U.S. patent application number 14/555028 was filed with the patent office on 2015-03-19 for polyol, polyol composition, and flexible polyurethane foam using the same.
The applicant listed for this patent is Mitsui Chemicals, Inc.. Invention is credited to Toru Hiraide, Tamotsu Kunihiro, Mikio Matsufuji, Shinsuke Matsumoto, Atsushi Miyata, Koichi Sano.
Application Number | 20150080488 14/555028 |
Document ID | / |
Family ID | 45559628 |
Filed Date | 2015-03-19 |
United States Patent
Application |
20150080488 |
Kind Code |
A1 |
Matsufuji; Mikio ; et
al. |
March 19, 2015 |
POLYOL, POLYOL COMPOSITION, AND FLEXIBLE POLYURETHANE FOAM USING
THE SAME
Abstract
Disclosed are a polyol with a molecular weight distribution
Mw/Mn of 4 or more, obtained by reacting a compound comprising an
alkylene oxide compound (II) having a hydroxyl group in a base
polyol (I) with a molecular weight of 2000 or more; and a polyol
composition for a flexible polyurethane foam, comprising a polyol
compound and a crosslinker, wherein the crosslinker comprises a
polyol (a) with a hydroxyl value of 50 to 1100 mgKOH/g and with a
primary hydroxylate ratio of 25% or more and 60% or less, which is
obtained by an addition of a compound comprising alkylene oxide
compound (ii) having a hydroxyl group to active hydrogen compound
(i).
Inventors: |
Matsufuji; Mikio;
(Ichihara-shi, JP) ; Kunihiro; Tamotsu;
(Kisarazu-shi, JP) ; Miyata; Atsushi;
(Ichihara-shi, JP) ; Matsumoto; Shinsuke;
(Ichihara-shi, JP) ; Sano; Koichi; (Ichihara-shi,
JP) ; Hiraide; Toru; (Syunan-shi, JP) |
|
Applicant: |
Name |
City |
State |
Country |
Type |
Mitsui Chemicals, Inc. |
Minato-ku |
|
JP |
|
|
Family ID: |
45559628 |
Appl. No.: |
14/555028 |
Filed: |
November 26, 2014 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
|
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13814437 |
Feb 5, 2013 |
|
|
|
PCT/JP2011/068035 |
Aug 8, 2011 |
|
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14555028 |
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Current U.S.
Class: |
521/170 ;
252/182.12; 252/183.11 |
Current CPC
Class: |
C07C 31/18 20130101;
C08G 18/4841 20130101; C08G 18/3206 20130101; C08G 2101/0083
20130101; C07C 41/03 20130101; C08G 18/48 20130101; C08G 18/3212
20130101; C08G 18/632 20130101; C08G 18/4072 20130101; C07C 41/02
20130101; C08G 18/7664 20130101; C08G 2101/0008 20130101; C07C
43/178 20130101; C08G 2101/005 20130101 |
Class at
Publication: |
521/170 ;
252/183.11; 252/182.12 |
International
Class: |
C08G 18/32 20060101
C08G018/32 |
Foreign Application Data
Date |
Code |
Application Number |
Aug 6, 2010 |
JP |
2010-177691 |
Claims
1. A polyol composition for a flexible polyurethane foam,
comprising a polyol compound and a crosslinker, wherein the
crosslinker comprises a polyol (a) with a hydroxyl value of 50 to
1100 mgKOH/g and with a primary hydroxylate ratio of 25% or more
and 60% or less, which is obtained by an addition of a compound
comprising an alkylene oxide compound (ii) having a hydroxyl group
to an active hydrogen compound (i).
2. The polyol composition for a flexible polyurethane foam
according to claim 1, wherein the active hydrogen compound (i)
comprises glycerin or glycidol.
3. The polyol composition for a flexible polyurethane foam
according to claim 1, wherein the compound (ii) comprises an
epoxide having a hydroxyl group.
4. The polyol composition for a flexible polyurethane foam
according to claim 3, wherein the epoxide having a hydroxyl group
comprises glycidol.
5. The polyol composition for a flexible polyurethane foam
according to claim 1, wherein the polyol compound comprises a
polyol (b) with a hydroxyl value of 10 to 80 mgKOH/g.
6. The polyol composition for a flexible polyurethane foam
according to claim 5, wherein the polyol (b) is at least one polyol
selected from polyether polyols and polymer dispersed polyols.
