U.S. patent application number 13/055999 was filed with the patent office on 2011-07-07 for polyester polyol composition for polyurethane, composition for polyurethane foam, polyurethane resin, and polyurethane foam.
This patent application is currently assigned to Mitsui Chemicals, Inc.. Invention is credited to Tamotsu Kunihiro, Shinsuke Matsumoto, Atsushi Miyata, Kanae Morishita, Tomoki Tsutsui.
Application Number | 20110166245 13/055999 |
Document ID | / |
Family ID | 41610410 |
Filed Date | 2011-07-07 |
United States Patent
Application |
20110166245 |
Kind Code |
A1 |
Kunihiro; Tamotsu ; et
al. |
July 7, 2011 |
POLYESTER POLYOL COMPOSITION FOR POLYURETHANE, COMPOSITION FOR
POLYURETHANE FOAM, POLYURETHANE RESIN, AND POLYURETHANE FOAM
Abstract
The present invention provides a polyester polyol, preferably a
plant-derived polyester polyol, suitable for a composition for
polyurethane foam that contributes to the reduction of load on the
environment and has a good balance of high resilience, moderate
hardness, and high durability as a cushioning material for vehicle
seat cushions. A polyester polyol having a hydroxyl value in the
range of 15 to 100 mgKOH/g according to the present invention is
produced by a condensation of raw materials comprising at least one
selected from the group consisting of fatty acids having a hydroxy
group and fatty acid esters having a hydroxy group with a
polyhydric alcohol having an average number of functional groups of
more than three but not more than eight. The raw materials contain
90% to 100% by mass of a fatty acid having a hydroxy group and a
fatty acid ester having a hydroxy group in total.
Inventors: |
Kunihiro; Tamotsu; (Chiba,
JP) ; Miyata; Atsushi; (Chiba, JP) ; Tsutsui;
Tomoki; (Chiba, JP) ; Matsumoto; Shinsuke;
(Chiba, JP) ; Morishita; Kanae; (Chiba,
JP) |
Assignee: |
Mitsui Chemicals, Inc.
|
Family ID: |
41610410 |
Appl. No.: |
13/055999 |
Filed: |
July 28, 2009 |
PCT Filed: |
July 28, 2009 |
PCT NO: |
PCT/JP2009/063423 |
371 Date: |
January 26, 2011 |
Current U.S.
Class: |
521/172 ; 528/80;
560/182 |
Current CPC
Class: |
C08G 18/4841 20130101;
C08G 2110/0083 20210101; C08J 9/12 20130101; C08G 2110/0008
20210101; C08G 18/4072 20130101; C08J 2375/06 20130101; C08G 63/60
20130101; C08G 18/4288 20130101; C08G 18/72 20130101; C08G 63/06
20130101; C08G 18/36 20130101; C08G 18/632 20130101; C08G 18/4266
20130101 |
Class at
Publication: |
521/172 ;
560/182; 528/80 |
International
Class: |
C08G 18/00 20060101
C08G018/00; C07C 69/66 20060101 C07C069/66 |
Foreign Application Data
Date |
Code |
Application Number |
Jul 30, 2008 |
JP |
2008-196479 |
Claims
1. A polyester polyol (A) that is produced by a condensation of raw
materials comprising at least one selected from the group
consisting of fatty acids having a hydroxy group and fatty acid
esters having a hydroxy group with a polyhydric alcohol having an
average number of functional groups of more than three but not more
than eight and that has a hydroxyl value in the range of 15 to 100
mgKOH/g, wherein the raw materials comprise 90% to 100% by mass of
a fatty acid having a hydroxy group and a fatty acid ester having a
hydroxy group in total.
2. A polyester polyol (A) that is produced by a condensation of raw
materials comprising at least one selected from the group
consisting of fatty acids having a hydroxy group and fatty acid
esters having a hydroxy group with a polyhydric alcohol having an
average number of functional groups of more than three but not more
than eight and that has a hydroxyl value in the range of 15 to 100
mgKOH/g, wherein the raw materials comprise 90% to 100% by mass of
the following (I), (II), or (III): (I) one type of fatty acid
having a hydroxy group, (II) one type of fatty acid ester having a
hydroxy group, and (III) a mixture of (i) one type of fatty acid
having a hydroxy group and an ester derived from (i) the one type
of fatty acid having a hydroxy group.
3. The polyester polyol (A) according to claim 1, wherein the at
least one selected from the group consisting of fatty acids having
a hydroxy group and fatty acid esters having a hydroxy group has a
carbon-carbon double bond.
4. The polyester polyol (A) according to any one of claim 1,
wherein the at least one selected from the group consisting of
fatty acids having a hydroxy group and fatty acid esters having a
hydroxy group is derived from castor oil.
5. The polyester polyol (A) according to claim 1, wherein the fatty
acid having a hydroxy group is ricinoleic acid, and the fatty acid
ester having a hydroxy group is a ricinoleate.
6. The polyester polyol (A) according to claim 1, wherein the mass
ratio of the polyhydric alcohol to the total amount of the fatty
acid having a hydroxy group and the fatty acid ester having a
hydroxy group ranges from 1:1 to 1:100.
7. A composition for polyurethane, comprising a polyol (P)
containing a polyester polyol (A) according to claim 1, a catalyst,
and a polyisocyanate, wherein the polyester polyol (A) accounts for
10% to 95% by mass of the polyol (P).
8. A composition for polyurethane foam, comprising the composition
for polyurethane according to claim 7, a foam stabilizer, and a
blowing agent.
9. The composition for polyurethane according to claim 7, wherein
the polyol (P) further comprises a low-monool-content polyol (B)
having a total degree of unsaturation of 0.035 meq/g or less.
10. The composition for polyurethane foam according to claim 8,
wherein the polyol (P) further comprises a low-monool-content
polyol (B) having a total degree of unsaturation of 0.035 meq/g or
less.
11. A polyurethane resin produced by a reaction of a composition
for polyurethane according to claim 7.
12. A polyurethane foam produced by a reaction of a composition for
polyurethane foam according to claim 8.
Description
TECHNICAL FIELD
[0001] The present invention relates to a polyester polyol, a
composition for polyurethane, a composition for polyurethane foam,
a polyurethane resin, and a polyurethane foam.
[0002] More particularly, the present invention relates to a
composition for polyurethane foam derived from castor oil for use
in applications, such as cushioning materials for vehicle seat
cushions, a polyester polyol derived from castor oil suitable for
the composition, a polyurethane resin, and a polyurethane foam, and
applications thereof. The composition can provide a polyurethane
foam having a good balance of high rebound resilience, moderate
hardness, and high durability.
BACKGROUND ART
[0003] Polyurethane foam, which is one of resin components, has
been widely used in seat cushions of vehicles, such as automobiles,
because of its excellent cushioning characteristics. In particular,
cushions having high rebound resilience can provide an ideal body
pressure distribution and are very comfortable to sit on. Thus,
there is a great demand for such cushions. Seat cushions are
required to have moderate hardness, neither too firm nor too soft,
and high durability for long-term use with small variations in
elasticity, hardness, and thickness.
[0004] From the recent perspective of the reduction of load on the
environment, there is a demand for plant-derived resins produced
from plant resources to take the place of petroleum-derived resins
produced from petroleum resources.
[0005] Plant-derived resins are produced from raw materials derived
from plants, which grow while consuming CO.sub.2 in the air by
photosynthesis. CO.sub.2 emitted into the atmosphere by the
combustion of used plant-derived resins therefore does not increase
the amount of CO.sub.2 in the air. This is called carbon
neutrality. Thus, plant-derived resins are receiving attention as
materials that contribute to the reduction of load on the
environment.
[0006] To meet the demand for plant-derived resins, plant-derived
castor oil polyols have been used as raw material polyol components
in polyurethane foam to reduce environmental load (see, for
example, Patent Literatures 1 to 4). However, these foams cannot
satisfy the physical properties required by the market, that is, a
good balance of moderate hardness and rebound resilience and high
durability.
[0007] Patent Literature 5 discloses a foam produced from a
polyester polyol produced by the condensation of 12-hydroxystearic
acid derived from castor oil. However, the foam according to Patent
Literature 5 has rebound resilience as low as approximately 50% and
cannot provide polyurethane foam having high rebound resilience as
a cushioning material for vehicle seat cushions.
[0008] Patent Literature 6 discloses a polyurethane foam having a
good balance of moderate hardness and rebound resilience and high
durability as a cushioning material for vehicle seat cushions. The
polyurethane foam is produced from a plant-derived composition for
polyurethane foam containing a plant-derived polyol and a
low-monool-content polyol in combination.
[0009] The polyurethane foam according to Patent Literature 6,
however, contains a low amount of plant-derived polyol. Thus, there
is still room for improvement in the reduction of load on the
environment, as well as improvement in rebound resilience.
CITATION LIST
Patent Literature
[0010] PTL 1: U.S. Pat. No. 2,787,601
[0011] PTL 2: Japanese Unexamined Patent Application Publication
No. 5-59144
[0012] PTL 3: Japanese Unexamined Patent Application Publication
No. 61-91216
[0013] PTL 4: Japanese Unexamined Patent Application Publication
No. 11-166155
[0014] PTL 5: WO 2006/118995 A1
[0015] PTL 6: WO 2007/020904 A1
SUMMARY OF INVENTION
Technical Problem
[0016] It is an object of the present invention to solve the
problems associated with related art as described above and provide
a composition, preferably a plant-derived composition, for a
polyurethane foam or polyurethane resin having a good balance of
high resilience, moderate hardness, and high durability as a
cushioning material for vehicle seat cushions and contributing to
the reduction of load on the environment, and a (plant-derived)
polyurethane resin or polyurethane foam having such physical
properties.
Solution to Problem
[0017] As a result of diligent research to solve the problems
described above, the present inventors completed the present
invention by finding that a polyurethane foam produced from a
composition for polyurethane foam comprising a particular polyester
polyol (A) contributes to the reduction of load on the environment
and has a good balance of high rebound resilience, moderate
hardness, and high durability as a cushioning material for vehicle
seat cushions.
[0018] For example, the present invention includes the following
aspects [1] to [12].
[0019] [1] A polyester polyol (A) according to the present
invention is produced by the condensation of raw materials that
comprise at least one selected from the group consisting of fatty
acids having a hydroxy group and fatty acid esters having a hydroxy
group with a polyhydric alcohol having an average number of
functional groups of more than three but not more than eight. The
polyester polyol (A) has a hydroxyl value in the range of 15 to 100
mgKOH/g. The raw materials comprise 90% to 100% by mass of a fatty
acid having a hydroxy group and a fatty acid ester having a hydroxy
group in total.
[0020] [2] A polyester polyol (A) according to the present
invention is produced by the condensation of raw materials that
comprise at least one selected from the group consisting of fatty
acids having a hydroxy group and fatty acid esters having a hydroxy
group with a polyhydric alcohol having an average number of
functional groups of more than three but not more than eight. The
polyester polyol (A) has a hydroxyl value in the range of 15 to 100
mgKOH/g. The raw materials comprise 90% to 100% by mass of the
following (I), (II), or (III):
[0021] (I) one type of fatty acid having a hydroxy group,
[0022] (II) one type of fatty acid ester having a hydroxy group,
and
[0023] (III) a mixture of (i) one type of fatty acid having a
hydroxy group and an ester derived from (i) the one type of fatty
acid having a hydroxy group.
[0024] [3] Preferably, the at least one selected from the group
consisting of fatty acids having a hydroxy group and fatty acid
esters having a hydroxy group has a carbon-carbon double bond.
[0025] [4] Preferably, the at least one selected from the group
consisting of fatty acids having a hydroxy group and fatty acid
esters having a hydroxy group is derived from castor oil.
Preferably, the (I), (II), or (III) is derived from castor oil.
[0026] [5] Preferably, the fatty acid having a hydroxy group is
ricinoleic acid, and the fatty acid ester having a hydroxy group is
a ricinoleate.
[0027] Preferably, the (I), (II), or (III) accounts for 50% by mole
or more based on 100% by mole of the fatty acid having a hydroxy
group and the fatty acid ester having a hydroxy group in total in
the raw materials.
[0028] [6] Preferably, the mass ratio of the polyhydric alcohol to
the total amount of the fatty acid having a hydroxy group and the
fatty acid ester having a hydroxy group ranges from 1:1 to 1:100.
Preferably, the mass ratio of the polyhydric alcohol to the (I),
(II), or (III) ranges from 1:1 to 1:100.
[0029] [7] A composition for polyurethane according to the present
invention comprises a polyol (P) containing the polyester polyol
(A), a catalyst, and a polyisocyanate. The polyester polyol (A)
accounts for 10% to 95% by mass of the polyol (P).
[0030] [8] A composition for polyurethane foam according to the
present invention comprises the composition for polyurethane, a
foam stabilizer, and a blowing agent.
[0031] [9] Preferably, the polyol (P) in the composition for
polyurethane further comprises a low-monool-content polyol (B)
having a total degree of unsaturation of 0.035 meq/g or less.
[0032] [10] Preferably, the polyol (P) in the composition for
polyurethane foam further comprises a low-monool-content polyol (B)
having a total degree of unsaturation of 0.035 meq/g or less.
[0033] [11] A polyurethane resin according to the present invention
is produced by the reaction of the composition for
polyurethane.
[0034] [12] A polyurethane foam according to the present invention
is produced by the reaction of the composition for polyurethane
foam.
Advantageous Effects of Invention
[0035] The present invention can provide a composition, preferably
a plant-derived composition, for polyurethane foam or polyurethane
resin having a good balance of high rebound resilience, moderate
hardness, and high durability, and a (plant-derived) polyurethane
foam or polyurethane resin having such physical properties.
[0036] Furthermore, in the present invention, a polyurethane foam
or polyurethane resin produced from a plant (castor oil)-derived
polyester polyol can contribute to the reduction of load on the
environment, complying with the recent social trends toward global
environmental conservation.
DESCRIPTION OF EMBODIMENTS
Composition for Polyurethane
[0037] A composition for polyurethane according to the present
invention comprises a polyol (P) comprising a particular polyester
polyol (A), a catalyst, and a polyisocyanate. The particular
polyester polyol (A) accounts for 10% to 95% by mass of the polyol
(P). Preferably, the composition optionally comprises a foam
stabilizer, a blowing agent, a cross-linker, and other aids.
Preferably, the polyol (P) optionally further comprises another
polyol, such as a low-monool-content polyol (B) having a total
degree of unsaturation of 0.035 meq/g or less. A composition for
polyurethane foam according to the present invention comprises a
composition for polyurethane according to the present invention, a
foam stabilizer, a blowing agent, and optionally a
low-monool-content polyol (B).
(P) Polyol
[0038] A polyol (P) used in the present invention comprises a
particular polyester polyol (A) and optionally a low-monool-content
polyol (B) and another polyol, such as a polymer-dispersed
polyol.
