants, coupling agents, solvents,
rheology promoters, adhesion promoters, thickeners, smoke
suppressants, anti-static agents, anti-microbial agents, and
combinations thereof.
[0029] Specific examples of suitable catalysts include POLYCAT.RTM.
77, DABCO.RTM. 33LV, DABCO.RTM. BL-11, DABCO.RTM. BL-17, and
DABCO.RTM. 8800, all commercially available from Air Products and
Chemicals of Allentown, Pa., and NIAX.RTM. A-1, commercially
available from Crompton OSi Specialties of Greenwich, Conn.
Specific examples of suitable surfactants include DC-198, DC-5043,
and DC-5164, all commercially available from Dow Corning
Corporation of Midland, Mich., DABCO.RTM. DC-5164, commercially
available from Air Products and Chemicals of Allentown, Pa., and
TEGOSTAB.RTM. B4113, commercially available from Degussa
Goldschmidt Chemical Corporation of Hopewell, Va. It is to be
appreciated that the additive component may include any combination
of the aforementioned additives.
[0030] The resin composition may further comprise a supplemental
polyol in addition to the hydrophilic polyol (A) and the
hydrophobic polyol (B), and optionally, the filler component and/or
the additive component, if employed. The supplemental polyol may be
any polyol or mixture of two or more polyols known in the
polyurethane art, such as diols, triols, or mixtures thereof. A
specific example of a suitable supplemental polyol is a
sucrose/glycerine initiated polyol having a nominal functionality
of 4 and a hydroxyl number of from about 360 to about 375 mg
KOH/gm, commercially available from BASF Corporation of Florham
Park, N.J.
[0031] The hydrophilic polyol (A) and the hydrophobic polyol (B)
may be present in the resin composition in various amounts
following the ratios described above. If at least one of the filler
component, the additive component, and the supplemental polyol is
employed, the hydrophilic polyol (A) and the hydrophobic polyol (B)
are typically present in the resin composition in a combined amount
of from about 70 to about 97, more typically from about 80 to about
90, and most typically from about 80 to about 85, parts by weight,
based on 100 parts by weight of the resin composition. Accordingly,
if employed in the resin composition, the filler component, the
additive component, and/or the supplemental polyol, is present in
the resin composition in the remaining 100 parts by weight of the
resin composition, e.g. from about 3 to about 30 parts by weight
based on 100 parts by weight of the resin composition. In certain
embodiments, the filler component is present in the resin
composition in an amount of from about 0.1 to about 30 parts by
weight, based on 100 parts by weight of the resin composition. In
other embodiments, the additive component is present in the resin
composition in an amount of from about 0.1 to about 15 parts by
weight, based on 100 parts by weight of the resin composition. In
yet other embodiments, the supplemental polyol is present in the
resin composition in an amount of from about 0.1 to about 15 parts
by weight, based on 100 parts by weight of the resin composition.
It is to be appreciated that the filler component, the additive
component, and the supplemental polyol are optional components, and
therefore, the hydrophilic polyol (A) and the hydrophobic polyol
(B) may be present in the resin composition in a combined amount of
100 parts by weight of the resin composition.
[0032] The present invention further provides a polyurethane system
for use in forming the polyurethane article. The polyurethane
system comprises the hydrophilic polyol (A), the hydrophobic polyol
(B), and an isocyanate component (C). The polyurethane system may
further comprise at least one of the filler component, the additive
component, and the supplemental polyol, as described above with
description of the resin composition. The hydrophilic polyol (A)
and the hydrophobic polyol (B) are present in the polyurethane
system in the weight ratio (A:B) of from 1.5:1 to 20:1, more
typically from 1.5:1 to 10:1, and most typically from 1.5:1 to 6:1.
Overall, the polyurethane system is considered hydrophilic, due to
the excess of the hydrophilic polyol (A) relative to the
hydrophobic polyol (B). As previously described and illustrated
above, the weight ratio (A:B) does not apply to any parts by weight
attributed to by the filler component, if included with the
hydrophilic polyol (A) and/or the hydrophobic polyol (B).
[0033] The polyurethane system may be supplied to consumers for use
by various means, such as in large sized drums and containers or
smaller sized kits and packets. For example, one kit can contain
the resin composition and another kit can contain the isocyanate
component (C). It is to be appreciated that the hydrophilic polyol
(A) and the hydrophobic polyol (B) may or may not already be
combined to form the resin composition, i.e., the polyurethane
system may comprise two, three, or more distinct components, such
as individual kits each including distinct components.
[0034] In one embodiment, the isocyanate component (C) is an
organic polyisocyanate. Suitable organic polyisocyanates include,
but are not limited to, conventional aliphatic, cycloaliphatic,
araliphatic and aromatic isocyanates. In one embodiment, the
isocyanate component (C) is selected from the group of
diphenylmethane diisocyanates (MDIs), polymeric diphenylmethane
diisocyanates (pMDIs), and combinations thereof. Examples of other
suitable isocyanates for purposes of the present invention include
toluene diisocyanates (TDIs), hexamethylene diisocyanates (HDIs),
isophorone diisocyanates (IPDIs), and combinations thereof.
Specific examples of suitable isocyanate components (C) include
LUPRANATE.RTM. M, LUPRANATE.RTM. ME, LUPRANATE.RTM. MI, and
LUPRANATE.RTM. M20S, all commercially available from BASF
Corporation of Florham Park, N.J.