7. A flexible polyurethane foam, obtained by reacting the polyol
composition according to claim 1 and an isocyanate compound.
8. A resin premix for a flexible polyurethane foam, comprising the
polyol composition for a flexible polyurethane foam according to
claim 1 and another additive.
9. The resin premix for a flexible polyurethane foam according to
claim 8, wherein the another additive comprises a catalyst.
10. The resin premix for a flexible polyurethane foam according to
claim 9, wherein the another additive further comprises a
surfactant and/or a foaming agent.
11. A flexible polyurethane foam, obtained by reacting the resin
premix according to claim 8 and an isocyanate compound.
Description
[0001] This application is a Divisional of U.S. application Ser.
No. 13/814,437, filed Feb. 5, 2013, which is a National Stage of
PCT/JP2011/068035, filed Aug. 8, 2011 which claims priority to
Japanese Application No. 2010-177691, filed Aug. 6, 2010 the
disclosures of which are hereby incorporated by reference in their
entirety.
TECHNICAL FIELD
[0002] The present invention relates to a polyol, a polyol
composition, and a flexible polyurethane foam using the same. For
more detail, the present invention relates to a polyol which is
useful for producing a flexible polyurethane foam having an
excellent resilience, a moderate hardness and an excellent
durability in a good balance.
BACKGROUND ART
[0003] Since flexible polyurethane foams have an excellent
cushioning property, they are widely used for the purpose of
cushion materials such as seat cushions for vehicles. In
particular, since cushion materials having a high resilience can
achieve an ideal body pressure dispersion and it is very
comfortable, the needs are extremely high. Also, in the seat
cushions, there are simultaneously required a moderate hardness
that is not too soft and too hard, as well as an excellent
durability that there is a little change of the elasticity, the
hardness and the thickness even if it is used for a long time.
[0004] In late years, in the field of flexible polyurethane foams,
in particular of seat cushions for vehicles such as automobiles, a
weight saving is required. However, when a weight saving of the
flexible polyurethane foam is progressed, the hardness is damaged
and the form properties tend to be deteriorated. Thus, various
studies regarding maintaining and improving the hardness have been
carried out.
[0005] As a method for improving the hardness of a flexible
polyurethane foam, it is generally known to increase the used
amount of a polymer dispersed polyol obtained by dispersing a vinyl
polymer in a polyether polyol. However, by this method, another
property is deteriorated.
[0006] As another method, there is a method using a specified
crosslinker. For example, Patent Document 1 discloses a technology
in which a polyglycerin is added as a part of a crosslinker to
improve a moldability. However, in this method, the sufficient
hardness of the flexible polyurethane foam is not developed.
[0007] Also, Patent Document 2 discloses a polymerization method of
glycidol using an alkali metal halide as a catalyst. However, in
this method, a polyol for developing a sufficient property of the
flexible polyurethane foam is not obtained.
[0008] Also, Patent Document 3 and Patent Document 4 disclose an
ester of a fatty acid and a polyglycerin with a primary OH of 50 wt
% or more as a composition in a high crystallized material.
However, these are not used for a flexible polyurethane foam.
[0009] Also, Patent Document 5 discloses a method in which a
polyglycerin is used as a crosslinker together with a specified
polyol to produce a flexible polyurethane foam. However, in this
method, a polyol for developing a sufficient property of the
flexible polyurethane foam is not obtained.
[0010] Also, Non-Patent Document 1 discloses a cyclic oligoglycidol
(C18, 6 glycidol). Also, Non-Patent Document 2 discloses a method
for synthesizing a polyglycidol by an addition of glycidol to a
monomer having terminal OH. However, these are not used for a
flexible polyurethane foam.
PRIOR ART DOCUMENT
Patent Document
[0011] Patent Document 1: JP 2003-313267 A [0012] Patent Document
2: JP 2002-30144 A [0013] Patent Document 3: JP 2008-143841 A
[0014] Patent Document 4: WO 2006/134886 [0015] Patent Document 5:
JP 2003-313267 A
Non-Patent Document
[0015] [0016] Non-Patent Document 1: Reactive & Functional
Polymers (2005, 65(3), P 259-) [0017] Non-Patent Document 2:
Reviews in Molecular Biotechnology (2002, 90, P 257-)
SUMMARY OF THE INVENTION
Problem to be Solved by the Invention
[0018] The present invention was realized in order to solve the
above-explained problems. That is, the object of the present
invention is to provide a polyol which is useful for producing a
flexible polyurethane foam having an excellent resilience, a
moderate hardness and an excellent durability in a good
balance.