[0039] The polyol (P) comprises 10% to 95% by mass, preferably 20%
to 95% by mass, more preferably 25% to 90% by mass, most preferably
51% to 90% by mass, of a polyester polyol (A) according to the
present invention, based on 100% by mass of all components of the
polyol (P). When the polyol (P) contains less than 10% by mass of
the polyester polyol (A), polyester polyols synthesized using a
high-purity castor oil fatty acid have unfavorably little
advantages over polyester polyols produced from a normal-purity
castor oil fatty acid. A polyol (P) containing more than 95% by
mass of the polyester polyol (A) unfavorably results in poor
formability. 51% by mass or more of the polyester polyol (A) can
provide a more environmentally-friendly polyurethane foam or
polyurethane resin.
[0040] The following is a detailed description.
(A) Polyester Polyol
[0041] A polyester polyol (A) having a hydroxyl value in the range
of 15 to 100 mgKOH/g according to the present invention is produced
by a condensation of raw materials containing at least one selected
from the group consisting of fatty acids having a hydroxy group and
fatty acid esters having a hydroxy group with a polyhydric alcohol
having an average number of functional groups of more than three
but not more than eight. The raw materials contain 90% to 100% by
mass, preferably 95% to 100% by mass, more preferably 97% to 100%
by mass, of a fatty acid having a hydroxy group and a fatty acid
ester having a hydroxy group in total. When the raw materials
comprise 90% by mass or more of a fatty acid having a hydroxy group
and a fatty acid ester having a hydroxy group in total, the
resulting polyurethane resin or polyurethane foam can have a good
balance of high rebound resilience, moderate hardness, and high
durability. In particular, a higher concentration of a fatty acid
having a hydroxy group and a fatty acid ester having a hydroxy
group in the raw materials can result in higher rebound resilience
of the resulting polyurethane resin or polyurethane foam.
[0042] A polyester polyol (A) having a hydroxyl value in the range
of 15 to 100 mgKOH/g according to the present invention is produced
by the condensation of raw materials that comprise at least one
selected from the group consisting of fatty acids having a hydroxy
group and fatty acid esters having a hydroxy group with a
polyhydric alcohol having an average number of functional groups of
more than three but not more than eight. The raw materials comprise
90% to 100% by mass of the following (I), (II), or (III):
[0043] (I) one type of fatty acid having a hydroxy group,
[0044] (II) one type of fatty acid ester having a hydroxy group,
and
[0045] (III) a mixture of (i) one type of fatty acid having a
hydroxy group and an ester derived from (i) the one type of fatty
acid having a hydroxy group.
[0046] In the term "(I) one type of fatty acid having a hydroxy
group" ("one type of" used herein may also be referred to as "a
single-component"), the optical isomers and cis-trans isomers of
the fatty acid are not discriminated and are collectively referred
to as "(I) one type of fatty acid having a hydroxy group" as a
single-component fatty acid.
[0047] Likewise, the term "(II) one type of fatty acid ester having
a hydroxy group" includes the optical isomers and cis-trans isomers
of the fatty acid ester. Alcohol-derived functional groups in the
ester do not contribute to the physical properties of the polyol
(A) and are therefore not particularly limited. These compounds are
collectively referred to as "(II) one type of fatty acid ester
having a hydroxy group" as a single-component fatty acid ester. As
an example of "(II) one type of fatty acid ester having a hydroxy
group", a mixture of methyl ricinoleate and ethyl ricinoleate is
referred to as one type of ricinoleate ((II) one type of fatty acid
ester having a hydroxy group).
[0048] In (III) (i) one type of fatty acid having a hydroxy group
and an ester derived from (i) the one type of fatty acid having a
hydroxy group, when (i) one type of fatty acid having a hydroxy
group is ricinoleic acid, the ester derived from (i) the one type
of fatty acid having a hydroxy group refers to a ricinoleate. The
aspect (III) means that the raw materials contain 90% to 100% by
mass of the mixture (for example, ricinoleic acid and a
ricinoleate). The term "one type of" in (III) a mixture of (i) one
type of fatty acid having a hydroxy group and an ester derived from
(i) the one type of fatty acid having a hydroxy group has the same
meaning as described above.
[0049] Examples of the fatty acid having a hydroxy group include
ricinoleic acid, 12-hydroxystearic acid, cerebronic acid, and
hydroxyundecanoic acid. Among these, ricinoleic acid and
12-hydroxystearic acid derived from castor oil can contribute to
the reduction of load on the environment and are preferred.
Examples of the fatty acid ester having a hydroxy group include
esters of the fatty acids described above: ricinoleates, such as
methyl ricinoleate, ethyl ricinoleate, propyl ricinoleate, and
butyl ricinoleate, 12-hydroxystearates, such as methyl
12-hydroxystearate, ethyl 12-hydroxystearate, propyl
12-hydroxystearate, and butyl 12-hydroxystearate, cerebronic acid
esters, such as cerebronic acid methyl ester, cerebronic acid ethyl
ester, cerebronic acid propyl ester, and cerebronic acid butyl
ester, and hydroxyundecanoic acid esters, such as hydroxyundecanoic
acid methyl ester, hydroxyundecanoic acid ethyl ester,
hydroxyundecanoic acid propyl ester, and hydroxyundecanoic acid
butyl ester. Among these, ricinoleates, such as methyl ricinoleate,
ethyl ricinoleate, propyl ricinoleate, and butyl ricinoleate, and
12-hydroxystearates, such as methyl 12-hydroxystearate, ethyl
12-hydroxystearate, propyl 12-hydroxystearate, and butyl
12-hydroxystearate, derived from castor oil can contribute to the
reduction of load on the environment and are therefore
preferred.
[0050] In the present invention, a fatty acid having a hydroxy
group and/or a fatty acid ester having a hydroxy group preferably
has a carbon-carbon double bond, because the resulting polyester
polyol has a low viscosity and is easy to handle in the production
of a polyurethane resin or polyurethane foam. While such fatty
acids and fatty acid esters are not particularly limited,
ricinoleic acid and ricinoleates are preferred, because such fatty
acids having a hydroxy group and a larger number of carbon atoms
can provide a polyester polyol having a lower viscosity. It is
preferable that the total amount of fatty acid having a hydroxy
group and a carbon-carbon double bond and/or fatty acid ester
having a hydroxy group and a carbon-carbon double bond in the raw
materials is 40% by mass or more, preferably 80% by mass or more,
because this can reduce the viscosity of a polyol in the production
of the polyol. The proportion of a carbon-carbon double bond in at
least one type of molecule selected from the group consisting of
fatty acids having a hydroxy group and fatty acid esters having a
hydroxy group can be calculated from 3E/2D, wherein E denotes the
peak area of protons bonded to the carbon-carbon double bond, and D
denotes the peak area of protons of a terminal methyl group of an
alkyl, as determined by .sup.1H-NMR.
[0051] In the present invention, the mass ratio of the polyhydric
alcohol having an average number of functional groups of more than
three but not more than eight described below to the total amount
of the fatty acid having a hydroxy group and the fatty acid ester
having a hydroxy group generally ranges from 1:1 to 1:100,
preferably 1:5 to 1:70, more preferably 1:5 to 1:50. It is
difficult to design a desired polyester polyol at a total amount
below one part by mass per part by mass of the polyhydric alcohol.
On the other hand, the total amount above 100 parts by mass results
in an excessively low hydroxyl value of the polyester polyol and
low activity in the production of a polyurethane resin or
polyurethane foam. This unfavorably causes difficulty in
molding.
Fatty Acid Having Hydroxy Group or Fatty Acid Ester Having Hydroxy
Group Derived from Castor Oil
[0052] In the present invention, one selected from fatty acids
having a hydroxy group and fatty acid esters having a hydroxy group
is preferably derived from castor oil, because it can contribute to
the reduction of load on the environment.
[0053] The raw materials according to the present invention are
preferably a mixture comprising 90% to 100% by mass of a fatty acid
having a hydroxy group and/or a fatty acid ester having a hydroxy
group produced by the hydrolysis, esterification, and
transesterification of castor oil. The hydrolysis, esterification,
and transesterification of castor oil may be performed in the same
way as described below.
[0054] The raw materials according to the present invention
preferably comprise 90% to 100% by mass of (I) one type of fatty
acid having a hydroxy group derived from castor oil, (II) one type
of fatty acid ester having a hydroxy group derived from castor oil,
or (III) a mixture of (i) one type of fatty acid having a hydroxy
group derived from castor oil and an ester derived from (i) the one
type of fatty acid having a hydroxy group, because the resulting
polyurethane foam or polyurethane resin can have a better balance
of high rebound resilience, moderate hardness, and high
durability.
[0055] The proportion of these compounds derived from castor oil or
a mixture thereof is 50% by mole or more, preferably in the range
of 70% to 100% by mole, more preferably 80% to 100% by mole, based
on 100% by mole of the fatty acid having a hydroxy group and the
fatty acid ester having a hydroxy group in total in the raw
materials. 50% by mole or more these compounds derived from castor
oil or a mixture thereof can contribute to the reduction of load on
the environment and are preferred.
[0056] The mass ratio of the polyhydric alcohol having an average
number of functional groups of more than three but not more than
eight described below to these compounds derived from castor oil or
a mixture thereof ranges from 1:1 to 1:100 (the polyhydric
alcohol:the compounds or the mixture thereof), preferably 1:5 to
1:70, more preferably 1:5 to 1:50. When the amount of compounds or
mixture thereof derived from castor oil is below one part by mass
per part by mass of the polyhydric alcohol, it is difficult to
design a polyester polyol for use in the production of a desired
flexible polyurethane foam. On the other hand, the amount above 100
parts by mass results in an excessively low hydroxyl value of the
polyester polyol and low reaction activity in the production of a
polyurethane resin and polyurethane foam. This unfavorably causes
difficulty in molding.
[0057] The raw materials containing a fatty acid having a hydroxy
group and a fatty acid ester having a hydroxy group derived from
castor oil can be obtained as described below.
[0058] (1) Castor oil is hydrolyzed to produce castor oil fatty
acid. The castor oil fatty acid is refined to produce a raw
material containing 90% to 100% by mass of a fatty acid having a
hydroxy group as a single component.
[0059] (2) The fatty acid produced in (1) is esterified to produce
a raw material containing 90% to 100% by mass of the fatty acid
ester.
[0060] (3) Castor oil is transesterified with an alcohol to produce
castor oil fatty acid ester. The castor oil fatty acid ester is
refined to produce a raw material containing 90% to 100% by mass of
the fatty acid ester.
[0061] In (1) to (3), castor oil and castor oil fatty acid may be
replaced with hydrogenated castor oil and hydrogenated castor oil
fatty acid, respectively, to produce the raw materials containing
90% to 100% by mass of 12-hydroxystearic acid and
12-hydroxystearate.
[0062] In (2) and (3), the esterification of the fatty acid may be
any common esterification, for example, esterification of the fatty
acid with methanol, ethanol, n-propanol, iso-propanol, n-butanol,
or tert-butanol. Such esterification may be performed by a known
method, for example, in the presence of an alkaline catalyst.
[0063] The raw materials derived from castor oil according to the
present invention may be a mixture of (1) and (2) or (3) provided
that the raw materials contain 90% to 100% by mass of a
single-component fatty acid having a hydroxy group and an ester of
the fatty acid in total in the raw materials.
[0064] In (1) and (3), the castor oil fatty acid or the castor oil
fatty acid ester can be refined by a known method, such as
distillation, extraction, or crystallization. Regarding the
distillation of castor oil fatty acid, since castor oil fatty acid
decomposes at approximately 200.degree. C. and undergoes a side
reaction of intramolecular dehydration, castor oil fatty acid is
preferably distilled with a thin-film evaporator at a temperature
of 180.degree. C. or less. A thin-film distillation apparatus used
is, but not limited to, a rotating thin film distillation apparatus
or a falling thin film distillation apparatus. In particular,
molecular distillation, which employs a rotating thin film
distillation apparatus under high vacuum, is preferred in terms of
evaporation efficiency.
[0065] Regarding the extraction of castor oil fatty acid, an
extraction method with a general solvent can be used. While the
solvent used is not particularly limited, hexane can be used in
consideration of the solubility of castor oil fatty acid and the
ease with which the solvent is removed after extraction. Castor oil
fatty acid and hexane can be mixed at a predetermined ratio and
left to stand at a predetermined temperature to separate a hexane
phase and a castor oil fatty acid phase. Hexane dissolved in castor
oil fatty acid can be removed to produce a high-purity castor oil
fatty acid.
[0066] 12-hydroxystearic acid can be purified by a widely used
crystallization method.
[0067] Examples of the fatty acid produced in (1) include
ricinoleic acid and 12-hydroxystearic acid.
[0068] A fatty acid ester having a hydroxy group in the raw
materials derived from castor oil can be produced in (2) or
(3).
[0069] Examples of the fatty acid ester produced in (2) or (3)
include ricinoleates, such as methyl ricinoleate, ethyl
ricinoleate, propyl ricinoleate, and butyl ricinoleate, and
12-hydroxystearates, such as methyl 12-hydroxystearate, ethyl
12-hydroxystearate, propyl 12-hydroxystearate, and butyl
12-hydroxystearate.
[0070] The proportion of the fatty acid contained in the raw
materials derived from castor oil as a single component ranges from
90% to 100% by mass, preferably 95% to 100% by mass, more
preferably 97% to 100% by mass. A polyurethane resin or
polyurethane foam produced from the raw materials containing
high-purity single-component fatty acid derived from castor oil can
contribute to the reduction of load on the environment and can have
a good balance of very high rebound resilience, moderate hardness,
and high durability. A proportion of the fatty acid in the raw
materials below 90% by mass results in a large amount of fatty acid
having no hydroxy group. Terminal hydroxy groups of the molecular
chain of a polyester polyol produced by the condensation of a
polyol with the fatty acid therefore are capped with the fatty acid
having no hydroxy group. Thus, in the reaction with an isocyanate
to produce a polyurethane resin or polyurethane foam, the
nonreactive terminals form dangling chains, unfavorably reducing
the rebound resilience of the polyurethane resin or polyurethane
foam. In contrast, a proportion of the fatty acid in the raw
materials in the range of 95% to 100% by mass results in a low
proportion of fatty acid having no hydroxy group. A low proportion
of hydroxy groups at the molecular ends therefore are capped with
the fatty acid having no hydroxy group. Thus, the resulting
polyurethane resin or urethane foam has high rebound resilience.
Hence, this range is most preferred.
[0071] The proportion of a fatty acid having a hydroxy group in the
raw materials that contain at least one selected from the group
consisting of fatty acids having a hydroxy group and fatty acid
esters having a hydroxy group is determined by the ratio A/B,
wherein A denotes the hydroxyl value of the fatty acid having a
hydroxy group as determined by a method according to JIS K1557-1,
and B denotes the acid value of the fatty acid having a hydroxy
group as determined by a method according to JIS K1557-5.