[0035] In another embodiment, the isocyanate component (C) is an
isocyanate-terminated prepolymer. The isocyanate-terminated
prepolymer is a reaction product of an isocyanate and an
isocyanate-reactive component. The isocyanate may be any type of
isocyanate known to those skilled in the art, such as one of the
organic polyisocyanates described above. The isocyanate-reactive
component may be a polyol selected from at least one of ethylene
glycol, diethylene glycol, propylene glycol, dipropylene glycol,
butane diol, glycerol, trimethylolpropane, triethanolamine,
pentaerythritol and sorbitol. The isocyanate-reactive component may
be a polyamine selected from, but not limited to, ethylene diamine,
toluene diamine, diaminodiphenylmethane and polymethylene
polyphenylene polyamines, and aminoalcohols. Examples of suitable
aminoalcohols include ethanolamine and diethanolamine,
triethanolamine, and combinations thereof. In one embodiment, the
isocyanate-reactive component is a polyol having a number-average
molecular weight greater than 1,000 and is present in an amount of
from 1 to 20 parts by weight based on 100 parts of the isocyanate
component (C). It is to be appreciated that the isocyanate
component (C) may include any combination of the aforementioned
isocyanates and isocyanate-terminated prepolymers. In addition, the
present invention is not limited to any particular method of making
the isocyanate component (C).
[0036] The present invention yet further provides a polyurethane
article. The polyurethane article comprises the reaction product of
the polyurethane system, i.e., the hydrophilic polyol (A), the
hydrophobic polyol (B), and the isocyanate component (C), in the
presence of a blowing agent component (D). The polyurethane article
may further comprise the reaction product of the supplemental
polyol, and/or include at least one of the filler component and the
additive component, as described above with description of the
resin composition.
[0037] The hydrophilic polyol (A) and the hydrophobic polyol (B)
are present in a weight ratio (A:B) of from 1.5:1 to 20:1, more
typically from 1.5:1 to 10:1, and most typically from 1.5:1 to 6:1,
prior to reaction of the polyurethane system to make the
polyurethane article. Accordingly, the polyurethane article is a
hydrophilic polyurethane foam. In addition, the polyurethane
article is typically classified as a viscoelastic polyurethane
foam. As previously described and illustrated above, the weight
ratio (A:B) does not apply to any parts by weight attributed to by
the filler component, if included with the hydrophilic polyol (A)
and/or the hydrophobic polyol (B), prior to reaction to make the
polyurethane article.
[0038] An isocyanate index, as is known in the polyurethane art, is
a ratio of NCO groups in the isocyanate component (C) to OH groups
in the hydrophilic polyol (A) and the hydrophobic polyol (B)
combined. The isocyanate component (C), the hydrophilic polyol (A),
and the hydrophobic polyol (B), and optionally, the supplemental
polyol, are typically reacted in an amount to have an isocyanate
index of from about 90 to about 120, more typically from about 95
to about 115, and most typically from about 100 to about 115, to
make the polyurethane article. The isocyanate index can be adjusted
in order to change hardness of the polyurethane article. For
example, to make the polyurethane article harder, the isocyanate
index can be increased from 110 to 115. If present in the
polyurethane article, the filler component, e.g. SAN, can also
increase hardness of the polyurethane article, and can also
increase tear strength of the polyurethane article. One skilled in
the polyurethane art appreciates that the amount of isocyanate
component (C) present prior to reaction to make the polyurethane
article can be determined by the isocyanate index in combination
with the combined amount of the hydrophilic polyol (A) and the
hydrophobic polyol (B), and optionally, the supplemental polyol,
present prior to reaction to make the polyurethane article.
[0039] The blowing agent component (D) may be any blowing agent
known in the art. For example, the blowing agent component (D) may
be selected from the group of chemical blowing agents, physical
blowing agents, and combinations thereof. In one embodiment, the
blowing agent component (D) is a chemical blowing agent. As known
to those skilled in the art, chemical blowing agents react with one
or more of the components employed to make the polyurethane
article, such as the isocyanate component (C) to produce a gas,
e.g. carbon dioxide, which physically foams the polyurethane
article while forming. If employed as the blowing agent component
(D), the chemical blowing agent is typically water, which reacts
with the isocyanate component (C) to produce carbon dioxide gas. In
another embodiment, the blowing agent component (D) is a physical
blowing agent. As used herein, physical blowing agents are blowing
agents that retain their original chemical structure throughout a
blowing process, i.e., the physical blowing agent does not react
with any of the components employed to make the polyurethane
article. If employed as the blowing agent component (D), the
physical blowing agent is typically a hydrofluorocarbon (HFC) due
to nonflammability and zero ozone depletion potential. Examples of
suitable physical blowing agents for purposes of the present
invention include HFC-134a, HFC-152a, HFC-245fa, HFC-365mfc,
HFC-22, and combinations thereof.
[0040] It is to be appreciated that some or all of the blowing
agent component (D) may already be present in one of the components
of the present invention. For example, the resin composition may
include water as the additive component, which serves as the
blowing agent component (D). In certain embodiments, the blowing
agent component (D) is water and is included in an amount of from
about 0.5 to about 5 parts by weight based on 100 parts by weight
of the hydrophilic polyol (A) and the hydrophobic polyol (B)
combined, prior to reaction to make the polyurethane article.