Means of Solving the Problem
[0019] The first present invention is a polyol with a molecular
weight distribution Mw/Mn of 4 or more, obtained by reacting a
compound comprising an alkylene oxide compound (II) having a
hydroxyl group in a base polyol (I) with a molecular weight of 2000
or more.
[0020] The second present invention is a polyol composition for a
flexible polyurethane foam, comprising a polyol compound and a
crosslinker, wherein the crosslinker comprises a polyol (a) with a
hydroxyl value of 100 to 1100 mgKOH/g and with a primary
hydroxylate ratio of 25% or more and 60% or less, which is obtained
by an addition of a compound comprising an alkylene oxide compound
(ii) having a hydroxyl group to an active hydrogen compound
(i).
Effect of the Invention
[0021] According to the present invention, even if a weight saving
of the flexible polyurethane foam proceeds in response to the
weight saving requirements of cushion materials such as car for
cushion seats for cars, the properties can be maintained or
improved. Specifically, when the polyol or the polyol composition
of the present invention is used, a flexible polyurethane foam
having an excellent resilience, a moderate hardness and an
excellent durability in a good balance can be obtained.
MODE FOR CARRYING OUT THE INVENTION
[0022] First, an embodiment of the first present invention is
explained.
[0023] The polyol of the first present invention is a polyol
(hereinafter, referred to as "polyol (A)") with a molecular weight
distribution Mw/Mn of 4 or more, which is obtained by reacting a
compound containing an alkylene oxide compound (II) having a
hydroxyl group in base polyol (I) with a molecular weight of 2000
or more.
[0024] The molecular weight distribution curve of the polyol (A)
preferably has at least one maximum value in an area of higher
molecular weight than that of the base polyol (I). This maximum
value is typically caused by a polyol obtained by an addition
polymerization of a compound containing the alkylene oxide compound
(II) having a hydroxyl group to a hydroxyl group of the base polyol
(I).
[0025] In the molecular weight distribution curve of the polyol
(A), there are typically existed an area S1 of the base polyol (I),
an area S2 of higher molecular weight, and an area S3 of lower
molecular weight. As mentioned above, the area S2 of higher
molecular weight is typically caused by a polyol obtained by an
addition polymerization of a compound containing the alkylene oxide
compound (II) having a hydroxyl group to a hydroxyl group of the
base polyol (I). Also, the area S3 of lower molecular weight is
typically caused by a polyol consisting of a polymer of a compound
containing the alkylene oxide compound (II) having a hydroxyl
group. That is, it can also be said that the polyol (A) is a
mixture of these various polyols. In the molecular weight
distribution curve, an area ratio (S1/S2) of area S1 and area S2 is
preferably 99/1 to 20/80 from the point of the viscosity of the
product or the like.
[0026] The average functional group number of the polyol (A) is
preferably larger than 6. When the average functional group number
is larger than 6, the hardness, the resilience and the durability
of the flexible polyurethane foam become good. Also, even if this
average functional group number is increased to approximately 700,
there is an effect for the developing a good balance of the
properties. This average functional group number is a value
represented by an integer which is calculated by adding, for
example, the added mol number of alkylene oxide compound (II)
having a hydroxyl group (in the case where the hydroxyl group
number of compound (II) is 1) to the functional group number of
base polyol (I) and by rounding off it to the nearest integer.
[0027] The base polyol (I) is a base polymer to function as an
initiator for the addition polymerization reaction of a compound
containing the alkylene oxide compound (II). It may be a polymer
having a hydroxyl group which functions in that manner, and the
kind is not particularly limited. The molecular weight of base
polyol (I) is 2000 or more, and is preferably 3000 to 7000.
[0028] Examples of the base polyol (I) used for the polyol (A)
include, for example, polyether compounds (2) obtained by adding
one or more alkylene oxides selected from ethylene oxide, propylene
oxide and butylene oxide to an organic compound (1) which has one
or more groups selected from hydroxyl group, amino group, thiol
group and carboxyl group and which does not have a polyether
structure.
[0029] Examples of organic compound (1) having a hydroxyl group in
a molecule include, for example, alcohols with a carbon number of 1
to 20 having 1 to 8 hydroxyl groups, sugars or derivatives thereof,
and aromatic compounds with a carbon number of 6 to 20 having 1 to
3 hydroxyl groups. Among these, alcohols with a carbon number of 1
to 20 having 1 to 8 hydroxyl groups are preferable, and
ethyleneglycol, propylene glycol, glycerin, trimethylolpropane,
pentaerythritol, sorbitol, sucrose and triethanolamine are more
preferable.