[0072] The proportion of a fatty acid ester having a hydroxy group
in the raw materials that contain at least one selected from the
group consisting of fatty acids having a hydroxy group and fatty
acid esters having a hydroxy group can be determined by 3C/F in the
case of a methyl ester, wherein C denotes the peak area of protons
bonded to carbon adjacent to the hydroxy group, and F denotes the
peak area of protons bonded to carbon adjacent to the oxygen atoms
of the ester group, as determined by .sup.1H-NMR. This proportion
can be determined by 2C/G for an ester of an alcohol having two or
more carbon atoms and a fatty acid having a hydroxy group, wherein
C denotes the peak area of protons bonded to carbon adjacent to the
hydroxy group, and G denotes the peak area of protons bonded to
carbon adjacent to the oxygen atoms of the ester group.
[0073] The total amount (purity: %) of fatty acid having a hydroxy
group and fatty acid ester having a hydroxy group in the raw
materials can be determined by 3C/D, wherein C denotes the peak
area of protons bonded to carbon adjacent to the hydroxy group, and
D denotes the peak area of protons of a terminal methyl group of an
alkyl, as determined by .sup.1H-NMR.
[0074] The proportion of a mixture of (i) one type of fatty acid
having a hydroxy group and an ester derived from (i) the one type
of fatty acid having a hydroxy group in the raw materials can also
be determined by .sup.1H-NMR measurements in the same manner as
described above.
[0075] When (i) one type of fatty acid having a hydroxy group is
difficult to identify by .sup.1H-NMR, the quality and quantity of
the one type of fatty acid having a hydroxy group can be determined
by gas chromatography (GC). The quality and quantity of an ester
derived from (i) the one type of fatty acid having a hydroxy group
can also be determined by GC.
[0076] Among fatty acids having a hydroxy group or fatty acid
esters having a hydroxy group thus produced, ricinoleic acid and
ricinoleates are preferred because they can reduce the viscosity of
a polyol in the production of the polyol.
Other Hydroxycarboxylic Acids and Hydroxycarboxylates
[0077] In the present invention, the raw materials that comprise at
least one selected from the group consisting of fatty acids having
a hydroxy group and fatty acid esters having a hydroxy group may
comprise 0% to 10% by mass, preferably 0% to 5% by mass, more
preferably 0% to 3% by mass, of an other hydroxycarboxylic acid
and/or a hydroxycarboxylate.
[0078] The amount of hydroxycarboxylic acid and/or
hydroxycarboxylate is preferably less than 50% by mole, more
preferably in the range of 0% to 30% by mole, still more preferably
0% to 20% by mole, based on 100% by mole of the fatty acid having a
hydroxy group and the fatty acid ester having a hydroxy group in
total in the raw materials. Less than 50% by mole of the
hydroxycarboxylic acid and/or the hydroxycarboxylate in total is
preferred because this can reduce the viscosity of the polyester
polyol.
[0079] Examples of the hydroxycarboxylic acid include lactic acid,
glycolic acid, 2-hydroxybutyric acid, 3-hydroxybutyric acid, and
.gamma.-hydroxybutyric acid. Examples of the hydroxycarboxylate
include lactate, glycolate, 2-hydroxybutyrate, 3-hydroxybutyrate,
and .gamma.-hydroxybutyrate. The esterification may be any common
esterification as described above, for example, esterification of
the hydroxycarboxylic acid with methanol, ethanol, n-propanol,
iso-propanol, n-butanol, or tert-butanol. Such esterification may
be performed by a known method, for example, in the presence of an
alkaline catalyst.
[0080] In the case that lactic acid and/or a lactate is used as the
hydroxycarboxylic acid in the present invention, the raw materials
can contain 90% to 100% by mass of any of the following (IV) to
(XI). In the following (IV) to (XI), "one type of" and "ester" have
the same definitions as described above.
[0081] (IV) A mixture of one type of fatty acid having a hydroxy
group and lactic acid.
[0082] (V) A mixture of one type of fatty acid having a hydroxy
group and a lactate.
[0083] (VI) A mixture of one type of fatty acid ester having a
hydroxy group and lactic acid.
[0084] (VII) A mixture of one type of fatty acid ester having a
hydroxy group and a lactate.
[0085] (VIII) A mixture of (i) one type of fatty acid having a
hydroxy group, an ester derived from (i) the one type of fatty acid
having a hydroxy group, and lactic acid.
[0086] (IX) A mixture of (i) one type of fatty acid having a
hydroxy group, an ester derived from (i) the one type of fatty acid
having a hydroxy group, and a lactate.
[0087] (X) A mixture of at least one selected from (i) one type of
fatty acid having a hydroxy group, an ester derived from (i) the
one type of fatty acid having a hydroxy group, lactic acid and
lactates.
[0088] (XI) A mixture of at least one selected from a fatty acid
having a hydroxy group, a fatty acid ester having a hydroxy group,
lactic acid and lactates.
Polyhydric Alcohol having Average Number of Functional Groups of
More than Three but not More than Eight
[0089] A polyhydric alcohol having an average number of functional
groups of more than three but not more than eight according to the
present invention used together with the raw materials, in
particular the raw materials derived from castor oil, in the
production of a polyester polyol (A) may be any common polyol for
use in the production of polyurethane foam provided that the common
polyol is the desired polyhydric alcohol.
[0090] In order to produce a polyester polyol (A) that allows the
cross-linking of a polyurethane resin or polyurethane foam to
proceed sufficiently to produce a polyurethane resin or
polyurethane foam having high rebound resilience, a polyhydric
alcohol (hereinafter also referred to as a polyol) preferably has
an average number of hydroxy groups (an average number of
functional groups) of more than three but not more than eight. In
order to increase the degree of cross-linking of the polyurethane
resin or polyurethane foam and ensure rebound resilience, the
average number of hydroxy groups more preferably ranges from 3.5 to
8. An average number of functional groups above eight results in an
increase in the viscosity of the polyol, unfavorably making the use
of the polyol in a foaming machine difficult in the production of a
polyurethane foam. An increase in the viscosity of the polyol also
unfavorably results in poor mixing in the production of a
polyurethane resin. Examples of the polyhydric alcohol having more
than three but not more than eight hydroxy groups include
polyhydric alcohols, polyoxyalkylene polyols, and polyester
polyols, each having four to eight hydroxy groups per molecule.
These polyhydric alcohols can be used alone or in combination.
[0091] A polyhydric alcohol having two or three hydroxy groups per
molecule or a polyoxyalkylene polyol or polyester polyol using the
polyhydric alcohol having two or three hydroxy groups per molecule
as an initiator may be used at the same time, provided that the
polyhydric alcohols have an average hydroxy group number of more
than three.
[0092] Examples of the polyhydric alcohol having four to eight
hydroxy groups per molecule include tetravalent alcohols, such as
diglycerin, pentaerythritol, and .alpha.-methylglucoside;
hexavalent alcohols, such as dipentaerythritol; saccharides, such
as glucose, sorbitol, dextrose, fructose, and sucrose, and
derivatives thereof; and phenols having seven to eight hydroxy
groups. Alkylene oxide adducts of the polyhydric alcohols described
above can also be used, in which ethylene oxide, propylene oxide,
and the like are bonded to the polyhydric alcohols. These
polyhydric alcohols can be used alone or in combination.
[0093] Polyoxyalkylene polyols are oligomers or polymers produced
by the ring-opening polymerization of alkylene oxides. In general,
polyoxyalkylene polyols are produced by the ring-opening
polymerization of alkylene oxides using an active hydrogen compound
as an initiator in the presence of a catalyst. Examples of alkylene
oxide compounds for use in the production of polyoxyalkylene
polyols include ethylene oxide, propylene oxide, 1,2-butylene
oxide, 2,3-butylene oxide, styrene oxide, cyclohexene oxide,
epichlorohydrin, epibromohydrin, methyl glycidyl ether, allyl
glycidyl ether, and phenyl glycidyl ether. Among these alkylene
oxide compounds, ethylene oxide, propylene oxide, 1,2-butylene
oxide, and styrene oxide are preferred, and ethylene oxide and
propylene oxide are more preferred. These can be used alone or in
combination. Polyoxyalkylene polyols are also referred to as
polyoxyalkylene polyether polyols. It is desirable that the
polyoxyalkylene polyols preferably have a hydroxyl value in the
range of 100 to 1800 mgKOH/g, more preferably 200 to 1200 mgKOH/g.
The polyoxyalkylene polyols can be used alone or in
combination.
[0094] In the present invention, a polyhydric alcohol having two to
three hydroxy groups per molecule can be used in combination with a
polyol having four to eight hydroxy groups per molecule provided
that the polyhydric alcohols have an average number of functional
groups of more than three. Examples of the polyhydric alcohol
having 2 to 3 hydroxy groups per molecule include dihydric alcohols
having 2 to 10 carbon atoms, such as ethylene glycol, propylene
glycol, diethylene glycol, dipropylene glycol, 1,3-propanediol,
1,3-butanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol,
and 1,4-cyclohexanediol; trivalent alcohols having 2 to 10 carbon
atoms, such as trimethylolpropane and glycerin; and phenols having
two or more hydroxy groups, such as bisphenol A. Alkylene oxide
adducts of the polyhydric alcohols described above can also be
used, in which ethylene oxide, propylene oxide, and the like are
bonded to the polyhydric alcohols. These polyhydric alcohols can be
used alone or in combination.
Polyester Polyol (A)
[0095] A polyester polyol (A) having a hydroxyl value in the range
of 15 to 100 mgKOH/g according to the present invention can be
produced by the condensation of a fatty acid having a hydroxy group
and a fatty acid ester having a hydroxy group, particularly derived
from castor oil, with the polyhydric alcohol having an average
number of functional groups of more than three but not more than
eight in the raw materials. In this case, the condensation of a
fatty acid having a hydroxy group and/or a fatty acid ester having
a hydroxy group may be followed by the condensation of the
condensate with a polyhydric alcohol. Alternatively, the
condensation of a polyhydric alcohol with a fatty acid having a
hydroxy group and/or a fatty acid ester having a hydroxy group may
be followed by the condensation of the fatty acid having a hydroxy
group and/or the fatty acid ester having a hydroxy group.
[0096] An apparatus for synthesizing a polyester polyol may be
provided with a distillation apparatus to remove water produced or
alcohols. These condensation reactions may be performed in an inert
gas, such as nitrogen gas, at a high temperature in the absence of
solvent. Another known method, such as solution polymerization, may
also be used. The temperature of condensation in the absence of
solvent may be any temperature at which dehydration condensation
can proceed. Considering that ricinoleic acid or 12-hydroxystearic
acid decomposes at approximately 200.degree. C. and undergoes
intramolecular dehydration, the condensation temperature preferably
ranges from 140.degree. C. to 200.degree. C., more preferably
160.degree. C. to 180.degree. C. While the reaction pressure may be
normal pressure, high pressure, or low pressure, normal pressure or
low pressure is preferred in terms of reaction efficiency. A tin
catalyst, such as tin octanoate or dibutyltin dilaurate, or another
catalyst, such as a titanium catalyst, may be used as an
esterification catalyst.
[0097] A polyester polyol (A) according to the present invention
has an acid value in the range of 0 to 5 mgKOH/g, preferably 0 to 3
mgKOH/g, more preferably 0 to 2 mgKOH/g. An acid value above 5
mgKOH/g unfavorably results in a delay in reactivity in a urethane
reaction. In terms of reactivity control, the acid value is
preferably 3 mgKOH/g or less, more preferably 2 mgKOH/g or
less.
[0098] A polyester polyol (A) according to the present invention
has a hydroxyl value in the range of 15 to 100 mgKOH/g, preferably
20 to 80 mgKOH/g, more preferably 25 to 60 mgKOH/g. A hydroxyl
value of 15 mgKOH/g or more is preferred because curing in the
production of foam proceeds in a short period of time. A hydroxyl
value of 100 mgKOH/g or less is preferred because of rebound
resilience and hardness suitable for flexible polyurethane foam
having high rebound resilience.
[0099] A polyester polyol (A) according to the present invention
has a viscosity of 20000 mPas or less, preferably 15000 mPas or
less, more preferably 10000 mPas or less, at 25.degree. C.
[0100] Use of a fatty acid having a hydroxy group derived from
castor oil and/or a fatty acid ester having a hydroxy group derived
from castor oil in the raw materials can markedly increase the
amount of plant-derived component in a polyurethane foam produced
using a polyester polyol (A) according to the present invention,
thereby further contributing to the reduction of load on the
environment. In accordance with the concept of carbon neutrality, a
polyol and polyurethane foam produced from plant-derived crude
glycerin can emit less carbon dioxide by combustion. Use of biomass
feedstocks in polymers can be determined by calculating the
proportion of carbon having a mass number of 14 (140 concentration)
from the content of carbon having a mass number of 14 and the
content of carbon having mass numbers of 12 and 13 in accordance
with ASTM D6866.
[0101] More specifically, in accordance with a standard examination
method in U.S.A. (ASTM) D6866 (Standard Test Method for Determining
the Biobased Content of Natural Range Materials Using Radiocarbon
and Isotope Ratio Mass Spectrometry Analysis), a sample is burned
into CO.sub.2, and a precise volume of CO.sub.2 gas is introduced
into an accelerated mass spectrometry (AMS) apparatus to measure
the content of carbon having a mass number of 14 and the content of
carbon having mass numbers of 12 and 13. Comparison with the
abundance of carbon having a mass number of 14 in the atmosphere or
petrochemical products allows for the determination.
[0102] Alternatively, a sample is burned into CO.sub.2, and
CO.sub.2 is absorbed into a CO.sub.2 absorbent or is converted into
benzene. The amount of carbon having a mass number of 14 is
measured with a liquid scintillation counter and is compared with a
compound derived from petroleum for the determination.
[0103] Carbon having a mass number of 14 cannot be observed in
polyols synthesized only using petroleum-derived raw materials. Use
of plant-derived raw materials allows carbon having a mass number
of 14 to be observed. In order to reduce carbon dioxide emissions,
the 14C concentration of polyurethane foam may be 10 percent modern
carbon (pMC) or more, preferably 20 pMC or more, more preferably 30
pMC.
[0104] A polyurethane foam produced from a polyester polyol (A)
according to the present invention can have a good balance of high
rebound resilience, moderate hardness, and high durability. In
particular, the polyurethane foam can be suitably used as an
environmentally-friendly cushioning material for vehicle seat
cushions.
[0105] A polyester polyol (A) according to the present invention
can also be used as a propylene oxide and/or ethylene oxide adduct
of the polyol.