[0041] The polyurethane articles of the present invention can be
used for various applications, and are especially suitable for use
in seating applications. For example, the polyurethane article can
be molded in a seat cushion mold to form a seat cushion, e.g. a car
seat cushion, a truck seat cushion, a heavy truck seat cushion, a
motorcycle seat cushion, a bike seat cushion, a tractor seat
cushion, an ATV seat cushion, a boat seat cushion, a jet-ski seat
cushion, a snowmobile seat cushion, etc. The seat cushion mold may
be any seat cushion mold known in the molding and forming art, such
as a closed-type or an open-type mold. If employed, the seat
cushion mold is typically heated, to promote curing of the
polyurethane article. Suitable temperatures for curing the
polyurethane article typically range from 100.degree. F. to
130.degree. F.; however, it is to be appreciated that lower or
higher temperatures may also be used to cure, such as room
temperature. In other words, the seat cushion mold may be
unheated.
[0042] In one embodiment, the polyurethane article is in
combination with an outer layer in contact with the polyurethane
article, which generally enables the use of a thinner and/or softer
seat cushion formed from the polyurethane article of the present
invention. If employed, the outer layer is typically an elastomeric
layer, which typically comprises the reaction product of a
sprayable elastomer composition. Suitable polyurethane elastomer
compositions for purposes of the present invention are disclosed in
U.S. Pat. No. 6,432,543 to Harrison et al., U.S. Pat. No. 6,649,107
to Harrison et al., U.S. Pat. No. 6,852,403 to Harrison et al., and
U.S. Pat. No. 6,352,658 to Chang et al., the disclosures of which
are incorporated herein by reference in their entirety. Examples of
other suitable outer layers for purposes of the present invention
include, but are not limited to, vinyl, cloth, leather, and
combinations thereof.
[0043] As alluded to above, the polyurethane article can be
configured to have various desired end properties such as a
hardness, e.g. a 25% IFD (indentation force deflection) of about 70
pound force (ibf), and/or a density, e.g. about a density of about
5 pounds per cubic foot (lbs/ft.sup.3). In one embodiment, the
polyurethane article has a hardness, specifically a 25% IFD, of
about 75 pound force (lbf). The polyurethane article typically has
a 25% IFD of from about 30 to about 100, more typically from about
40 to about 80, and most typically from about 50 to about 80, lbf.
The polyurethane article typically has excellent fatigue
properties, typically the polyurethane article has a 40% IFD change
of less than about 8, more typically, less than about 5, and most
typically less than about 3, percent loss. In one embodiment, the
polyurethane article has a density of less than 10 lbs/ft.sup.3.
The polyurethane article typically has a density of from about 1 to
about 10, more typically from about 3 to 7, and most typically from
about 4 to about 6, lbs/ft.sup.3. Hardness, fatigue, and density of
the polyurethane articles can be determined according to ASTM D
3574. Other physical properties of the polyurethane articles, such
as hysteresis, can be better appreciated by reference to the
examples described below.
[0044] Generally, two important physical properties of the
polyurethane articles relate to vibration transmissivity,
specifically peak vibration transmissivity and resonance frequency.
These vibration transmissivity properties are usually important
when the polyurethane article is used for making seat cushions, as
previously described above. Generally, a lower resonance frequency
and peak vibration transmissivity are desired, because less
vibration is transmitted to a rider using the seat cushion. In one
embodiment, the polyurethane article has a peak vibration
transmissivity less than 3. In certain embodiments, the
polyurethane article has a thickness of about 4 inches and a peak
vibration transmissivity less than 3. It is to be appreciated that
the polyurethane article may be configured to have various
thicknesses that are thicker or thinner than 4 inches. The
aforementioned embodiments are generally important for meeting
certain comfort requirements for automobile seating as generally
dictated, for example, by JASO B-407. In addition to peak vibration
transmissivity and resonance frequency, dynamic modulus is
generally important for determining creep characteristics of the
polyurethane article.
[0045] There is a link between dynamic modulus and vibration
transmissivity of the polyurethane articles. The resonance
frequency generally increases with the square root of the dynamic
modulus, as illustrated by the following formula:
.omega. 0 = E A d m ##EQU00001##
where .omega..sub.0 is the resonance frequency (in rad/s), E is the
dynamic modulus, A is the cross sectional area covered by a mass, d
is a compressed thickness of the polyurethane article and m is the
mass. The dynamic modulus is a slope of a force deflection curve,
i.e., it is the amount of additional force required to further
deflect the polyurethane article. Generally, a lower dynamic
modulus value is more desirable, since it leads to a lower
resonance frequency of the polyurethane article in addition to less
pressure felt by a rider when exposed to vibrations such as when
riding in a vehicle. As described above, the polyurethane article
may be of various thicknesses, such as those typically used in
seating applications, e.g. about 1 to about 4 inches in
thickness.
[0046] The following examples, illustrating the resin compositions,
polyurethane systems, and polyurethane articles of the present
invention, are intended to illustrate and not to limit the
invention.
EXAMPLES
[0047] Six examples, specifically Examples 1-6, of the polyurethane
article of the present invention are prepared. In addition, two
control polyurethane articles, specifically Comparative (Comp.)
Examples 1 and 2, are prepared for comparison with Examples 1-6.