[0030] Examples of the organic compound (1) having an amino group
in a molecule include, for example, aliphatic or aromatic primary
amines with a carbon number of 1 to 20, aliphatic or aromatic
secondary amines with a carbon number of 2 to 20, polyvalent amines
with a carbon number of 2 to 20 having 2 to 3 primary or secondary
amino groups in a molecule, saturated cyclic secondary amines with
a carbon number of 4 to 20, unsaturated cyclic secondary amines
with a carbon number of 4 to 20, and cyclic polyvalent amines with
a carbon number of 4 to 20 having 2 to 3 secondary amino groups in
a molecule. Among these, aliphatic or aromatic primary amines with
a carbon number of 1 to 20 and aliphatic or aromatic secondary
amines with a carbon number of 2 to 20 are preferable, and
monoethanolamine, diethanolamine, ethylenediamine, piperazines,
aniline, toluidine, 2,4-tolylenediamine, 2,6-tolylenediamine,
2,3-tolylenediamine, 4,4'-diaminodiphenylmethane are more
preferable.
[0031] Compound (II) used for the polyol (A) is an alkylene oxide
compound having a hydroxyl group. The carbon number of the alkylene
oxide is preferably 2 to 12. Specific examples thereof include
2-hydroxytetrahydrofuran, 3-hydroxyoxetane, glycidol,
1,2-epoxy-3-butanol, 3-hydroxycyclopentene oxide,
2,3-epoxy-2-methyl-1-propanol, 2,3-epoxybutanol,
3,4-epoxy-3-methyl-2-pentanol, 3,4-epoxy-4-methyl-2-pentanol,
2,3-epoxycyclohexanol, 2,3-epoxy-4-hydroxyhexane,
6-oxabicyclo[3.1.0]hexane-2,4-diol,
6-oxabicyclo[3.1.0]hexane-2,3-diol, 2,3-epoxy-1,4-butanediol,
1,2-epoxy-3-pentanol, and 2,3-epoxy-4-heptanol. Among these,
epoxides having a hydroxyl group are preferable, and glycidol is
particularly preferable. Also, glycidol and an alkylene oxide other
than it may be used together.
[0032] Further, the alkylene oxide compound (II) which has a
hydroxyl group and an alkylene oxide which does not have a hydroxyl
group may be used together. That is, an alkylene oxide compound
containing the alkylene oxide compound (II) having a hydroxyl group
may be reacted in the base polyol (I). Specific examples of the
alkylene oxide which does not have a hydroxyl group include
ethylene oxide, propylene oxide, 1,2-butylene oxide, 2,3-butylene
oxide, styrene oxide, cyclohexane oxide, epichlorohydrin,
epibromohydrin, methyl glycidyl ether, allyl glycidyl ether, and
phenyl glycidyl ether. Among these, ethylene oxide, propylene
oxide, 1,2-butylene oxide, 2,3-butylene oxide and styrene oxide are
preferable. In particular, ethylene oxide, propylene oxide,
1,2-butylene oxide and 2,3-butylene oxide are more preferable.
[0033] Some alkylene oxides having a hydroxyl group such as
glycidol contain an anion-containing impurity such as chlorine
(.alpha.-chlorohydrin in the case of glycidol) depending on the
production method. The alkylene oxides containing such an impurity
can be used in the present invention. In this case, the
polymerization is carried out with keeping the reaction system
basic that the mol number of the anion such as chlorine does not
become larger than the mol number of the cation of the
polymerization catalyst described below.
[0034] The amount of glycidol is preferably 50 to 100 mol % in 100
mol % of the compound containing the alkylene oxide compound (II)
having a hydroxyl group. When the amount is 50 mol % or more, the
effect regarding the hardness of the flexible polyurethane foam is
sufficiently developed and the balance of the properties becomes
good.
[0035] Specific examples of the reaction for addition
polymerization of the compound containing the alkylene oxide
compound (II) having a hydroxyl group to the base polyol (I)
include, for example, a method by a simultaneous addition
polymerization of a mixture consisting of glycidol and an alkylene
oxide other than glycidol in a random form, a method by an addition
polymerization of only glycidol, a method by an addition
polymerization of glycidol in a block form and thereafter by an
addition polymerization of an alkylene oxide other than glycidol in
a block form, and a method by addition polymerizations of glycidol
and of an alkylene oxide other than glycidol in a sequential block
form.