[0106] A polyester polyol (A) according to the present invention
can also be used as a lactone adduct. Examples of lactone include
.beta.-lactones, such as .beta.-propiolactone, .gamma.-lactones,
such as .gamma.-butyrolactone, .delta.-lactones, such as
.delta.-valerolactone, and .epsilon.-lactones, such as
.epsilon.-caprolactone. .beta.-propiolactone and
.epsilon.-caprolactone are preferred.
[0107] A polyester polyol (A) according to the present invention
can be used as a castor-oil-derived prepolymer having a terminal
hydroxy group, which is produced by the reaction of the polyester
polyol (A) with a polyisocyanate. Preferred examples of the
polyisocyanate contained in the prepolymer include, but are not
limited to, conventionally known tolylene diisocyanate (although
the ratio of isomers, such as 2,4-isomer and 2,6-isomer, is not
particularly limited, the ratio of 2,4-isomer/2,6-isomer is
preferably 80/20), diphenylmethane diisocyanate, polymethylene
polyphenyl polyisocyanate, and a mixture of tolylene diisocyanate
and polymethylene polyphenyl polyisocyanate. A urethane-modified
product or a carbodiimide-modified product of any of these
polyisocyanates or a mixture of the urethane-modified
polyisocyanate or the carbodiimide-modified polyisocyanate and
tolylene diisocyanate can also preferably be used.
Other Polyols
(B) Low-Monool-Content Polyol
[0108] In the present invention, a low-monool-content polyol (B)
may be used. The low-monool-content polyol (B) is a polyol
generally used in the production of polyurethane foam and has a
total degree of unsaturation of 0.035 meq/g or less, preferably
0.030 meq/g or less, more preferably 0.025 meq/g or less. The lower
limit of the total degree of unsaturation may be, but is not
limited to, 0.001 meq/g. A modified product of the
low-monool-content polyol (B) may also be used. These
low-monool-content polyols (B) can be used alone or in
combination.
[0109] The polyol (P) contains 5% to 95% by mass, preferably 5% to
90% by mass, more preferably 10% to 80% by mass, most preferably
10% or more but less than 50% by mass, of the low-monool-content
polyol (B) based on 100% by mass of all components of the polyol
(P). Less than 5% by mass of the low-monool-content polyol (B) is
unfavorable in terms of formability. More than 80% by mass of the
low-monool-content polyol (B) cannot contribute to the reduction of
load on the environment and is unfavorable.
[0110] Preferred examples of the low-monool-content polyol (B)
include polyether polyols having a total degree of unsaturation in
the range described above (hereinafter also referred to as a
"polyether polyol (B1)") and modified products thereof. These
low-monool-content polyols can be used alone or in combination.
Polyether Polyol (B1)
[0111] The polyether polyol (B1) may be an oligomer or polymer that
is produced by the ring-opening polymerization of an alkylene oxide
using an active hydrogen compound initiator generally in the
presence of a catalyst and that has a total degree of unsaturation
in the range described above.
[0112] In the production of polyether polyols, it is generally
known that the ring-opening polymerization of an alkylene oxide
using an initiator in the presence of a catalyst also produces a
monool having a terminal unsaturated group as the molecular weight
of the polyether polyol increases. The monool content is generally
expressed by the total degree of unsaturation of the polyether
polyol. A lower total degree of unsaturation indicates a lower
monool content.
[0113] The monool in the polyether polyol has a lower molecular
weight than the main component, the polyether polyol. The monool
therefore greatly increases the molecular weight distribution of
the polyether polyol and reduces the average number of functional
groups. Use of such a polyether polyol having a high monool content
in the production of polyurethane foam may result in deterioration
in the physical properties of the polyurethane foam, such as high
hysteresis loss, low hardness, low extensibility, low durability,
and poor curing characteristics. The term "durability", as used
herein, specifically refers to, for example, wet heat compression
set, which is a measure of a decrease in the thickness of a cushion
after long-term use. Use of such a polyether polyol having a high
monool content in the production of polyurethane resin may also
result in deterioration in extensibility and durability.
[0114] An increase in the monool content of the polyether polyol
tends to increase lattice defects in polyurethane foam produced
from the polyether polyol. This decreases cross-linking density,
resulting in an increase in the degree of swelling of the
polyurethane foam in a polar organic solvent, such as
dimethylformamide. In general, the relationship between the degree
of swelling and cross-linking density is expressed by a
Flory-Rehner equation described in P. J. Flory, "Principle of
Polymer Chemistry", Cornell University Press (1953). The
relationship between monool content and the degree of swelling in a
polar organic solvent is disclosed in Usaka et al., "A Raw
Materials System Concept for Wider Ranging Demands of Flexible
Polyurethane Molded Foam", Polyurethane Expo 2002 Conference
Proceedings (2002), pp. 75-82. Likewise, an increase in the monool
content of the polyether polyol may also result in a decrease in
the cross-linking density of a polyurethane resin and an increase
in the degree of swelling of the polyurethane resin in a polar
solvent.
[0115] Thus, the monool content responsible for the deterioration
in the physical properties of a polyurethane foam or polyurethane
resin is preferably reduced.
Catalysts
[0116] A polyether polyol (B1) having a low total degree of
unsaturation, that is, a low monool content can be produced at
least using at least one compound selected from compounds having a
nitrogen-phosphorus double bond, cesium hydroxide, and rubidium
hydroxide as a catalyst. Use of such a compound as a catalyst can
reduce the amount of monool as compared with the case where a
conventionally known alkali metal hydroxide, such as potassium
hydroxide, is used as a catalyst, thus improving the physical
properties of the resulting polyurethane foam or polyurethane
resin. For example, it is difficult to achieve a good balance of
moderate hardness and rebound resilience and high durability using
an alkali metal hydroxide as a catalyst. However, use of the
above-mentioned compound as a catalyst can achieve a good balance
of these properties. In particular, these beneficial effects of the
low-monool-content polyol are remarkable in the case that the
low-monool-content polyol is used in combination with a
plant-derived polyol, which generally contains impurities and is
often inferior in performance to petroleum-derived polyols.
[0117] Examples of the compounds having a nitrogen-phosphorus
double bond include, but are not limited to, compounds described in
Japanese Unexamined Patent Application Publication Nos. 11-106500,
2000-297131, and 2001-106780. Among these, phosphazenium compounds
are preferred.
Active Hydrogen Compounds
[0118] Examples of the active hydrogen compound include active
hydrogen compounds having an active hydrogen atom on an oxygen atom
and active hydrogen compounds having an active hydrogen atom on a
nitrogen atom. Active hydrogen compounds having a number of
functional groups in the range of two to eight are preferred.
[0119] Examples of the active hydrogen compounds having an active
hydrogen atom on an oxygen atom include water, carboxylic acids
having 1 to 20 carbon atoms, polyvalent carboxylic acids having 2
to 6 carboxy groups per molecule and 2 to 20 carbon atoms, carbamic
acids, alcohols having 1 to 20 carbon atoms, polyhydric alcohols
having 2 to 8 hydroxy groups per molecule and 2 to 20 carbon atoms,
saccharides and derivatives thereof, aromatic compounds having 1 to
3 hydroxy groups per molecule and 6 to 20 carbon atoms, and
poly(alkylene oxide)s having 2 to 8 terminals per molecule and a
hydroxy group on at least one of the terminals.
[0120] Examples of the active hydrogen compounds having an active
hydrogen atom on a nitrogen atom include aliphatic or aromatic
primary amines having 1 to 20 carbon atoms, aliphatic or aromatic
secondary amines having 2 to 20 carbon atoms, polyvalent amines
having 2 to 3 primary or secondary amino groups per molecule and 2
to 20 carbon atoms, saturated cyclic secondary amines having 4 to
20 carbon atoms, unsaturated cyclic secondary amines having 4 to 20
carbon atoms, cyclic polyvalent amines having 2 to 3 secondary
amino groups per molecule and 4 to 20 carbon atoms, unsubstituted
or N-monosubstituted acid amides having 2 to 20 carbon atoms, 5- to
7-membered cyclic amides, and dicarboximides having 4 to 10 carbon
atoms.
[0121] These active hydrogen compounds can be used alone or in
combination. Among these active hydrogen compounds, polyhydric
alcohols having 2 to 20 carbon atoms and 2 to 8 hydroxy groups per
molecule are preferred, and ethylene glycol, propylene glycol,
diethylene glycol, dipropylene glycol, glycerin, diglycerin, and
pentaerythritol are more preferred.
Alkylene Oxides
[0122] Among the alkylene oxides described above, alkylene oxides
having 2 to 12 carbon atoms are preferred. Specific examples
include ethylene oxide, propylene oxide, 1,2-butylene oxide,
2,3-butylene oxide, styrene oxide, cyclohexene oxide,
epichlorohydrin, epibromohydrin, methyl glycidyl ether, allyl
glycidyl ether, and phenyl glycidyl ether. Ethylene oxide,
propylene oxide, 1,2-butylene oxide, and styrene oxide are more
preferred. Ethylene oxide and propylene oxide are particularly
preferred.
[0123] These alkylene oxides can be used alone or in combination.
In the combined use of these alkylene oxides, a plurality of
alkylene oxides may be simultaneously or sequentially subjected to
addition polymerization, or sequential addition polymerization may
be performed repeatedly.
[0124] The polyether polyol (B1) can be produced in accordance with
reaction conditions and production methods described in Japanese
Unexamined Patent Application Publication Nos. 2000-297131 and
2001-106780.
[0125] Among polyether polyols (B1) thus produced, polyether
polyols produced by the addition polymerization of an alkylene
oxide including ethylene oxide are preferred. The polyether polyol
(B1) preferably has a hydroxyl value in the range of 10 to 40
mgKOH/g, more preferably 20 to 38 mgKOH/g. The content of a
constitutional unit derived from ethylene oxide (the total
oxyethylene group content) preferably ranges from 5% to 30% by
mass, more preferably 10% to 20% by mass, based on 100% by mass of
all the constitutional units derived from the alkylene oxides
constituting the polyether polyol (B1).
(PB) Polymer-Dispersed Polyol
[0126] In the present invention, the (A) polyester polyol or the
(B) low-monool-content polyol may be used directly or in the form
of a polymer-dispersed polyol. In the polymer-dispersed polyol,
polymer fine particles produced in these polyols by the radical
polymerization of a compound having an unsaturated bond are
dispersed in these polyols. These polyols may be used in
combination with a polymer-dispersed polyol.
[0127] The polyol (P) contains 0% to 80% by mass, preferably 0% to
50% by mass, more preferably 0% to 30% by mass, of the
polymer-dispersed polyol based on 100% by mass of all components of
the polyol (P). More than 80% by mass of the polymer-dispersed
polyol cannot contribute to the reduction of load on the
environment and is unfavorable.
[0128] The polymer-dispersed polyol is preferably a polymer polyol
derived from the low-monool-content polyol (B) (hereinafter also
referred to as a "polymer polyol (PB)"), more preferably a polymer
polyol derived from the polyether polyol (B1) (hereinafter also
referred to as a "polymer polyol (PB1)"), particularly preferably a
polymer polyol derived from a polyether polyol (B1) having a
hydroxyl value in the range of 15 to 60 mgKOH/g.
[0129] The polymer-dispersed polyol can be a dispersion containing
vinyl polymer particles dispersed in the (A) polyester polyol or
the (B) low-monool-content polyol. The dispersion can be produced
by the dispersion polymerization of a compound having an
unsaturated bond in the (A) polyester polyol or the (B)
low-monool-content polyol using a radical initiator, such as
azobisisobutyronitrile. The vinyl polymer particles may be formed
of a polymer of the compound having an unsaturated bond. In
preferred polymer particles, at least part of the compound having
an unsaturated bond is grafted to the dispersion medium polyol
during dispersion polymerization.
[0130] The compound having an unsaturated bond has an unsaturated
bond in the molecule and may be acrylonitrile, styrene, or
acrylamide. These compounds having an unsaturated bond can be used
alone or in combination.
[0131] In addition to the compound having an unsaturated bond, a
dispersion stabilizer and/or a chain transfer agent may be added in
the production of the polymer-dispersed polyol.
[0132] In the production of flexible polyurethane foam having high
rebound resilience applicable to seat pads for vehicles, such as
automobiles, the polyester polyol (A) is preferably used in
combination with the low-monool-content polyol (B) and the polymer
polyol (PB) and is more preferably used in combination with the
polyether polyol (B1) and the polymer polyol (PB1).
Polyols other than Low-Monool-Content Polyol (B) and
Polymer-Dispersed Polyol
[0133] A composition for polyurethane foam according to the present
invention may contain another polyol generally used in the
production of polyurethane foam, as well as the polyester polyol
(A), the low-monool-content polyol (B), and the polymer-dispersed
polyol. Examples of such polyols include polyether polyols having a
total degree of unsaturation above 0.035 meq/g, polymer polyols
derived from these polyether polyols, and polyester polyols. The
polyol (P) contains 5% to 95% by mass, preferably 10% to 80% by
mass, more preferably 10% to 70% by mass, of such a polyol based on
100% by mass of all components of the polyol (P). Less than 5% by
mass of such a polyol is unfavorable in terms of formability. More
than 95% by mass of such a polyol cannot contribute to the
reduction of load on the environment and is unfavorable.
Polyether Polyol (C)
[0134] A polyether polyol having a total degree of unsaturation
above 0.035 meq/g (hereinafter also referred to as a "polyether
polyol (C)") may be an oligomer or polymer produced by the
ring-opening polymerization of an alkylene oxide and having a total
degree of unsaturation above 0.035 meq/g. Such a polyether polyol
(C) is generally produced by the ring-opening polymerization of an
alkylene oxide using an active hydrogen compound initiator in the
presence of a catalyst, for example, an alkali metal hydroxide,
such as potassium hydroxide.
Active Hydrogen Compounds
[0135] The active hydrogen compound may be the active hydrogen
compound exemplified for the polyether polyol (B1). These active
hydrogen compounds can be used alone or in combination. Among these
active hydrogen compounds, polyhydric alcohols having 2 to 20
carbon atoms and 2 to 8 hydroxy groups per molecule are preferred,
and ethylene glycol, propylene glycol, diethylene glycol,
dipropylene glycol, glycerin, diglycerin, and pentaerythritol are
more preferred.
Alkylene Oxides
[0136] The alkylene oxide may be the alkylene oxide exemplified for
the polyether polyol (B1) and is more preferably ethylene oxide,
propylene oxide, 1,2-butylene oxide, or styrene oxide, particularly
preferably ethylene oxide or propylene oxide.
[0137] These alkylene oxides can be used alone or in combination.
In the combined use of these alkylene oxides, a plurality of
alkylene oxides may be simultaneously or sequentially subjected to
addition polymerization, or sequential addition polymerization may
be performed repeatedly.