The polyurethane articles are prepared using standard hand-mix
techniques. All of the components, except for Isocyanate 1, are
blended using a 3-inch diameter mix blade for 45 seconds at 3000
rpm to form a resin composition. Isocyanate 1 is then added to the
resin composition to form a foam mixture, which is then mixed for
an additional 6 seconds. The foam mixture is then poured into a
water-jacketed electrically-heated 15.times.15.times.4 inch
rectangular block mold and a surface temperature of the block mold
is maintained at 120.degree. F. to form blocks of the polyurethane
articles. Configuration of the block mold requires application of a
solvent-based mold release agent and an open mold pour. The
polyurethane articles are de-molded after 7 minutes and are
immediately crushed by hand. The amount and type of each component
used to form the polyurethane articles is indicated in Table 1
below with all values in parts by weight based on 100 parts by
weight of all of the components prior to reaction to make the
polyurethane article unless otherwise indicated.
TABLE-US-00001 TABLE 1 Example Component Comp. 1 Comp. 2 1 2 3 4 5
6 Polyol 1 97.52 -- -- -- -- -- -- -- Polyol 2 -- 77.00 77.00 77.00
59.00 77.00 59.00 68.00 Polyol 3 -- -- -- 18.00 36.00 18.00 36.00
27.00 Polyol 4 -- 2.00 18.00 -- -- -- -- -- Polyol 5 -- 16.00 -- --
-- -- -- -- Catalyst 1 0.165 -- -- -- -- -- -- -- Catalyst 2 0.165
-- -- -- -- -- -- -- Catalyst 3 -- 0.15 0.15 0.15 0.15 0.15 0.15
0.15 Catalyst 4 -- 0.40 0.40 0.40 0.40 0.40 0.40 0.40 Surfactant 1
0.50 -- -- -- -- -- -- -- Surfactant 2 -- 1.00 1.00 1.00 -- 1.00 --
-- Surfactant 3 -- -- -- -- 1.00 -- 1.00 1.00 Water 1.65 1.65 1.65
1.65 1.65 1.65 1.65 1.65 Isocyanate 1 29.68 32.45 31.72 31.30 30.44
34.59 33.65 32.49 Isocyanate 100 95 95 95 95 105 105 100 Index
[0048] Polyol 1 is a high molecular weight polyol having about 21
wt % ethylene oxide, a nominal functionality of 3 and a hydroxyl
number of from 26.5 to 28.5 mg KOH/gm, commercially available from
BASF Corporation of Florham Park, N.J.
[0049] Polyol 2 is an ethylene oxide rich hydrophilic polyol having
about 75 wt % ethylene oxide, a nominal functionality of 3, a
hydroxyl number of from 44.0 to 47.0 mg KOH/gm, and a
number-average molecular weight of about 3650, commercially
available from BASF Corporation of Florham Park, N.J.
[0050] Polyol 3 is a propylene oxide rich hydrophobic graft polyol
comprising a carrier polyol having a terminal ethylene oxide cap of
about 13 wt % and having about 32% SAN solids, a nominal
functionality of 3, and a hydroxyl number of from 23 to 26 mg
KOH/gm, commercially available from BASF Corporation of Florham
Park, N.J.
[0051] Polyol 4 is a high molecular weight polyol having a terminal
ethylene oxide cap of about 13 wt %, a nominal functionality of 3,
a hydroxyl number of from 34.0 to 36.0 mg KOH/gm, and a
number-average molecular weight of about 4800, commercially
available from BASF Corporation of Florham Park, N.J.
[0052] Polyol 5 is a hydroxyl terminated polypropylene glycol
having a number-average molecular weight of about 2000,
commercially from BASF Corporation of Florham Park, N.J.
[0053] Catalyst 1 is a tertiary amine catalyst comprising
bis-(dimethylaminopropyl)methylamine, commercially available from
Air Products and Chemicals of Allentown, Pa.
[0054] Catalyst 2 is an amine blowing catalyst comprising
bis-(2-dimethylamino ethyl)ether, commercially available from Air
Products and Chemicals of Allentown, Pa.
[0055] Catalyst 3 is an amine blowing catalyst comprising about 70
wt % bis-(2-dimethylaminoethyl)ether and about 30 wt % dipropylene
glycol, commercially available from Air Products and Chemicals of
Allentown, Pa.
[0056] Catalyst 4 is a gelling catalyst comprising about 33 wt %
triethylenediamine and about 67 wt % dipropylene glycol,
commercially available from Air Products and Chemicals of
Allentown, Pa.
[0057] Surfactant 1 is a cell-regulating silicone surfactant,
commercially available from Degussa Goldschmidt Chemical
Corporation of Hopewell, Va.
[0058] Surfactant 2 is a nonionic silicone glycol surfactant,
commercially available from Dow Corning Corporation of Midland,
Mich.
[0059] Surfactant 3 is a silicone surfactant, commercially
available from Dow Corning Corporation of Midland, Mich.
[0060] Isocyanate 1 is a blend of three isocyanates comprising:
[0061] 1) about 36 wt % of polymethylene polyphenylpolyisocyanate
having a functionality of about 2.7 and an NCO content of about
31.5 wt %; [0062] 2) about 33.0 wt % of an essentially pure
4,4'-diphenylmethane diisocyanate having a functionality of about
2.0 and an NCO content of about 33.5 wt %; and [0063] 3) about 31
wt % of a mixture of about 50 wt % of 2,4'-diphenylmethane
diisocyanate and about 50 wt % of 4,4'-diphenylmethane
diisocyanate, the mixture having a functionality of about 2 and an
NCO content of about 33.5 wt %; all commercially available from
BASF Corporation of Florham Park, N.J.