[0036] In the alkylene oxide contained in the whole of the polyol
(A), the mol ratio of the alkylene oxide other than glycidol and
glycidol is preferably 99/1 to 20/80.
[0037] When the compound containing the alkylene oxide compound
(II) having a hydroxyl group is reacted in the base polyol (I) to
obtain the polyol (A), it is preferable to use a basic compound as
a catalyst. By a reaction in the presence of a basic compound,
above-explained suitable polyol (A) can be obtained well.
[0038] Specific examples of the basic compound include alkali metal
compounds and alkaline-earth metal compounds such as hydroxides and
carbonates, and tertiary amine compounds such as triethylamine,
dimethyloctylamine, dimethylpalmitylamine, phosphazene compounds
and phosphazenium compounds.
[0039] As a phosphazene compound, it is possible to use, for
example, a compound represented by following formula (2) described
in JP 2001-106780 A.
##STR00001##
[In formula (2), R each independently represent a hydrocarbon group
with a carbon number of 1 to 10, and x is a content (mol ratio) of
water contained and represents 0 to 5.]
[0040] Compound represented by above-mentioned formula (2) is
typically tris[tris(dimethylamino)phosphoranylideneamino]phosphine
oxide or tris[tris(diethylamino)phosphoranylideneamino]phosphine
oxide.
[0041] As a phosphazenium compound, it is possible to use, for
example, a compound represented by following formula (1) described
in JP 2001-106780 A.
##STR00002##
[In formula (1), a, b, c and d each are an integer of 0 to 3.
However, it is excluded that all of a, b, c and d are 0. R each
independently represent a hydrocarbon group with a carbon number of
1 to 10, and it is included that two R on the same nitrogen atom
are connected each other to form a ring structure. Q.sup.-
represents hydroxy anion, an alkoxy anion, an aryloxy anion or an
carboxy anion.]
[0042] Compound represented by above-mentioned formula (1) is
typically
tetrakis[tris(dimethylamino)phosphoranylideneamino]phosphonium
hydroxide,
tetrakis[tris(dimethylamino)phosphoranylideneamino]phosphonium
methoxide,
tetrakis[tris(dimethylamino)phosphoranylideneamino]phosphonium
ethoxide, or
tetrakis[tri(pyrrolidine-1-yl)phosphoranylideneamino]phosphonium
tert-butoxide.
[0043] The lower limit of the used amount of the basic compound for
the reaction is 0.0001 mol % with respect to 1 mol of the active
hydrogen in the polyol (A), is preferably 0.0005 mol %, and is more
preferably 0.001 mol % while the upper limit is 10 mol %, is
preferably 1 mol %, and is more preferably 0.5 mol %. If the amount
of the basic compound is less than the above-mentioned range, the
reaction time becomes longer. Also, if it is more than the
above-mentioned range, the production is not economically
preferable. And, in the case where the post processing is carried
out, the neutralization salt is hardly removed, and a polyether
polyol, by which a good balance of the properties of the flexible
polyurethane foam physical property is developed, cannot be
obtained.
[0044] Also, when an alkylene oxide containing an anion-containing
impurity is used as described above, it is preferable to carry out
the polymerization with keeping a reaction system basic. If the
reaction system is not basic, the molecular weight distribution
becomes narrow and the high molecular weight body is tend not to be
formed.
[0045] It is desirable to sequentially charge an alkylene oxide
having a hydroxyl group to a reaction system. In the case where an
alkylene oxide having a hydroxyl group stays in a reaction system
in a large amount, a self-polymerization preferentially occurs and
a high molecular weight body is hardly formed, and the molecular
weight distribution tends to become narrow. Thus, it desirably
takes a certain time to charge it. Further, the initial
concentration a of the catalyst cation to OH of a base polyol that
is an initiator is preferably higher, depending on catalytic
activity, because the reaction of the base polyol and alkylene
oxide (II) having a hydroxyl group is promoted. Also, when the OH
concentration (mol/kg) in the initiator is higher, the reaction
with alkylene oxide (II) having a hydroxyl group is promoted, and
it is preferable.
[0046] In view of these, when the initial concentration of the
catalyst cation to OH of the initiator is .alpha. (mol/initiator OH
mol), the concentration of the initiator OH is .beta. (mol/kg), and
the charging speed of the alkylene oxide having a hydroxyl group is
.gamma. (mol/Hrkg), .gamma./(.alpha..times..beta.) is preferably
20000 or less and is more preferably 10000 or less because a high
molecular weight body can definitely be formed.