[0138] The polyether polyol (C) can be produced using catalysts,
reaction conditions, and production methods described in Otsu
Takayuki, "Kaitei Kobunshi Gosei no Kagaku", the first impression
of the second edition, Kagaku-Dojin Publishing Company, Inc (1989)
pp. 172-180, and Matsudaira Nobutaka and Maeda Tetsuro,
"Poriuretan", the eighth impression, Maki Shyoten (1964) pp.
41-45.
[0139] Among polyether polyols (C) thus produced, polyether polyols
produced by the addition polymerization of an alkylene oxide
including ethylene oxide are preferred. The content of a
constitutional unit derived from ethylene oxide (the total
oxyethylene group content) preferably ranges from 5% to 30% by
mass, more preferably 10% to 20% by mass, based on 100% by mass of
all the constitutional units derived from the alkylene oxides
constituting the polyether polyol (C).
Polymer Polyol (PC)
[0140] A polymer polyol used as another polyol may be a polymer
polyol derived from the polyether polyol (C) (hereinafter also
referred to as a "polymer polyol (PC)") and is preferably a polymer
polyol derived from the polyether polyol (C) having a hydroxyl
value in the range of 15 to 60 mgKOH/g.
[0141] The polymer polyol (PC) can be a dispersion containing vinyl
polymer particles dispersed in the polyether polyol (C). The
dispersion can be produced by the dispersion polymerization of a
compound having an unsaturated bond in the polyether polyol (C)
using a radical initiator, such as azobisisobutyronitrile. The
vinyl polymer particles may be formed of a polymer of the compound
having an unsaturated bond. In preferred polymer particles, at
least part of the compound having an unsaturated bond is grafted to
the dispersion medium polyether polyol (C) during dispersion
polymerization.
[0142] The compound having an unsaturated bond may be the compound
having an unsaturated bond exemplified for the specific polymer
polyol described above. These compounds having an unsaturated bond
can be used alone or in combination. In the production of the
polymer polyol (PC), the compound having an unsaturated bond may be
used in combination with a dispersion stabilizer and/or a chain
transfer agent.
Polyester Polyol
[0143] Examples of the polyester polyol include condensates between
low-molecular polyols and carboxylic acids, and lactone polyols,
such as products of the ring-opening polymerization of
.epsilon.-caprolactone and products of the ring-opening
polymerization of .beta.-methyl-.delta.-valerolactone.
[0144] Examples of the low-molecular polyols include dihydric
alcohols having 2 to 10 carbon atoms, such as ethylene glycol and
propylene glycol, trivalent alcohols having 2 to 10 carbon atoms,
such as glycerin, trimethylolpropane, and trimethylolethane,
tetravalent alcohols, such as pentaerythritol and diglycerin, and
saccharides, such as sorbitol and sucrose.
[0145] Examples of the carboxylic acids include dicarboxylic acids
having 2 to 10 carbon atoms, such as succinic acid, adipic acid,
maleic acid, fumaric acid, phthalic acid, and isophthalic acid, and
acid anhydrides having 2 to 10 carbon atoms, such as succinic
anhydride, maleic anhydride, and phthalic anhydride.
Blowing Agents
[0146] A blowing agent according to the present invention may be a
physical foaming agent, such as liquefied carbon dioxide, and is
most preferably water.
[0147] When water is used as a blowing agent, the amount of water
preferably ranges from 1.3 to 6.0 parts by mass, more preferably
1.8 to 5.0 parts by mass, particularly preferably 2.0 to 4.0 parts
by mass, based on 100 parts by mass of all the components of the
polyol (P). This amount of water serving as a blowing agent can
effectively stabilize foams.
[0148] As the blowing agent, physical foaming agents, such as
hydroxyfluorocarbons (such as HFC-245fa) developed for the purpose
of global environmental protection, hydrocarbons (such as
cyclopentane), carbon dioxide, and liquefied carbon dioxide can be
used in combination with water. Among these, carbon dioxide and
liquefied carbon dioxide are preferred in terms of the reduction of
load on the environment.
Catalysts
[0149] Catalysts for use in the present invention are used for the
reaction between the polyol (P) and a polyisocyanate and may be,
but are not limited to, conventionally known catalysts. Preferred
examples of the catalysts include aliphatic amines, such as
triethylenediamine, bis(2-dimethylaminoethyl)ether,
1-isobutyl-2-methylimidazole, and morpholine, and organic tin
compounds, such as stannous octoate and dibutyltin dilaurate.
[0150] These catalysts can be used alone or in combination. The
amount of catalyst preferably ranges from 0.1 to 10 parts by mass
per 100 parts by mass of all the components of the polyol (P).
Foam Stabilizers
[0151] Foam stabilizers for use in the present invention may be
conventionally known foam stabilizers and are not particularly
limited. In general, organic silicon surfactants are preferably
used.
[0152] Preferred examples of foam stabilizers include FV-1013-16,
SRX-274C, SF-2969, SF-2961, SF-2962, L-5309, L-3601, L-5307,
L-3600, L-5366, SZ-1325, SZ-1328, and Y-10366, manufactured by Dow
Corning Toray Silicone Co., Ltd. The amount of foam stabilizer
preferably ranges from 0.1 to 10 parts by mass, more preferably 0.5
to 5 parts by mass, per 100 parts by mass of all the components of
the polyol (P).
Polyisocyanates
[0153] Polyisocyanates for use in the present invention may be, but
are not limited to, conventionally known polyisocyanates described
in "Poriuretan Jushi Handobukku", edited by Iwata Keiji, the first
impression, Nikkan Kogyo Shimbun Ltd., (1987) pp. 71-98. Among
these, polyisocyanates preferably used to produce foam are
toluoylene diisocyanate (although the ratio of isomers, such as
2,4-isomer and 2,6-isomer, is not particularly limited, the ratio
of 2,4-isomer/2,6-isomer is preferably 80/20), polymethylene
polyphenyl polyisocyanate (for example, Cosmonate M-200
manufactured by Mitsui Chemicals Polyurethane Co., Ltd.),
urethane-modified products thereof, and mixtures thereof.
[0154] In the case that the polyisocyanate is a mixture of
toluoylene diisocyanate and another polyisocyanate, it is desirable
that the amount of toluoylene diisocyanate preferably range from
50% to 99% by mass, more preferably 70% to 90% by mass,
particularly preferably 75% to 85% by mass, of the total amount of
the polyisocyanates in terms of a balance of the durability and the
mechanical strength of foam.
[0155] Polyisocyanates used to produce polyurethane resins include
toluoylene diisocyanate (although the ratio of isomers, such as
2,4-isomer and 2,6-isomer, is not particularly limited, the ratio
of 2,4-isomer/2,6-isomer is preferably 80/20), diphenylmethane
diisocyanate (for example, Cosmonate PH manufactured by Mitsui
Chemicals, Inc.), xylylene diisocyanate, norbornene diisocyanate,
naphthalene diisocyanate, bis(isocyanatomethyl)cyclohexane, and
hexamethylene diisocyanate.
[0156] In the present invention, it is desirable that each
component be used such that the NCO index preferably ranges from
0.70 to 1.30, more preferably 0.80 to 1.20. The NCO index in this
range can result in the production of a polyurethane foam or
polyurethane resin that has moderate hardness and mechanical
strength, as well as moderate rebound resilience, elongation
percentage, and formability, suitable for a cushioning material.
The term "NCO index", as used herein, refers to a value calculated
by dividing the total number of isocyanate groups of the
polyisocyanate by the total number of active hydrogen atoms
reactive with the isocyanate groups, such as hydroxy groups of a
polyol, amino groups of a cross-linker, or water. When the number
of active hydrogen atoms reactive with the isocyanate groups is
stoichiometrically equivalent to the number of isocyanate groups of
the polyisocyanate, the NCO index is 1.0.
Other Aids
[0157] In addition to the components described above, a composition
for polyurethane according to the present invention can contain a
chain extending agent, a cross-linker, a communicating agent, an
antifoaming agent, and other aids, such as additive agents
generally used in the production of polyurethane foam or
polyurethane resins, for example, a flame retardant, a pigment, an
ultraviolet absorber, and an antioxidant, without compromising the
objects of the present invention.
[0158] The additive agents include those described in Matsudaira
Nobutaka and Maeda Tetsuro, "Poriuretan", the eighth impression,
Maki Shyoten, (1964) pp. 134-137, and Matsuo Hitoshi, Kunii
Nobuaki, and Tanabe Kiyoshi, "Kinousei Poriuretan", the first
impression, CMC Publishing Co., Ltd., (1989) pp. 54-68.
Cross-Linkers
[0159] A cross-linker can be used in a polyurethane foam or
polyurethane resin according to the present invention described
below. Thus, a composition for polyurethane according to the
present invention can contain a cross-linker. The cross-linker is
preferably a compound having a hydroxyl value in the range of 200
to 1800 mgKOH/g.
[0160] Examples of the cross-linker include aliphatic polyhydric
alcohols, such as glycerin, and alkanolamines, such as
diethanolamine and triethanolamine.
[0161] Polyoxyalkylene polyols having a hydroxyl value in the range
of 200 to 1800 mgKOH/g can also be used as cross-linkers.
Conventionally known cross-linkers can also be used as
cross-linkers. The amount of cross-linker preferably ranges from
0.5 to 10 parts by mass per 100 parts by mass of all the components
of the polyol (P).
Polyurethane Resin and Method for Producing Polyurethane Resin
[0162] A method for producing a polyurethane resin according to the
present invention is not particularly limited. A conventionally
known production method can be appropriately employed. More
specifically, a polyol (P) containing a polyester polyol (A) can be
mixed with a catalyst, an antifoaming agent, another polyol, such
as a low-monool-content polyol (B), other aids, and a cross-linker
to produce a resin premix. The resin premix is then mixed with a
polyisocyanate. The mixture cures to yield a polyurethane resin.
Alternatively, a polyol (P) containing a polyester polyol (A) is
reacted with an excessive amount of isocyanate to synthesize a
prepolymer having terminal isocyanate groups. The prepolymer is
then mixed with a catalyst and a necessary cross-linker to produce
a polyurethane resin.
[0163] A polyurethane resin according to the present invention has
a good balance of high rebound resilience, moderate hardness, and
high durability. In particular, use of raw materials derived from
castor oil can contribute to the reduction of load on the
environment. The polyurethane resin can preferably be used in
applications requiring high rebound resilience, such as adhesives
and sealants.
[0164] The polyurethane resin has a Shore A hardness generally in
the range of 30 to 90, preferably 35 to 90, more preferably 40 to
70, under conditions in conformity with JIS K6253, a rebound
resilience (%) of generally 50% or more, preferably in the range of
60% to 80%, more preferably 65% to 80%, under conditions in
conformity with JIS K6255, a maximum stress (MPa) of generally 0.5
MPa or more, preferably 0.8 MPa or more, under conditions in
conformity with JIS K6251, and a maximum elongation percentage (%)
in the range of 50% to 400%, preferably 60% to 200%, under
conditions in conformity with JIS K6251.
Polyurethane Foam and Method for Producing Polyurethane Foam
[0165] A method for producing a polyurethane foam according to the
present invention is not particularly limited. A conventionally
known production method can be appropriately employed. More
specifically, slab forming, hot cure molding, or cold cure molding
can be employed. Cold cure molding is preferred in the production
of seat pads for vehicles, such as automobiles.
[0166] A method for producing a polyurethane foam by cold cure
molding may be a known cold cure molding method. For example, a
polyol (P) containing a polyester polyol (A) can be mixed with a
blowing agent, a catalyst, a foam stabilizer, another polyol, such
as a low-monool-content polyol (B), other aids, and a cross-linker
to produce a resin premix. The resin premix is then mixed with a
polyisocyanate in a high-pressure foaming machine or a low-pressure
foaming machine at a predetermined NCO index. The mixture is then
injected into a metal mold and is allowed to foam and cure to yield
a polyurethane foam having a predetermined shape.
[0167] The curing time generally ranges from 30 seconds to 30
minutes. The mold temperature generally ranges from room
temperature to approximately 80.degree. C. The curing temperature
preferably ranges from room temperature to approximately
150.degree. C. The hardened material may be heated at a temperature
in the range of 80.degree. C. to 180.degree. C. without
compromising the objects and advantageous effects of the present
invention.
[0168] The resin premix is generally mixed with a polyisocyanate in
a high-pressure foaming machine or a low-pressure foaming machine.
When a hydrolyzable compound, such as an organotin catalyst, is
used as a catalyst, in order to prevent the organotin catalyst from
coming into contact with a blowing agent water, the water component
and the organotin catalyst component are preferably injected into
the foaming machine through different paths and are mixed in a
mixing head of the foaming machine. The resin premix used
preferably has a viscosity of 2500 mPas or less in view of mixing
and formability of foam in the foaming machine.
[0169] Thus, use of raw materials derived from castor oil can
provide a castor-oil-derived polyurethane foam that contributes to
the reduction of load on the environment and that has a good
balance of high rebound resilience, moderate hardness, and high
durability. The rebound resilience range, moderate hardness range,
and high durability range of polyurethane foams generally depend on
the applications. A polyurethane foam according to the present
invention is preferably used for seat cushions and seat backs of
vehicles, such as automobiles, which require high rebound
resilience.
[0170] In the case of seat cushions of vehicles, such as
automobiles, which generally have a core density in the range of 40
to 75 kg/m.sup.3, the moderate hardness range is preferably in the
range of 140 to 280 N/314 cm.sup.2, more preferably 200 to 260
N/314 cm.sup.2, at 25% ILD. The moderate rebound resilience range
is preferably in the range of 45% to 75%, more preferably 55% to
70%, most preferably 60% to 70%. The high durability range is
preferably a wet heat compression set of 14% or less, more
preferably 12% or less.
[0171] The phrase "achieve a good balance of moderate hardness
range, rebound resilience range, and high durability range" means
that hardness, high rebound resilience, and durability are
simultaneously achieved in preferred ranges.
[0172] A polyurethane foam according to the present invention has
an elongation percentage in the range of 50% to 200%, preferably
60% to 150%.
[0173] A polyurethane foam according to the present invention can
be suitably used as a cushioning material, in particular seat pads
for seat cushions and seat backs of vehicles, such as
automobiles.
EXAMPLES
[0174] Although the present invention will be further described in
detail in the following Examples, the present invention is not
limited to these Examples. "Part" and "%" in the Examples represent
"part by mass" and "% by mass", respectively. The analyses and
measurements in the Examples and Comparative Examples were
performed by the following methods.
(1) Core Density (Core Density is Abbreviated as "Dco" in Tables in
the Examples)
[0175] The core density was measured in accordance with a method
for measuring apparent density described in JIS K-6400. In the
present invention, a skin was removed from a polyurethane foam
sample to prepare a rectangular parallelepiped foam sample. The
core density of the rectangular parallelepiped foam sample was
measured.