[0064] Various physical properties of the polyurethane articles are
tested. For example, IFD, tensile strength, falling ball
resilience, and heat aging, density, block tear, air flow, and
compression sets, etc., are measured in accordance with ASTM D
3574. Vibration transmissivity is conducted on the polyurethane
articles using a testing apparatus. The testing apparatus includes
a shaker, a table above the shaker, accelerometers, and a mass
above the table. The mass is an 8-inch diameter disk weighing 50
lbs. The block of the polyurethane article is placed on the shaker
between the table and the mass. Accelerometers are placed on the
table and the mass. After loading the polyurethane article, the
mass is allowed to rest on the polyurethane article for 30 seconds.
A sinusoidal waveform is then applied to the table, and frequencies
between 1 and 10 Hz are scanned within 150 seconds, recording data
every 0.1 Hz. Peak acceleration at the table is controlled at a
constant 0.2 g. Data is recorded as a ratio of acceleration at the
mass to acceleration at the table. Digital filtering is employed to
reduce noise in the data.
[0065] DMA (Dynamic Mechanical Analysis) is performed in accordance
with ASTM D 4065, using a Rheometrics RSA III and disk-shaped DMA
samples of the polyurethane articles. The DMA samples have a
diameter of 25 mm and a height of 13 mm. Data is collected using a
temperature sweep between -100.degree. C. and +200.degree. C., a
heating rate of 5.degree. C./min, a frequency of 1 Hz and a strain
amplitude of 0.2%.
[0066] Dynamic Creep analysis is performed using the Rheometrics
RSA III and disk-shaped creep samples of polyurethane articles. The
creep samples have a diameter of 25 mm and a height of 25 mm. Force
required for compressing the creep samples 40% of the original
height (25 mm) is measured using the Rheometrics RSA III, and the
samples are allowed to relax for 24 hours. The creep samples are
then loaded into the Rheometrics RSA III, and statically compressed
to the predetermined force. An oscillatory strain with amplitude of
1 mm and a frequency of 1 Hz is applied to the creep sample. An
auto-tension feature is used to maintain a static force constant at
the value originally measured, resulting in a steady decrease of
thickness of the creep sample due to creep. Dynamic modulus and
sample thickness of the samples are recorded for two hours. Various
physical properties of the examples are shown below in Table 2.
Vibration transmissivity and percent deflection of Comp. Example 1
and Example 6 are also illustrated in FIGS. 1, 2 and 3, wherein
Example 6 shows dramatic improvements relative to Comp. Example
1.
TABLE-US-00002 TABLE 2 Example Comp. 1 Comp. 2 1 2 3 4 5 6
Mechanical Properties Core Density (lbs/ft.sup.3) 5.00 4.90 5.03
4.81 5.07 4.84 4.91 5.04 Original 25% IFD (lbf) 73.18 32.73 48.70
61.55 61.05 69.40 70.25 65.00 Original 25% R IFD (lbf) 61.98 32.05
46.11 59.12 58.01 66.54 66.58 62.45 Original 65% IFD (lbf) 184.01
80.42 99.06 131.24 138.02 146.47 160.75 148.60 SAG Factor 2.51 2.46
2.03 2.13 2.26 2.11 2.29 2.29 Recovery (%) 84.70 97.92 94.68 96.05
95.02 95.88 94.78 96.08 Hysteresis (%) 24.60 6.00 9.70 9.30 11.60
9.40 11.60 8.90 Air Flow (cfm) 1.25 6.00 0.41 0.17 0.17 0.18 7.14
0.62 Block Tear (ppi) 1.65 1.20 0.45 0.42 0.80 0.56 0.91 0.65 Break
Elongation (%) 75.73 105.87 41.70 42.87 60.97 39.17 59.53 48.70
Tensile Strength (psi) 12.66 10.18 4.73 6.77 11.26 7.21 12.47 10.03
Original 50% CFD (psi) 1.45 0.59 0.80 1.04 1.06 1.20 1.24 1.19
Humid Aged (3 hrs 220.degree. F.) 82.09 62.52 62.11 66.86 67.90
69.04 70.85 71.32 CFD % of Original (%) Comp Set 50% Ambient (%)
2.82 0.68 1.07 0.92 1.50 0.79 0.94 0.86 Comp Set 90% Ambient (%)
2.63 0.36 -0.61 1.13 1.57 1.23 1.62 -0.05 Core Resilience (%) 63 62
43 41 34 37 39 60 Pounding Fatigue % Thickness Loss 1.06 0.58 0.63
0.92 0.63 0.92 0.77 0.77 40% IFD (% Loss) 8.70 2.16 4.22 2.74 5.73
2.45 2.42 2.57 Vibration Transmissivity Resonance Frequency (Hz)
7.54 3.05 3.37 5.25 5.53 6.41 5.07 3.73 Peak Transmissivity 6.21
2.92 2.13 1.55 1.53 2.41 2.95 2.67 DMA Peak Tan Delta 0.87 0.71
0.78 0.74 0.53 0.72 0.55 0.65 Tg (.degree. C.) -50.5 -14.7 -17.6
-19.6 -7.6 -17.8 -10.1 -15.9
[0067] All of the Examples 1-6 perform well in both the dynamic
creep and vibration tests relative to Comp. Example 1. Peak
transmissivity is consistently less than the Comp. Example 1, and
the resonance frequency is better than Comp. Example 1. Hardness
for all of the Examples 1-6 is consistently higher than Comp.
Example 2. Fatigue is reduced for all of the Examples 1-6 relative
to Comp. Example 1. Example 6 shows the best combination of
hardness and performance in the vibration transmissivity
testing.