[0047] The reaction conditions are not particularly limited, but
the temperature is preferably 80 to 160.degree. C. and is more
preferably 90 to 140.degree. C. Also, the pressure is preferably
0.5 MPaG or less.
[0048] In the case where the above-mentioned basic compound is used
as a catalyst, a step for removing a catalyst from the polyol (A)
obtained may be carried out, or may not be carried out. In both
cases, the polyol (A) can be used for producing a flexible
polyurethane foam.
[0049] The polyol (A) can be mixed with another polyol to be used.
In particular, a polyol composition containing 1 to 200 parts by
mass of the polyol (A) and 100 parts by mass of polyol (B) with a
hydroxyl value of 10 to 80 mgKOH/g is preferable, and a polyol
composition containing 1 to 100 parts by mass of the polyol (A) and
100 parts by mass of polyol (B) with a hydroxyl value of 10 to 80
mgKOH/g is more preferable. This polyol (B) is particularly
preferably at least one polyol selected from polyether polyols and
polymer dispersed polyols.
[0050] Next, the second present invention is explained.
[0051] The second present invention is a polyol composition for a
flexible polyurethane foam, which contains a polyol compound and a
crosslinker, in which the crosslinker contains the polyol (a) with
a hydroxyl value of 50 to 1100 mgKOH/g and with a primary
hydroxylate ratio of 25% or more and 60% or less, which is obtained
by an addition of a compound containing the alkylene oxide compound
(ii) having a hydroxyl group to active hydrogen compound (i).
[0052] Active hydrogen compound (i) used for the polyol (a) is a
compound having an active hydrogen showing reactivity. Examples of
active hydrogen compound (i) include, for example, the organic
compounds (1) which have one or more groups selected from hydroxyl
group, amino group, thiol group and carboxyl group and which do not
have a polyether structure. Also, examples include the polyether
compounds (2) which are obtained by adding one or more alkylene
oxides selected from ethylene oxide, propylene oxide and butylene
oxide to this organic compound (1). In particular, an organic
compound having a hydroxyl group or an amino group, or having a
hydroxyl group and an amino group is preferable, and an organic
compound having 1 to 8 hydroxyl groups or amino groups, or having 1
to 8 hydroxyl groups and amino groups is more preferable. Specific
examples of this organic compound (1) include the same compounds as
those described in the explanation of the first invention. And,
active hydrogen compound (i) can be used alone, or in a mixture
with two or more kinds, which is selected from the group consisting
of the organic compounds (1), water, ammonia, and the polyether
compounds (2). Also, active hydrogen compound (i) preferably
contains glycerin or glycidol. In the case where active hydrogen
compound (i) is glycidol, glycidol functions as both of compound
(i) and compound (ii).
[0053] The kind, the reaction conditions and the catalyst of
compound (ii) used for the polyol (a) are the same as the kind, the
reaction conditions and the catalyst of compound (II) in the first
invention.
[0054] The lower limit of the hydroxyl value of the polyol (a) is
50 mgKOH/g, and is preferably 100 mgKOH/g from the point of the
hardness of the flexible polyurethane foam. Also, the upper limit
1100 mgKOH/g, is preferably 1050 mgKOH/g, and is more preferably
1000 mgKOH/g from the points that the hardness of the flexible
polyurethane foam is moderately suppressed and that the balance of
resilience and durability is made good.
[0055] The lower limit of the primary hydroxylate ratio of the
polyol (a) is 25%, is preferably 40%, and is more preferably 45%
from the point that the balance of the foam properties is made
good. Also, the upper limit is 60%, is preferably 58%, and is more
preferably 57% from the point that the balance of the foam
properties is made good.
[0056] The polyol (A) of the first invention and the polyol (a)
used in the second invention explained above are purified as
necessary. After a basic compound in the crude polyol is
neutralized with an acid such as an inorganic acid, a purification
step, in which a salt precipitated by dehydration and drying is
filtered, can be carried out to produce the polyol.
[0057] The catalyst can be adsorbed by an inorganic adsorbent, and
the basic compound can be filtered. Also, after it is neutralized
with an acid such as an inorganic acid, the surplus acidic
component and basic component are adsorbed by an inorganic
adsorbent, and it can be filtered. Examples of the inorganic
adsorbent include, for example, synthetic silicates (such as
magnesium silicate and aluminum silicate), ion exchange resins, and
activated white earths.