(2) Hardness of Foam (Abbreviated as "25% ILD" in Tables in the
Examples)
[0176] The foam hardness was measured in a polyurethane foam having
a thickness of 100 mm in accordance with the A method described in
JIS K-6400.
(3) Rebound Resilience (Abbreviated as "BR" in Tables in the
Examples)
[0177] The rebound resilience was measured in accordance with a
method described in JIS K-6400.
(4) Wet Heat Compression Set (Abbreviated as "WS" in Tables in the
Examples)
[0178] The wet heat compression set was measured in accordance with
a method described in JIS K-6400. In the measurements, a core of
polyurethane foam formed was cut into 50 mm.times.50 mm.times.25
mm, which was used as a test specimen. The test specimen was
pressed to the 50% thickness, was placed between parallel plates,
and was left to stand at 50.degree. C. and a relative humidity of
95% for 22 hours. Thirty minutes after the test specimen was
removed, the thickness of the test specimen was measured and
compared with the thickness before the test to determine the
strain.
(5) Elongation Percentage
[0179] The elongation percentage was measured in accordance with a
method described in JIS K-6400.
(6) Evaluation of Balance of Characteristics
[0180] In the foam hardness, rebound resilience, and wet heat
compression set measured as described above, when the physical
properties of foam satisfy the foam hardness in the range of 140 to
280 N/314 cm.sup.2, the rebound resilience in the range of 60% to
75%, and the wet heat compression set of 14% or less, the
characteristic balance of the foam was considered as good. When any
of these physical properties was outside these ranges, the
characteristic balance of the foam was considered as poor.
(7) Acid Value
[0181] The acid value was measured in accordance with a method
described in JIS K-1557-5.
(8) Hydroxyl Value (OHV)
[0182] The hydroxyl value was measured in accordance with a method
described in JIS K-1557-1.
(9) Total Degree of Unsaturation
[0183] The total degree of unsaturation was measured in accordance
with a method described in JIS K-1557-3.
(10) Viscosity (mPas/25.degree. C.)
[0184] A cone-and-plate viscometer (E-type viscometer) was used to
measure the viscosity at 25.degree. C.
(11) Measurement of the Purity of a Fatty Acid Having a Hydroxy
Group
[0185] The proportion of a fatty acid having a hydroxy group in the
raw materials that contain at least one selected from the group
consisting of fatty acids having a hydroxy group and fatty acid
esters having a hydroxy group was determined by the ratio A/B,
wherein A denotes the hydroxyl value of the fatty acid having a
hydroxy group as determined by a method according to JIS K1557-1,
and B denotes the acid value of the fatty acid having a hydroxy
group as determined by a method according to JIS K1557-5.
(12) Measurement of the Purity of a Fatty Acid Ester Having a
Hydroxy Group by .sup.1H-NMR
[0186] Raw materials that contain at least one selected from the
group consisting of fatty acids having a hydroxy group and fatty
acid esters having a hydroxy group were dissolved in
deuteriochloroform and were subjected to .sup.1H-NMR measurement
with a nuclear magnetic resonance spectrometer AL-400 manufactured
by JEOL Datum Co. After the chemical shift peaks were identified,
the proportion (%) of a fatty acid having a hydroxy group and a
fatty acid ester having a hydroxy group in total was determined by
3C/D.times.100, wherein C denotes the peak area of protons bonded
to a carbon atom adjacent to a hydroxy group, and D denotes the
peak area D of protons of a terminal methyl group of an alkyl. The
proportion of a fatty acid having a hydroxy group determined by the
method described above was subtracted from the proportion (%) of a
fatty acid having a hydroxy group and a fatty acid ester having a
hydroxy group in total to calculate the proportion of a fatty acid
ester having a hydroxy group. The proportion of a mixture of (i)
one type of fatty acid having a hydroxy group and an ester derived
from (i) the one type of fatty acid having a hydroxy group in the
raw materials was also determined in the same manner as the NMR
measurements described above. The proportion of an ester derived
from (i) the one type of fatty acid having a hydroxy group was
calculated by subtracting the proportion of a fatty acid having a
hydroxy group determined by the method described above from the
proportion of the mixture. The total amount (purity: %) of fatty
acid having a hydroxy group and fatty acid ester having a hydroxy
group in the raw materials was calculated from the measurements of
(11) and (12).
(13) Proportion of Carbon-Carbon Double Bond in the Molecule
[0187] The proportion of a fatty acid having a hydroxy group and a
carbon-carbon double bond and/or a fatty acid ester having a
hydroxy group and a carbon-carbon double bond in the raw materials
that contain at least one selected from the group consisting of
fatty acids having a hydroxy group and fatty acid esters having a
hydroxy group was determined by .sup.1H-NMR in the same manner as
the purity measurement in (12). The proportion (%) was calculated
by 3E/2D.times.100, wherein E denotes the peak area of protons
bonded to the carbon-carbon double bonds, and D denotes the peak
area of protons of a terminal methyl group of an alkyl, as
determined by .sup.1H-NMR.
(14) Shore A hardness
[0188] The Shore A hardness of a sample for hardness measurement
prepared by the method described in the resin preparation method
was measured in accordance with a method described in JIS K6253
with a hardness meter manufactured by Kobunshi Keiki Co., Ltd.
(15) Rebound Resilience (%)
[0189] The rebound resilience of a sample for the measurement of
rebound resilience prepared by the method described in the resin
preparation method was measured in accordance with a Lubke process
(Lubke method) described in JIS K6255 with a rebound resilience
tester manufactured by Ueshima Seisakusho Co., Ltd.
(16) Tensile Strength (Maximum Stress: MPa, Maximum Elongation
Percentage: %)
[0190] A specimen was punched out with a JIS No. 3 dumbbell from a
sample for the measurement of tensile strength prepared by the
method described in the resin preparation method. The tensile
strength (the maximum stress and the maximum elongation percentage)
of the specimen was measured by a method described in JIS
K6251.
Purification of Castor Oil Fatty Acid
Purification Example 1
[0191] Castor oil fatty acid, which is a raw material derived from
castor oil, was used as a raw material that contained at least one
selected from the group consisting of fatty acids having a hydroxy
group and fatty acid esters having a hydroxy group.
[0192] Components having no hydroxy group, which were low-boiling
components, were removed with a molecular distillation apparatus
having an evaporation area of 0.03 m.sup.2 (manufactured by Sibata
Scientific Technology Ltd.) from castor oil fatty acid (trade name
CO-FA manufactured by Itoh Oil Chemicals Co., Ltd., purity: 86%)
produced by the hydrolysis of castor oil. Thus, a high-purity
castor oil fatty acid was produced. The evaporation conditions were
as follows: feed rate=200 g/h, evaporation surface
temperature=160.degree. C., pressure=15 Pa, and the number of
revolutions of a wiper=300 rpm. The resulting high-purity castor
oil fatty acid had an acid value of 180.7 mgKOH/g and a hydroxyl
value of 172.9 mgKOH/g. On the basis of these values, the purity of
the high-purity castor oil fatty acid (1) was determined to be
95.7%. The high-purity castor oil fatty acid (1) was identified as
ricinoleic acid.
Purification Example 2
[0193] The same procedures as in Purification Example 1 were
performed except that the feed rate was 220 g/h and the evaporation
surface temperature was 170.degree. C. The resulting high-purity
castor oil fatty acid had an acid value of 176.3 mgKOH/g and a
hydroxyl value of 173.5 mgKOH/g. On the basis of these values, the
purity of the high-purity castor oil fatty acid (2) was determined
to be 98.4%. The high-purity castor oil fatty acid (2) was
identified as ricinoleic acid.
Purification Example 3
[0194] The same procedures as in Purification Example 1 were
performed except that the feed rate was 75 g/h, the evaporation
surface temperature was 150.degree. C., and the pressure was 20 Pa.
The resulting high-purity castor oil fatty acid had an acid value
of 185.3 mgKOH/g and a hydroxyl value of 169.6 mgKOH/g. On the
basis of these values, the purity of the high-purity castor oil
fatty acid (3) was determined to be 91.5%. The high-purity castor
oil fatty acid (3) was identified as ricinoleic acid.
Purification Example 4
[0195] Components having no hydroxy group, which were low-boiling
components, were removed with a molecular distillation apparatus
having an evaporation area of 0.03 m.sup.2 (manufactured by Sibata
Scientific Technology Ltd.) from a castor oil fatty acid ester
(trade name CO-FA methyl ester D manufactured by Itoh Oil Chemicals
Co., Ltd.) produced by the hydrolysis of castor oil and subsequent
transesterification. Thus, a high-purity castor oil fatty acid
methyl ester was produced. The evaporation conditions were as
follows: feed rate=220 g/h, evaporation surface
temperature=120.degree. C., pressure=7 Pa, and the number of
revolutions of a wiper=300 rpm. The resulting high-purity castor
oil fatty acid methyl ester was further purified three times under
the same conditions to produce a high-purity castor oil fatty acid
methyl ester (4). This high-purity castor oil fatty acid methyl
ester (4) had a purity of 98.6% as determined by .sup.1H-NMR. The
high-purity castor oil fatty acid methyl ester (4) was identified
as methyl ricinoleate.
Purification Example 5
[0196] Four hundred grams of 12-hydroxystearic acid (12-HSA)
manufactured by Itoh Oil Chemicals Co., Ltd. was added to 600 g of
butanol and was heated to 50.degree. C. to completely dissolve
12-HSA. Leaving the solution to stand in a room at 25.degree. C.
for four hours crystallized 12-HSA.
[0197] After vacuum filtration, the solid content was dried in a
vacuum dryer at 25.degree. C. for 24 hours to produce high-purity
12-HSA. This high-purity 12-HSA had a purity of 92.0% as determined
by .sup.1H-NMR.
Synthesis of Polyester Polyols
Synthesis Example 1
Polyester Polyol A-1
[0198] The high-purity castor oil fatty acid (1) produced in
Purification Example 1 was mixed with castor oil fatty acid (trade
name CO-FA manufactured by Itoh Oil Chemicals Co., Ltd., purity:
86%) such that the purity was 95.0%. 1944 g of this mixture, 78 g
of SOR-400 (manufactured by Mitsui Chemicals Polyurethane Co.,
Ltd., a propylene oxide adduct of sorbitol, hydroxyl value=400
mgKOH/g), and 97 g of PE-450 (manufactured by Mitsui Chemicals
Polyurethane Co., Ltd., a propylene oxide adduct of
pentaerythritol, hydroxyl value=450 mgKOH/g) (the average number of
functional groups of the polyhydric alcohols=4.6) were charged in a
2-L glass flask equipped with a thermometer, an agitator, and an
apparatus for removing water produced. The condensation reaction
was performed at 180.degree. C. in a nitrogen stream. At an acid
value of 10 mgKOH/g or less, 0.2 g of tetrabutyl orthotitanate (a
reagent manufactured by Tokyo Chemical Industry Co., Ltd.) was
added as a catalyst. The condensation reaction was continued at
180.degree. C. for 109 hours. Table 1 shows the hydroxyl value
(OHV), the average number of functional groups (calculated value),
and the viscosity of the resulting polyester polyol A-1 (polyol
A-1).
Synthesis Examples 2 to 8
Polyester Polyols A-2 to A-8
[0199] Polyols A-2 to A-8 were produced in the same manner as
Synthesis Example 1 except that the amounts of high-purity castor
oil fatty acids (1) and (3), high-purity castor oil fatty acid
methyl ester (4), SOR-400, PE-450, and glycerin (Gly, manufactured
by Wako Pure Chemical Industries, Ltd., guaranteed reagent) and the
condensation reaction conditions were changed as shown in Table 1.
As described in Synthesis Example 1, the high-purity castor oil
fatty acid or the high-purity castor oil fatty acid methyl ester
was mixed in advance with castor oil fatty acid (trade name CO-FA
manufactured by Itoh Oil Chemicals Co., Ltd., purity: 86%) so as to
have a predetermined purity shown in Table 1. In Synthesis Examples
A-5 to A-7, castor oil fatty acid (CO-FA) was used in the
synthesis.
[0200] Table 1 shows the hydroxyl value (OHV), the average number
of functional groups (calculated value), and the viscosity of the
resulting polyester polyols A-2 to A-8 (polyols A-2 to A-8).
Synthesis Examples 9 to 20
Polyester Polyols A-9 to A-20
[0201] Polyols A-9 to A-20 were produced in the same manner as
Synthesis Example 1 except that the amounts of high-purity castor
oil fatty acids (1) to (3), high-purity 12-HSA, SOR-400, and PE-450
and the condensation reaction conditions were changed as shown in
Table 2 or 3. As described in Synthesis Example 1, the high-purity
castor oil fatty acid was mixed in advance with castor oil fatty
acid (CO-FA, purity: 86%) so as to have a predetermined purity
shown in Table 2 or 3. In Synthesis Example 13, the total amount
(purity) of castor oil fatty acid and 12-hydroxystearic acid in the
raw materials was 93%. In Synthesis Example A-20, 12-hydroxystearic
acid (manufactured by Itoh Oil Chemicals Co., Ltd., purity: 86%)
was used in the synthesis.
[0202] Tables 2 and 3 show the hydroxyl value (OHV), the average
number of functional groups (calculated value), and the viscosity
of the resulting polyester polyols A-9 to A-20 (polyols A-9 to
A-20).