[0068] Three additional examples, specifically Examples 7-9, of the
polyurethane article of the present invention are prepared. In
addition, one control polyurethane article, specifically Comp.
Example 3, is prepared for comparison with the Examples 7-9. The
foam mixtures are dispensed through an EMB high-pressure urethane
metering machine. Total output of the foam mixture is maintained at
a rate of 250 g/s. Resin and isocyanate component temperatures are
both maintained at 80.degree. F. The surface temperature of the
block mold is maintained at 120.degree. F. to form blocks of the
polyurethane articles. The polyurethane articles are de-molded
after about 3 minutes. Immediately upon de-molding, the
polyurethane articles are crushed by hand. The amount and type of
each component used to form the polyurethane articles is indicated
in Table 3 below with all values in parts by weight based on 100
parts by weight of all of the components prior to reaction to make
the polyurethane article unless otherwise indicated.
TABLE-US-00003 TABLE 3 Example Component Comp. 3 7 8 9 Polyol 1
97.52 -- -- -- Polyol 2 -- 68.00 68.00 68.00 Polyol 3 -- 27.00
27.00 27.00 Catalyst 1 0.165 -- -- -- Catalyst 2 0.165 -- -- --
Catalyst 3 -- 0.15 0.15 0.15 Catalyst 4 -- 0.40 0.40 0.40
Surfactant 1 0.50 -- -- -- Surfactant 3 -- 1.00 1.00 1.00 Water
1.65 1.65 1.65 1.65 Isocyanate 1 29.68 32.49 35.80 37.40
[0069] Various physical properties of the polyurethane articles are
tested as described above with Examples 1-6 and illustrated in
Table 4 below. Peak transmissivity is consistently less for
Examples 7-9 relative to Comp. Example 3.
TABLE-US-00004 TABLE 4 Example Comp. 3 7 8 9 Mechanical Properties
Core Density (lbs/ft.sup.3) 4.93 5.12 5.07 5.05 Original 25% IFD
(lbf) 75.16 54.23 65.44 73.41 Original 25% R IFD (lbf) 62.80 51.85
62.67 69.94 Original 65% IFD (lbf) 206.85 119.55 146.37 160.22 SAG
Factor 2.75 2.20 2.24 2.18 Recovery (%) 83.56 95.61 95.77 95.27
Hysteresis (%) 26.90 10.40 10.20 11.20 Air Flow (cfm) 0.53 0.12
0.23 0.18 Block Tear (ppi) 1.39 0.66 0.79 0.93 Break Elongation (%)
72.13 57.37 60.00 58.13 Tensile Strength (psi) 20.00 9.79 12.55
13.20 Original 50% CFD (psi) 1.43 0.99 1.17 1.37 Humid Aged (3 hrs
220.degree. F.) 88.68 75.38 78.79 79.08 CFD % of Original (%) Comp
Set 50% Ambient 2.96 1.93 2.67 2.12 Humid Aged (3 hrs 220.degree.
F.) -- 1.39 0.15 0.65 50% Compr. Set (%) Core Resilience (%) 52.00
28.00 32.00 38.00 Vibration Transmissivity Resonance Frequency (Hz)
6.90 6.60 5.20 5.70 Peak Transmissivity 5.40 1.90 1.80 2.20 DMA
Peak Tan Delta 0.79 0.59 0.55 0.49 Tg (.degree. C.) -49.00 -12.03
-9.78 -6.52
[0070] One additional example, specifically Example 10, of the
polyurethane article of the present invention is prepared. In
addition, one control polyurethane article, specifically Comp.
Example 4, is prepared for comparison with Example 10. The
polyurethane articles are made like the polyurethane articles
described above with Examples 1-6.
[0071] The amount and type of each component used to form the
polyurethane articles is indicated in Table 5 below with all values
in parts by weight based on 100 parts by weight of all of the
components prior to reaction to make the polyurethane article
unless otherwise indicated.
TABLE-US-00005 TABLE 5 Example Component Comp. 4 10 Polyol 6 --
69.10 Polyol 7 91.60 -- Polyol 8 -- 30.90 Polyol 9 3.50 -- Polyol
10 0.60 -- Catalyst 3 0.05 -- Catalyst 4 0.60 0.25 Catalyst 5 --
0.54 Catalyst 6 0.40 -- Catalyst 7 0.50 -- Surfactant 1 0.30 --
Surfactant 2 -- 0.50 Water 2.45 2.20 Isocyanate 2 54 -- Isocyanate
3 -- 50.8 Isocyanate 100 100 Index
[0072] Polyol 6 is an ethylene oxide rich hydrophilic polyol having
a terminal ethylene oxide cap of about 5 wt % and about 75 total wt
% ethylene oxide, a nominal functionality of 3, and a hydroxyl
number of about 41.0 mg KOH/gm, commercially available from BASF AG
of Ludwigshafen, Germany.
[0073] Polyol 7 is a glycerine initiated polyether polyol having a
terminal ethylene oxide cap of about 14 wt % ethylene oxide, a
nominal functionality of 3, and a hydroxyl number of about 28.0 mg
KOH/gm, commercially available from BASF AG of Ludwigshafen,
Germany.
[0074] Polyol 8 is a graft polyol having about 45% SAN solids, a
nominal functionality of 3, and a hydroxyl number of from 23 to 26
mg KOH/gm, commercially available from BASF AG of Ludwigshafen,
Germany.