[0058] Also, a well-known stabilizer may be added as necessary
before or after the purification of the polyols (A) and (a). In the
case where the polyols (A) and (a) are stored for a long time, an
antioxidant or an anticorrosive can be added to prevent the
deterioration of polyols (A) and (a). In particular, an antioxidant
is preferably added to prevent the deterioration of polyols (A) and
(a). The antioxidant may be used alone, or in combination with two
or more kinds. Examples of the antioxidant include, for example,
tert-butyl hydroxy toluene (BHT),
pentaerythrityl-tetrakis-3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate,
octadecyl-3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate,
ethylhexylphosphite, tri(nonylphenyl)phosphite,
4,4'-bis-.alpha.,.alpha.'-dimethylbenzyldiphenylamine,
2-tert-butyl-4-ethylphenol, and
2,6-di-tert-butyl-4-ethylphenol.
[0059] The added amount of the antioxidant is not particularly
limited as long as the effect can be obtained in the concentration,
but is usually approximately 100 to 5000 ppm to the polyols (A) and
(a). For example, as a stabilizer, at least one selected from the
group consisting of hindered phenol compounds and
nitrogen-containing compounds can be used. In the case where a
stabilizer is used, the added amount is not particularly limited as
long as the effect can be obtained in the concentration, but is
usually approximately 100 to 5000 ppm to the polyols (A) and
(a).
<Polyol Composition>
[0060] The polyol (A) of the first invention and the polyol (a)
used in the second invention explained above are preferably used as
a polyol composition mixed with another polyol.
[0061] As another polyol, all polyol compounds commonly used for a
polyurethane foam purpose can be used. Specific examples thereof
include polyether polyols, polyester polyols, polyester ether
polyols, polycarbonate polyols, polybutadiene polyols, bio polyols
derived from a nature fat described in WO 2007/020904, WO
2010/013710 and the like, and polymer dispersed polyols. In
particular, in order to produce a flexible polyurethane foam used
for the purpose of seat pads for vehicles such as automobiles, one
or more polyols selected from polyether polyols and polymer
dispersed polyols are preferably used as another polyol.
[0062] Examples of the polyether polyols and polymer dispersed
polyols also include polyols described in JP 2001-107680 A.
[0063] For example, as a polyether polyol, the polyether compound
(2) explained in the second invention can also be used.
[0064] The polymer dispersed polyol is a polyol in which a vinyl
polymer particle obtained by a radical polymerization of a compound
having an unsaturated bond in a polyol is dispersed in this polyol.
In particular, a polymer dispersed polyol is preferable. Polymer
dispersed polyol provided from polyether polyol obtained from a
polyether polyol is preferable. Examples of the radical
polymerization initiator used for the polymerization include, for
example, azo compounds such as azobisisobutyronitrile and peroxide
compounds such as benzoyl peroxide, dialkyl peroxides and peroxy
ketals. Also, in the polymerization, a dispersion stabilizer and a
chain transfer agent may be added. The vinyl polymer particle
dispersed in this polyol is a particle consisting of a polymer of a
compound having an unsaturated bond. However, at least a part of
this compound is preferably polymerized with a polyether polyol at
the time of the polymerization. Specific examples of the compound
having an unsaturated bond include (meth)acrylonitrile, styrene,
vinyl pyridine, (meth)acrylamide, and (meth)acrylates such as
methyl(meth)acrylate and 2-hydroxyethyl(meth)acrylate. This may be
used alone, or in a mixture with two or more kinds
[0065] In the present invention, the preferred polyol compositions
include a polyol composition containing the polyol (A) and the
polyol (B) with a hydroxyl value of 10 to 80 mgKOH/g and a polyol
composition containing the polyol (a) and the polyol (b) with a
hydroxyl value of 10 to 80 mgKOH/g. As mentioned above, the polyols
(B) and (b) are preferably one or more polyol selected from
polyether polyols and polymer dispersed polyols. Also, when the
amount of polyols (B) and (b) is assumed to be 100 parts by mass,
the amount of polyols (A) and (a) is preferably 1 to 200 parts by
mass and is more preferably 1 to 100 parts by mass. Further, in 100
mass % of polyol composition, 0.5 to 20 mass % of a constitutional
unit consisting of an alkylene oxide having a hydroxyl group is
preferably contained.