TABLE-US-00001 TABLE 1 Synthesis Synthesis Synthesis Synthesis
example 1 example 2 example 3 example 4 Polyol A-1 Polyol A-2
Polyol A-3 Polyol A-4 Fatty acid having hydroxy group and
High-purity High-purity High-purity High-purity castor fatty acid
ester having hydroxy group castor oil fatty castor oil fatty castor
oil fatty oil fatty acid acid (1) + castor acid (1) + castor acid
(3) + castor methyl ester (4) + oil fatty acid oil fatty acid oil
fatty acid castor oil fatty acid Purity of castor oil fatty acid
(ester) 95 95 95 99 (%) Purity of 12-hydroxystearic acid (%) -- --
-- -- Proportion of fatty acid (ester) having 98 98 98 99 hydroxy
group and carbon-carbon double bond (%) Polyhydric alcohol
PE450/SOR400 PE450/SOR400 PE450/SOR400 PE450/SOR400 Average number
of functional groups 4.6 5.2 5.8 4.9 of polyhydric alcohol OHV
(mgKOH/g) 30.9 55.2 33.3 27.5 Average number of functional groups
3.5 4.4 4.4 4.4 (calculated) Viscosity (mPa s/25.degree. C.) 5640
6570 14,000 16,300 Mass ratio of castor oil fatty acid (per 11.1
6.5 10.5 15.2 mole of polyhydric alcohol) Amount charged (g) PE-450
97 80 12 49.87 SOR-400 78 202 173 63.12 MN-400 Glycerin Castor oil
fatty acid, 1944 1821 1933 1716 High-purity castor oil fatty acid,
High-purity castor oil fatty acid ester High-purity
12-hydroxystearic acid Tetrabutyl orthotitanate 0.2 0.2 0.2 7.3
Condensation reaction conditions 180.degree. C. .times. 109 h
180.degree. C. .times. 84 h 180.degree. C. .times. 102 h
180.degree. C. .times. 296 h Synthesis Synthesis Synthesis
Synthesis example 5 example 6 example 7 example 8 Polyol A-5 Polyol
A-6 Polyol A-7 Polyol A-8 Fatty acid having hydroxy group and
Castor oil Castor oil Castor oil High-purity fatty acid ester
having hydroxy group fatty acid fatty acid fatty acid castor oil
fatty acid (1) + castor oil fatty acid Purity of castor oil fatty
acid (ester) 86 86 86 95 (%) Purity of 12-hydroxystearic acid (%)
-- -- -- -- Proportion of fatty acid (ester) having 99 99 99 98
hydroxy group and carbon-carbon double bond (%) Polyhydric alcohol
SOR400 SOR400 Gly/PE450 Gly Average number of functional groups 6 6
3.6 3 of polyhydric alcohol OHV (mgKOH/g) 34 53.9 59.2 57.8 Average
number of functional groups 3.5 4.4 2.6 2.6 (calculated) Viscosity
(mPa s/25.degree. C.) 3780 2620 1630 2250 Mass ratio of castor oil
fatty acid (per 7.7 5.1 6.9 26.8 mole of polyhydric alcohol) Amount
charged (g) PE-450 234 SOR-400 547 368 MN-400 Glycerin 32 76 Castor
oil fatty acid, 4218 1867 1845 2048 High-purity castor oil fatty
acid, High-purity castor oil fatty acid ester High-purity
12-hydroxystearic acid Tetrabutyl orthotitanate 0.5 0.2 0.2 0.2
Condensation reaction conditions 180.degree. C. .times. 94 h
180.degree. C. .times. 84 h 180.degree. C. .times. 66 h 180.degree.
C. .times. 57 h
TABLE-US-00002 TABLE 2 Synthesis Synthesis Synthesis Synthesis
Synthesis example 9 example 10 example 11 example 12 example 13
Polyol A-9 Polyol A-10 Polyol A-11 Polyol A-12 Polyol A-13 Fatty
acid having hydroxy group and High-purity High-purity High-purity
High-purity High-purity castor oil fatty acid ester having hydroxy
group castor oil fatty castor oil fatty castor oil fatty castor oil
fatty fatty acid (1) + castor acid (2) + castor acid (2) + castor
acid (3) + castor acid (3) + castor oil fatty acid + oil fatty acid
oil fatty acid oil fatty acid oil fatty acid high-purity 12-HSA
Purity of castor oil fatty acid (%) 90 90 95 97 95 Purity of
12-hydroxystearic acid (%) -- -- -- -- 91 Proportion of fatty acid
having hydroxy 98 98 98 98 49 group and carbon-carbon double bond
(%) Polyhydric alcohol PE450/SOR400 PE450/SOR400 PE450/SOR400
PE450/SOR400 PE450/SOR400 Average number of functional groups 5.6
5.9 4 4.9 5.4 of polyhydric alcohol OHV (mgKOH/g) 34.5 53.1 54.4
50.6 54.3 Average number of functional groups 3.5 4.4 3.5 4.4 4.4
(calculated) Viscosity (mPa s/25.degree. C.) 4280 3410 3130 3730
4750 Mass ratio of castor oil fatty acid (per 8.0 5.3 7.2 7.0 3.0
mole of polyhydric alcohol) Amount charged (g) PE-450 76 25 620 274
30 SOR-400 514 800 26 379 117 MN-400 Glycerin Castor oil fatty
acid, high-purity castor 4698 4387 4635 4570 447 oil fatty acid, or
high-purity castor oil fatty acid ester High-purity
12-hydroxystearic acid 450 Tetrabutyl orthotitanate 0.8 2.0 0.5 2.0
0.4 Condensation reaction conditions 180.degree. C. .times. 91 h
180.degree. C. .times. 59 h 180.degree. C. .times. 72 h 180.degree.
C. .times. 59 h 180.degree. C. .times. 37 h Synthesis Synthesis
Synthesis Synthesis Synthesis example 14 example 15 example 16
example 17 example 18 Polyol A-14 Polyol A-15 Polyol A-16 Polyol
A-17 Polyol A-18 Fatty acid having hydroxy group and High-purity
High-purity High-purity High-purity High-purity fatty acid ester
having hydroxy group castor oil fatty 12-HSA castor oil fatty
castor oil fatty 12-HSA acid (1) + castor acid (1) + castor acid
(1) + castor oil fatty acid oil fatty acid oil fatty acid Purity of
castor oil fatty acid (%) 95 -- 95 92 -- Purity of
12-hydroxystearic acid (%) -- 92 -- -- 92 Proportion of fatty acid
having hydroxy 98 0 98 98 0 group and carbon-carbon double bond (%)
Polyhydric alcohol PE450/SOR400 PE450/SOR400 PE450/SOR400
PE450/SOR400 PE450/SOR400 Average number of functional groups 4.7
5.6 5.2 5.6 5.6 of polyhydric alcohol OHV (mgKOH/g) 122 30.4 49.7
52.9 52.9 Average number of functional groups 4.5 3.5 4.4 4.4 4.4
(calculated) Viscosity (mPa s/25.degree. C.) 2120 8400 4550 3600
5000 Mass ratio of castor oil fatty acid (per 2.5 9.4 7.2 6.0 5.7
mole of polyhydric alcohol) Amount charged (g) PE-450 781 199.5 231
140.5 145.7 SOR-400 710 505 551 1037 984.1 MN-400 Glycerin Castor
oil fatty acid, high-purity castor 3765 5662 6736 oil fatty acid,
or high-purity castor oil fatty acid ester High-purity
12-hydroxystearic acid 6595 6825 Tetrabutyl orthotitanate 1.0 2.3
2.6 3.2 3.2 Condensation reaction conditions 180.degree. C. .times.
41 h 180.degree. C. .times. 52 h 180.degree. C. .times. 34 h
180.degree. C. .times. 45 h 180.degree. C. .times. 54 h
TABLE-US-00003 TABLE 3 Synthesis example 19 Synthesis example 20
Polyol A-19 Polyol A-20 Fatty acid having hydroxy group and fatty
acid High-purity castor oil 12-HSA ester having hydroxy group fatty
acid (2) + castor oil fatty acid Purity of castor oil fatty acid
(%) 90 -- Purity of 12-hydroxystearic acid (%) -- 86 Proportion of
fatty acid having hydroxy group 98 0 and carbon-carbon double bond
(%) Polyhydric alcohol PE450/SOR400 SOR400 Average number of
functional groups of 5.9 6 polyhydric alcohol OHV (mgKOH/g) 52.0
53.3 Average number of functional groups (calculated) 4.4 4.2
Viscosity (mPa s/25.degree. C.) 3100 4110 Mass ratio of castor oil
fatty acid (per mole of 5.2 4.9 polyhydric alcohol) Amount charged
(g) PE-450 30 SOR-400 505 379 Castor oil fatty acid, High-purity
castor oil fatty 2791 acid, or High-purity castor oil fatty acid
ester High-purity 12-hydroxystearic acid 1841 Tetrabutyl
orthotitanate 0.3 0.2 Condensation reaction conditions 180.degree.
C. .times. 117 h 180.degree. C. .times. 66 h
Synthesis of Low-Monool-Content Polyols
Synthesis Example 21
Polyether Polyol (B1-1)
[0203] 0.01 mole of
tetrakis[tris(dimethylamino)phosphoranylideneamino]phosphonium
hydroxide was added to one mole of glycerin. After vacuum
dehydration at 100.degree. C. for six hours, the addition
polymerization of propylene oxide was performed at a reaction
temperature of 80.degree. C. and a maximum reaction pressure of 3.8
kg/cm.sup.2. The addition polymerization of ethylene oxide was then
performed at a reaction temperature of 100.degree. C. and a maximum
reaction pressure of 3.8 kg/cm.sup.2 to produce a polyether polyol
(B1-1). The polyol (B1-1) had a total degree of unsaturation of
0.025 meq/g, a hydroxyl value of 24 mgKOH/g, and a terminal
oxyethylene group content of 15% by mass.
Synthesis Example 22
Polyether Polyol (C1-1)
[0204] 0.37 mole of potassium hydroxide was added to one mole of
glycerin. After vacuum dehydration at 100.degree. C. for six hours,
the addition polymerization of propylene oxide was performed at a
reaction temperature of 115.degree. C. and a maximum reaction
pressure of 5.0 kg/cm.sup.2. The addition polymerization of
ethylene oxide was then performed at a reaction temperature of
115.degree. C. and a maximum reaction pressure of 3.8 kg/cm.sup.2
to produce a polyether polyol (C1-1). The polyol (C1-1) had a total
degree of unsaturation of 0.062 meq/g, a hydroxyl value of 28
mgKOH/g, and a terminal oxyethylene group content of 15% by
mass.
Synthesis Example 23
Polyether Polyol (C1-2)
[0205] 0.37 mole of potassium hydroxide was added to one mole of
glycerin. After vacuum dehydration at 100.degree. C. for six hours,
the addition polymerization of propylene oxide was performed at a
reaction temperature of 115.degree. C. and a maximum reaction
pressure of 5.0 kg/cm.sup.2. The addition polymerization of
ethylene oxide was then performed at a reaction temperature of
115.degree. C. and a maximum reaction pressure of 3.8 kg/cm.sup.2
to produce a polyether polyol (C1-2). The polyol (C1-2) had a total
degree of unsaturation of 0.051 meq/g, a hydroxyl value of 34
mgKOH/g, and a terminal oxyethylene group content of 15% by
mass.
Synthesis of Polymer Polyols
Synthesis Example 24
Polymer polyol (PB1-1)
[0206] A 1-liter autoclave equipped with a thermometer, an
agitator, a pressure gauge, and a feeder was fully charged with the
polyether polyol (31-1) having a hydroxyl value of 24 mgKOH/g
produced in Synthesis Example 21 and was heated to 120.degree. C.
while stirring. A liquid mixture of the polyether polyol (B1-1), a
radical polymerization initiator, acrylonitrile, and a dispersion
stabilizer was continuously added to the autoclave. The graft
polymerization of acrylonitrile was performed at a reaction
temperature of 120.degree. C., a reaction pressure of 400 kPa, and
a residence time of 50 minutes. After the initial fraction was
removed from an outlet, a reaction solution was continuously
obtained. The amounts of the raw materials were as follows:
[0207] Polyether polyol (B1-1): 7200 g (the total amount of
polyether polyol (B1-1) contained in the autoclave and the liquid
mixture)
[0208] Radical polymerization initiator: 50 g
[0209] Acrylonitrile: 1800 g
[0210] The radical polymerization initiator was as follows:
[0211] Radical polymerization initiator:
2,2'-azobis(2-isobutyronitrile)
[0212] The resulting reaction solution was heated at 120.degree. C.
under a reduced pressure of 655 Pa or less for three hours to
remove unreacted acrylonitrile and decomposition products of the
radical polymerization initiator, thus yielding a polymer polyol
(PB1-1) having a hydroxyl value of 19 mgKOH/g. The polymer polyol
(PB1-1) had a vinyl polymer content of 20% by mass (the total
amount of acrylonitrile used was 20% by mass based on 100% by mass
of the total amount of polyether polyol (B1-1) and acrylonitrile
used).
Synthesis Example 25
Polymer polyol (PC1-1)
[0213] A 1-liter autoclave equipped with a thermometer, an
agitator, a pressure gauge, and a feeder was fully charged with the
polyether polyol (C1-2) having a hydroxyl value of 34 mgKOH/g
produced in Synthesis Example 23 and was heated to 120.degree. C.
while stirring. A liquid mixture of the polyether polyol (C1-2), a
radical polymerization initiator, acrylonitrile, and a dispersion
stabilizer was continuously added to the autoclave. The graft
polymerization of acrylonitrile was performed at a reaction
temperature of 120.degree. C., a reaction pressure of 400 kPa, and
a residence time of 50 minutes. After the initial fraction was
removed from an outlet, a reaction solution was continuously
obtained. The amounts of the raw materials were as follows:
[0214] Polyether polyol (C1-2): 7800 g (the total amount of
polyether polyol (C1-2) contained in the autoclave and the liquid
mixture)
[0215] Radical polymerization initiator: 80 g
[0216] Acrylonitrile: 3000 g
[0217] The radical polymerization initiator was as follows:
[0218] Radical polymerization initiator:
2,2'-azobis(2-isobutyronitrile)
[0219] The resulting reaction solution was heated at 120.degree. C.
under a reduced pressure of 655 Pa or less for three hours to
remove unreacted acrylonitrile and decomposition products of the
radical polymerization initiator, thus yielding a polymer polyol
(PC1-1) having a hydroxyl value of 23 mgKOH/g. The polymer polyol
(PC1-1) had a vinyl polymer content of 30% by mass (the total
amount of acrylonitrile used was 30% by mass based on 100% by mass
of the total amount of polyether polyol (C1-2) and acrylonitrile
used).
Preparation of Polyurethane Foam
Example 1
[0220] A resin premix was prepared by mixing 58 parts of the
polyester polyol (A-1) produced in Synthesis Example 1, 30 parts of
the low-monool-content polyol (B-1) synthesized in Synthesis
Example 21, 12 parts of the polymer polyol (PB1-1) synthesized in
Synthesis Example 24, 2.0 parts of a cross-linker Actcol KL-210
(manufactured by Mitsui Chemicals Polyurethane Co., Ltd.), 2.5
parts of a communicating agent Actcol EP-505S (manufactured by
Mitsui Chemicals Polyurethane Co., Ltd.), 0.7 parts of a foam
stabilizer FV-1013-16 (manufactured by Dow Corning Toray Co.,
Ltd.), 2.3 parts of water, and 1.2 parts of a catalyst R-9000
(manufactured by Katsuzai Chemicals Co.). The resin premix was
mixed with 32 parts of polyisocyanate (manufactured by Mitsui
Chemicals Polyurethane Co., Ltd., trade name Cosmonate TM-20, NCO
index 1.00) and was immediately injected in a metal mold having
inside dimensions of 300 mm.times.300 mm.times.100 mm at 60.degree.
C. After the metal mold was closed, the mixture was expanded. The
metal mold was maintained at 60.degree. C. for eight minutes to
allow the curing reaction to proceed. A flexible polyurethane foam
was removed from the metal mold. Various physical properties of the
foam were measured. Table 4 shows the physical properties of the
flexible polyurethane foam.