[0075] Polyol 9 is an ethylene oxide rich cell opening polyol,
commercially available from Dow Chemical Company of Midland,
Mich.
[0076] Polyol 10 is 1,4-butandiol, commercially available from BASF
Corporation of Florham Park, N.J.
[0077] Catalyst 5 comprises about 33 wt % 1,4-diazabicyclooctane
and about 67 wt % dipropylene glycol, commercially available from
BASF Corporation of Florham Park, N.J.
[0078] Catalyst 6 comprises dimethylaminoethoxyethanol (DMEE),
commercially available from BASF Corporation of Florham Park,
N.J.
[0079] Catalyst 7 comprises N,N-dimethylethanolamine S (DMEA),
commercially available from BASF Corporation of Florham Park,
N.J.
[0080] Isocyanate 2 is an isocyanate-terminated prepolymer
comprising: [0081] 1) about 24.50 wt % of 4,4'-diphenylmethane
diisocyanate having a functionality of about 2 and an NCO content
of about 33.5 wt %; [0082] 2) about 11.90 wt % of a mixture of
about 50 wt % of 2,4'-diphenylmethane diisocyanate and about 50 wt
% of 4,4'-diphenylmethane diisocyanate, the mixture having a
functionality of about 2 and an NCO content of about 33.5 wt %;
[0083] 3) about 54.50 wt % of a polymethylene
polyphenylpolyisocyanate having a functionality of about 2.7 and an
NCO content of about 31.5 wt %; and [0084] 4) about 9.10 wt % of
Polyol 6; all commercially available from BASF AG of Ludwigshafen,
Germany.
[0085] Isocyanate 3 is an isocyanate-terminated prepolymer
comprising: [0086] 1) about 39.76 wt % of a pure
4,4'-diphenylmethane diisocyanate; [0087] 2) about 31.62 wt % of a
mixture of about 50 wt % of 2,4'-diphenylmethane diisocyanate and
about 50 wt % of 4,4'-diphenylmethane diisocyanate, the mixture
having a functionality of about 2 and an NCO content of about 33.5
wt %; [0088] 3) about 9.00 wt % of a polymethylene
polyphenylpolyisocyanate having a functionality of about 2.7 and an
NCO content of about 31.5 wt %; and [0089] 4) about 19.62 wt % of
Polyol 6; all commercially available from BASF AG of Ludwigshafen,
Germany.
[0090] Various physical properties of the polyurethane articles are
tested and illustrated in Table 6 below. Vibration transmissivity
testing is conducted on the polyurethane articles. A vibration
table including upper and lower plates, a mass, and a
servo-hydraulic apparatus is used to test the polyurethane
articles. A 100.times.100.times.50 mm sample of the polyurethane
article is placed between the upper and lower plates, with the
plates completely overlapping the sample. The plates are
constructed according to ISO 3386-1. The lower plate is perforated
with 6 mm diameter holes spaced 20 mm apart. A frictionless bearing
is placed on top of the upper plate. An 8 mm diameter guiding rod
is passed through the frictionless bearing, through the center of
the upper plate, and through a hole bored through the center of the
sample. The mass is placed over the upper plate and guiding rod,
and allowed to rest for 30 minutes. The guiding rod restricts the
movement of the mass and the sample to a single axis. The table is
accelerated by the servo-hydraulic apparatus generating sinusoidal
displacement with an amplitude of 0.25 mm. Frequency is
continuously increased from 1 to 21 Hz within 600 seconds,
specifically at a rate of 2 Hz per minute. Displacement of both the
mass and the table is measured by a high resolution laser
extensometer. Through addition of weights, the mass is adjusted to
a compression stress value of the sample at 40% deflection, which
is previously measured for the sample (according to ISO 3386-1).
The transmissivity, calculated as the ratio of the displacement
amplitudes at the upper and the lower plates, is plotted against
frequency, as illustrated in FIG. 4 for Comp. Example 4 and Example
10.
[0091] Loss of thickness under dynamic condition testing is
conducted on the polyurethane articles. A 100.times.100.times.50 mm
sample of the polyurethane article is placed between the upper and
lower plates, with the plates completely overlapping the sample, as
described above. The sample is compressed four times/cycles to 70%
deflection at a rate of 100 mm per minute. Upon reaching 45%
deflection in the fourth cycle, the initial static force required
to achieve this deflection is recorded. Following completion of the
fourth cycle, the initial static force is maintained through
continuous adjustment of displacement, and a sinusoidal
displacement of 1 Hz frequency and 0.25 mm amplitude is
superimposed using the servo-hydraulic apparatus. Air temperature
is maintained at 40.degree. C., and the relative humidity is
changed every two hours, alternating between an initial relative
humidity of 25% and 80%. The duration of the measurement is 80,000
cycles. Thickness of the sample is recorded as a function of time,
as illustrated in FIG. 4 for Comp. Example 4 and Example 10.
Referring to FIGS. 4 and 5, Example 10 shows dramatic improvement
relative to Comp. Example 4.
TABLE-US-00006 TABLE 6 Example Mechanical Properties Comp. 4 10
Core Density (lbs/ft.sup.3) 5.38 5.92 Density (lbs/ft.sup.3) 5.41
5.93 CLD (40%) (kPa) 11.5 10 Hysterisis (%) 14.3 11.8 Break
Elongation (%) 84 116 Tensile Strength (kPa) 165 148 Shear Strength
(BMW-Norm) (N/mm) 1.9 2.3 Compression Set (BMW-Norm) (%) 2.6 1.9
Wet Compression Set (%) 6.6 -2.5 Resilience (pendulum) (%) 72 35
Resilience (ball) (%) 67 32
[0092] Four resin compositions, specifically Resins A-D, of the
present invention are prepared. The resin compositions are made
like the resin compositions described above with Examples 1-6.