Examples 2 to 4 and Comparative Examples 1 to 4
[0221] Flexible polyurethane foams (Examples 2 to 4 and Comparative
Examples 1 to 4) were produced in the same manner as Example 1
except that the amounts of the following raw materials were changed
as shown in Table 4: the polyester polyols (A-2 to A-8) produced in
Synthesis Examples 2 to 8, the low-monool-content polyol (B-1), the
polymer polyol (PB1-1), the cross-linker (Actcol KL-210), the
communicating agent (Actcol EP-505S), the foam stabilizer
(FV-1013-16), water, the catalyst (R-9000), and the foam stabilizer
(trade name Y-10366 manufactured by GE Toshiba Silicones Co.,
Ltd.). Table 4 shows the physical properties of the flexible
polyurethane foam.
Examples 5 to 12 and Comparative Examples 5 to 7
[0222] Flexible polyurethane foams (Examples 5 to 12 and
Comparative Examples 5 to 7) were produced in the same manner as
Example 1 except that the amounts of the following raw materials
were changed as shown in Table 5: the polyester polyols (A-9 to
A-14, A-16, and A-18) produced in Synthesis Examples 9 to 14, 16,
and 18, the low-monool-content polyol (B-1), the low-monool-content
polyol (C-1), the polymer polyol (PB1-1), the polymer polyol
(PC1-1), the cross-linker (Actcol KL-210), the cross-linker
(glycerin manufactured by Wako Pure Chemical Industries, Ltd.), the
communicating agent (Actcol EP-505S), the foam stabilizer
(FV-1013-16), water, the catalyst (R-9000), a catalyst (dibutyltin
dilaurate DBTDL (Neostam U-100 manufactured by Nitto Kasei Co.,
Ltd.), a catalyst (70% dipropylene glycol solution of
bis(2-dimethylaminoethyl)ether: NIAX A-1 manufactured by Momentive
Performance Materials Inc.), and the foam stabilizer (Y-10366).
Table 5 shows the physical properties of the flexible polyurethane
foam.
TABLE-US-00004 TABLE 4 Example 1 Example 2 Example 3 Example 4 Type
of polyester polyol Polyol A-1 Polyol A-2 Polyol A-3 Polyol A-4
Fatty acid having hydroxy group and High-purity High-purity
High-purity High-purity castor fatty acid ester having hydroxy
group castor oil fatty castor oil fatty castor oil fatty oil fatty
acid acid (1) + castor acid (1) + castor acid (3) + castor methyl
ester (4) + oil fatty acid oil fatty acid oil fatty acid castor oil
fatty acid Purity of castor oil fatty acid (ester) (%) 95 95 95 99
Purity of 12-hydroxystearic acid (%) Proportion of fatty acid
having hydroxy 98 98 98 99 group and carbon-carbon double bond (%)
Polyhydric alcohol PE450/SOR400 PE450/SOR400 PE450/SOR400
PE450/SOR400 Average number of functional groups of 4.6 5.2 5.8 4.9
polyhydric alcohol OHV (mgKOH/g) 30.9 55.2 33.3 27.5 Average number
of functional groups 3.5 4.4 4.4 4.4 (calculated) Mass ratio of
castor oil fatty acid 11.1 6.5 10.5 15.2 (per mole of polyhydric
alcohol) Amount charged (g) Polyisocyanate 32 34 32 32 NCO index
1.00 1.00 1.00 1.00 Type of polyester polyol Polyol A-1 Polyol A-2
Polyol A-3 Polyol A-4 Polyester polyol 58 58 58 58 Polyether polyol
B1-1 30 42 30 30 Polymer polyol PB1-1 12 0 12 12 Polyether polyol
C1-1 Polymer polyol PC1-1 KL-210 2.0 2.0 2.0 2.0 Glycerin EP-505S
2.5 2.5 2.5 2.5 Water 2.3 2.3 2.3 2.3 Y-10366 -- 1 -- 1 FV-1013-16
0.7 -- 0.5 -- DBTDL A-1 R-9000 1.2 1.2 1.2 1.2 Dco (kg/cm.sup.3)
60.0 60.8 59.5 59 BR (%) 60 62 65 65 25% ILD (N/314 cm.sup.2) 218
263 237 233 Elongation (%) 74 63 78 61 WS (%) 12.2 7.9 8.8 10.9
Characteristics balance (hardness, BR, WS) Good Good Good Good
Comparative Comparative Comparative Comparative example 1 example 2
example 3 example 4 Type of polyester polyol Polyol A-5 Polyol A-6
Polyol A-7 Polyol A-8 Fatty acid having hydroxy group and Castor
oil Castor oil Castor oil High-purity fatty acid ester having
hydroxy group fatty acid fatty acid fatty acid castor oil fatty
acid (1) + castor oil fatty acid Purity of castor oil fatty acid
(ester) (%) 86 86 86 95 Purity of 12-hydroxystearic acid (%)
Proportion of fatty acid having hydroxy 99 99 99 98 group and
carbon-carbon double bond (%) Polyhydric alcohol SOR400 SOR400
Gly/PE450 Gly Average number of functional groups of 6 6 3.6 3
polyhydric alcohol OHV (mgKOH/g) 34 53.9 59.2 57.8 Average number
of functional groups 3.5 4.4 2.6 2.6 (calculated) Mass ratio of
castor oil fatty acid 7.7 5.1 6.9 26.8 (per mole of polyhydric
alcohol) Amount charged (g) Polyisocyanate 32 34 34 34 NCO index
1.00 1.00 1.00 1.00 Type of polyester polyol Polyol A-5 Polyol A-6
Polyol A-7 Polyol A-8 Polyester polyol 58 58 58 58 Polyether polyol
B1-1 10 30 30 30 Polymer polyol PB1-1 32 12 12 12 Polyether polyol
C1-1 Polymer polyol PC1-1 KL-210 2.0 2.0 2.0 2.0 Glycerin EP-505S
2.5 2.5 2.5 2.5 Water 2.3 2.3 2.3 2.3 Y-10366 -- 1 -- -- FV-1013-16
0.5 -- 0.7 0.7 DBTDL A-1 R-9000 1.2 1.2 1.2 1.2 Dco (kg/cm.sup.3)
57.6 60.7 61.7 60.8 BR (%) 54 56 50 54 25% ILD (N/314 cm.sup.2) 220
268 207 218 Elongation (%) 78 73 62 69 WS (%) 9.2 8.3 6.3 7.1
Characteristics balance (hardness, BR, WS) Poor Poor Poor Poor
TABLE-US-00005 TABLE 5 Example 5 Example 6 Example 7 Example 8
Example 9 Type of polyester polyol Polyol A-9 Polyol A-10 Polyol
A-11 Polyol A-12 Polyol A-13 Fatty acid having hydroxy group and
High-purity High-purity High-purity High-purity High-purity castor
oil fatty acid ester having hydroxy group castor oil fatty castor
oil fatty castor oil fatty castor oil fatty fatty acid (1) + acid
(2) + castor acid (2) + castor acid (1) + castor acid (3) + castor
castor oil fatty acid + oil fatty acid oil fatty acid oil fatty
acid oil fatty acid high-purity 12-HSA Purity of castor oil fatty
acid (ester) (%) 90 90 95 97 95 Purity of 12-hydroxystearic acid
(%) 91 Proportion of fatty acid having hydroxy group 98 98 98 98 49
and carbon-carbon double bond (%) Polyhydric alcohol PE450/SOR400
PE450/SOR400 PE450/SOR400 PE450/SOR400 PE450/SOR400 Average number
of functional groups of 5.6 5.9 4.1 4.9 5.4 polyhydric alcohol OHV
(mgKOH/g) 34.5 53.1 54.4 50.6 54.3 Average number of functional
groups 3.5 4.4 3.5 4.4 4.4 (calculated) Mass ratio of castor oil
fatty acid 8.0 5.3 7.2 7.0 3.0 (per mole of polyhydric alcohol)
Amount charged (g) Polyisocyanate 33 34 34 34 35 NCO index 1.00
1.00 1.00 1.00 1.00 Type of polyester polyol Polyol A-9 Polyol A-10
Polyol A-11 Polyol A-12 Polyol A-13 Polyester polyol 58 58 58 58 58
Polyether polyol B1-1 42 42 30 42 42 Polymer polyol PB1-1 12
Polyether polyol C1-1 Polymer polyol PC1-1 KL-210 1.2 2.0 2.0 2.0
1.2 Glycerin EP-505S 2.5 2.5 2.5 2.5 2.5 Water 2.5 2.3 2.3 2.3 2.5
Y-10366 -- -- -- -- -- FV-1013-16 12 0.5 0.7 1.0 0.7 DBTDL NIAX A-1
R-9000 1.2 1.2 1.2 1.2 1.2 Dco (kg/cm.sup.3) 58.5 61.3 61.4 60.2
58.7 BR (%) 60 60 60 63 60 25% ILD (N/314 cm.sup.2) 195 216 279 239
245 Elongation (%) 72 58 75 54 65 WS (%) 10.7 9 7.7 9.2 8.6
Characteristics balance (hardness, BR, WS) Good Good Good Good Good
Comparative Comparative Comparative Example 10 Example 11 Example
12 example 5 example 6 example 7 Type of polyester polyol Polyol
A-16 Polyol A-16 Polyol A-18 Polyol A-14 Polyol A-6 Polyol A-6
Fatty acid having hydroxy group and High-purity High-purity
High-purity High-purity Castor oil Castor oil fatty acid ester
having hydroxy group castor oil fatty castor oil fatty 12-HSA
castor oil fatty fatty acid fatty acid acid (1) + castor acid (1) +
castor acid (1) + castor oil fatty acid oil fatty acid oil fatty
acid Purity of castor oil fatty acid (ester) (%) 95 95 95 86 86
Purity of 12-hydroxystearic acid (%) 92 Proportion of fatty acid
having hydroxy group 98 98 0 98 99 99 and carbon-carbon double bond
(%) Polyhydric alcohol PE450/SOR400 PE450/SOR400 PE450/SOR400
PE450/SOR400 SOR400 SOR400 Average number of functional groups of
5.2 5.2 5.6 4.7 6 6 polyhydric alcohol OHV (mgKOH/g) 49.7 49.7 52.9
12.2 53.9 53.9 Average number of functional groups 4.4 4.4 4.4 4.5
4.4 4.4 (calculated) Mass ratio of castor oil fatty acid 7.2 7.2
6.0 2.5 5.1 5.1 (per mole of polyhydric alcohol) Amount charged (g)
Polyisocyanate 38 38 34 41 38 38 NCO index 1.00 1.00 1.00 1.00 1.00
1.00 Type of polyester polyol Polyol A-16 Polyol A-16 Polyol A-18
Polyol A-14 Polyol A-6 Polyol A-6 Polyester polyol 31 31 58 58 31
31 Polyether polyol B1-1 54 42 42 42 Polymer polyol PB1-1 15 27
Polyether polyol C1-1 39 44 Polymer polyol PC1-1 10 30 25 KL-210
1.0 1.0 2.0 2.0 2.0 2.0 Glycerin 0.5 0.5 EP-505S 2.5 2.5 2.5 2.5
2.0 2.0 Water 2.3 2.3 2.3 2.3 2.3 2.3 Y-10366 -- -- 0.2 -- --
FV-1013-16 0.8 0.7 0.7 -- 0.7 0.7 DBTDL 0.05 NIAX A-1 0.05 0.05
0.05 R-9000 0.7 0.7 1.2 1.2 0.7 0.7 Dco (kg/cm.sup.3) 62.2 61.2
61.7 cannot expanded 57.7 59 BR (%) 71 64 61 59 58 25% ILD (N/314
cm.sup.2) 227 267 215 237 265 Elongation (%) 83 86 73 87 96 WS (%)
6.3 11.2 8.6 12.8 13.1 Characteristics balance (hardness, BR, WS)
Good Good Good Poor Poor Poor
Preparation of Polyurethane Resin
Example 13
[0223] A polyol (A-19) at 40.degree. C. and Cosmonate PH (MDI-PH
manufactured by Mitsui Chemicals, Inc.) at 50.degree. C. were mixed
with an agitator having blades at an NCO index of 1.00 for one
minute. After degassing under a reduced pressure for one minute,
the mixture was cured at 80.degree. C. for 24 hours in molds for
the measurement of physical properties (of a sheet type for the
measurement of hardness, 2 mm in thickness.times.12 mm.times.32 mm,
and of a button type for the measurement of rebound resilience, 11
mm in thickness.times.28 mm in diameter). After curing, the IR
measurement of a sample showed no unreacted NCO remained. Table 6
shows the physical properties of the resulting polyurethane
resin.
Examples 14 and 15 and Comparative Examples 8 and 9
[0224] Cured samples were produced in the same manner as Example 13
except that the polyols (A-2, A-4, A-7, and A-20) produced in
Synthesis Example 2, Synthesis Example 4, Synthesis Example 7, and
Synthesis Example 20 were used as shown in Table 6. After curing,
the IR measurement of each of the samples showed no unreacted NCO
remained. Table 6 shows the physical properties of the resulting
polyurethane resin.
TABLE-US-00006 TABLE 6 Comparative Comparative Example 13 Example
14 Example 15 example 8 example 9 Type of polyester polyol Polyol
A-19 Polyol A-2 Polyol A-4 Polyol A-7 Polyol A-20 Fatty acid having
hydroxy group and High-purity castor High-purity castor High-purity
castor oil Castor oil fatty 12-HSA fatty acid ester having hydroxy
group oil fatty acid (2) + oil fatty acid (1) + fatty acid methyl
ester acid castor oil fatty acid castor oil fatty acid (4) + castor
oil fatty acid Purity of castor oil fatty acid (ester) (%) 90 95 99
86 Purity of 12-hydroxystearic acid (%) 86 Proportion of fatty acid
(ester) having 98 98 99 99 0 hydroxy group and carbon-carbon double
bond (%) Polyhydric alcohol PE450/SOR400 PE450/SOR400 PE450/SOR400
SOR400 SOR400 Average number of functional groups 5.9 5.2 4.9 6 6
of polyhydric alcohol OHV (mgKOH/g) 52.0 55.2 27.5 53.9 53.3
Average number of functional groups 4.4 4.4 4.4 4.4 4.2 Mass ratio
of castor oil fatty acid (per 5.3 6.5 15.2 5.1 4.9 mole of
polyhydric alcohol) Amount charged (g) Polyisocyanate (MDI-PH) 18.6
19.6 9.8 18.3 19.0 NCO index 1.00 1.00 1.00 1.00 1.00 Type of
polyester polyol Polyol A-19 Polyol A-2 Polyol A-4 Polyol A-7
Polyol A-20 Polyester polyol 160 160 160 160 160 Shore A hardness
51 56 42 46 45 Rebound resilience (%) 69 71 73 67 57 Tensile
Maximum stress (MPa) 1.1 1.2 1.0 0.6 0.9 strength Maximum
elongation (%) 60.5 75.0 94.0 36.7 56.2
* * * * *