Phase separation of the resin compositions is a possible concern.
Therefore, Resins A and B are mixed and stored in quart glass jars
at ambient temperature. After two months, no phase separation is
observed for either resin. The viscosity of Resin A is 1373 cP, and
the viscosity of Resin B is 2160 cP, both measured at 23.degree. C.
The amount and type of each component used to form the resin
compositions is indicated in Table 7 below with all values in parts
by weight based on 100 parts by weight of resin composition unless
otherwise indicated.
TABLE-US-00007 TABLE 7 Resin Component A B C D Polyol 2 77.00 68.00
68.00 68.00 Polyol 3 18.00 27.00 27.00 27.00 Catalyst 3 0.15 0.15
0.15 0.15 Catalyst 4 0.60 0.60 0.60 0.60 Surfactant 2 0.70 -- -- --
Surfactant 3 -- 1.00 1.50 1.50 Water 1.65 1.65 1.40 1.65
[0093] One additional example, specifically Example 11, of the
polyurethane article of the present invention is prepared. In
addition, two control polyurethane articles are prepared,
specifically Comp. Examples 5 and 6, for comparison with Example
11. Blocks of the polyurethane articles are prepared as described
above with Examples 1-6. The amount and type of each component used
to form the polyurethane articles is indicated in Table 8 below
with all values in parts by weight based on 100 parts by weight of
all of the components prior to reaction to make the polyurethane
article unless otherwise indicated.
TABLE-US-00008 TABLE 8 Example Component Comp. 5 Comp. 6 11 Polyol
2 -- -- 68.00 Polyol 3 -- -- 27.00 Polyol 11 65.5 65.5 -- Polyol 12
34.5 34.5 -- Catalyst 3 0.32 0.32 1.00 Catalyst 5 0.08 0.08 0.10
Catalyst 8 1.40 1.40 -- Surfactant 2 -- -- 1.10 Surfactant 4 1.00
1.00 -- Water 1.20 1.20 1.10 Isocyanate 4 19.4 21.5 19.2 Isocyanate
90 100 110 Index
[0094] Polyol 11 is glycerol/sorbitol co-initiated polyol having a
terminal ethylene oxide cap of about 20 wt %, a nominal
functionality of 2.9, and a hydroxyl number of 31 mg KOH/gm,
commercially available from BASF Corporation of Florham Park,
N.J.
[0095] Polyol 12 is a graft polyol having about 43% SAN solids, a
nominal functionality of 3, a hydroxyl number of 19.8 mg KOH/gm,
and a carrier polyol portion having a terminal ethylene oxide cap
of about 19 wt %, commercially available from BASF Corporation of
Florham Park, N.J.
[0096] Catalyst 8 is a blend comprising about 85 wt %
diethanolamine (DEOA) and about 15 wt % water, commercially
available from Air Products and Chemicals of Allentown, Pa.
[0097] Surfactant 4 is a polyalkyleneoxymethyl silicone surfactant,
commercially available from Dow Coming Corporation of Midland,
Mich.
[0098] Isocyanate 4 is a mixture of about 80 wt % 2,4'-toluene
diisocyanate and about 20 wt % 2,6'-toluene diisocyanate,
commercially available from BASF Corporation of Florham Park,
N.J.
[0099] Various physical properties of the polyurethane articles are
tested as described above with Examples 1-6 and illustrated in
Table 9 below. Example 11 has a peak transmissivity lower than both
Comp. Examples 5 and 6.
TABLE-US-00009 TABLE 9 Comp. 5 Comp. 6 11 Mechanical Properties
Core Density (lbs/ft.sup.3) 4.81 4.86 4.75 Original 25% IFD (lbf)
58.14 77.65 64.38 Original 25% R IFD (lbf) 51.30 68.53 57.33
Original 65% IFD (lbf) 165.18 215.70 153.64 SAG Factor 2.84 2.78
2.39 Hysteresis (%) 19.40 19.50 17.00 Air Flow (cfm) 0.72 1.10 0.59
Block Tear (ppi) 1.13 1.10 0.82 Elongation (%) 104.03 80.60 68.93
Tensile Strength (%) 20.61 19.68 10.77 Original 50% CFD (psi) 1.39
1.81 1.19 50% CFD Humid Aged 74.51 69.02 64.36 (3 hrs. 105.degree.
C., 95% RH), % of Original (psi) Comp Set 50% Ambient (%) 2.98 1.50
1.44 Comp Set 50% Humid Aged 4.35 3.69 2.78 (3 hrs. 105.degree. C.,
95% RH) (%) Resilience (%) 66 70 64 Vibration Transmissivity
Resonance Frequency (Hz) 7.74 7.42 6.18 Peak Transmissivity 3.37
3.03 1.95 DMA Peak Tan Delta 1.06 0.95 0.60 Tg (.degree. C.) -46.91
-46.60 -32.96
[0100] The present invention has been described herein in an
illustrative manner, and it is to be understood that the
terminology which has been used is intended to be in the nature of
words of description rather than of limitation. Obviously, many
modifications and variations of the present invention are possible
in light of the above teachings. The invention may be practiced
otherwise than as specifically described within the scope of the
appended claims.
* * * * *