[0066] The lower limit of the hydroxyl value of polyols (B) and (b)
is 10 mgKOH/g, is preferably 15 mgKOH/g, and is more preferably 20
mgKOH/g. Also, the upper limit is 80 mgKOH/g, is preferably 70
mgKOH/g, and is more preferably 60 mgKOH/g. Each lower limit is
valid at the point that the flexible polyurethane foam is made not
too soft, and each upper limit is valid at the point that the
flexible polyurethane foam is made not too hard, i.e. the hardness
is not too high. The moderate hardness is important for the purpose
of seats for vehicles.
[0067] The polyols (B) and (b) may be a mixture of two or more
polyols. In that case, the average hydroxyl value of the mixture
should be within the above-mentioned range. Also, a polyol other
than the polyols (A) and (a) and the polyols (B) and (b) may be
used as long as it does not affect the foam property.
<Flexible Polyurethane Foam>
[0068] A flexible polyurethane foam is obtained by reacting a
polyol composition containing the polyol (A) and/or the polyol (a)
explained above with an isocyanate compound. The reaction is
carried out in the presence of, for example, an arbitrary component
such as a catalyst, a foaming agent, a surfactant, or another
auxiliary agent.
<Isocyanate Compound>
[0069] The isocyanate compound is not particularly limited. For
example, a well-known isocyanate compound, which is described in
Keiji Iwata, "Polyurethane Resin Handbook", first edition, Nikkan
Kogyo Shimbun Ltd., (1987) pp. 71-98, can be used.
[0070] The isocyanate compound for obtaining a foam is preferably
toluylene diisocyanate (the isomer ratio such as 2,4-body and
2,6-body is not particularly limited but 2,4-body/2,6-body is
preferably a ratio of 80/20), a polymethylene polyphenyl
polyisocyanate (for example, produced by Mitsui Chemicals, Inc.,
trade name: COSMONATE M-200) or a urethane modified body thereof,
or a mixture thereof.
[0071] Also, diphenylmethane diisocyanate (for example, produced by
Mitsui Chemicals, Inc., trade name: COSMONATE PH), xylylene
diisocyanate, norbornene diisocyanate, naphthalene diisocyanate,
bis(isocyanatomethyl)cyclohexane or hexamethylene diisocyanate can
be used.
[0072] In the case where a mixture of toluylene diisocyanate and
another isocyanate compound is used, from a point of the balance of
the durability and the mechanical strength of the flexible
polyurethane foam, the content of toluylene diisocyanate in 100
mass % of the total amount of the isocyanate compounds is
preferably 50 to 99 mass %, is more preferably 70 to 90 mass %, and
is particularly preferably 75 to 85 mass %.
<Catalyst for Producing Flexible Polyurethane Foam>
[0073] When a flexible polyurethane foam is produced, a well-known
catalyst can be used without a particular limitation. For example,
aliphatic amines such as triethylenediamine,
bis(2-dimethylaminoethyl) ether, 1-isobutyl-2-methyl imidazole, and
morpholine; and organic tin compounds such as tin octanoate and
dibutyl tin dilaurate are preferable. This may be used alone, or in
combination with two or more kinds. The used amount of the catalyst
for producing a flexible polyurethane foam is preferably 0.1 to 10
parts by mass with respect to 100 parts by mass of the polyol
composition.
<Foaming Agent>
[0074] When a flexible polyurethane foam is produced, a physical
foaming agent such as liquefied carbon dioxide can be used as a
foaming agent, but water is most preferably used. In the case where
water is used as a foaming agent, from a point of the foaming
stability and the validity, the used amount of water is preferably
1.3 to 6.0 parts by mass with respect to 100 parts by mass of the
polyol composition, is more preferably 1.8 to 5.0 parts by mass,
and is particularly preferably 2.0 to 4.5 parts by mass. Also, a
physical foaming agent such as a hydroxy fluorocarbon (HFC-245fa or
the like) which is developed for the purpose of global environment
protection, a hydrocarbon (cyclopentane or the like), carbon
dioxide, or liquefied carbon dioxide can also be used together with
water. In particular, from a point of reducing the environmental
load, it is preferable to use carbon dioxide or liquefied carbon
dioxide with water.
<Surfactant>
[0075] When a flexible polyurethane foam is produced, a well-known
surfactant can be used without a particular limitation. Usually, it
is preferable to use an organic silicon surfactant. Examples of the
preferred commercial surfactant include, for example, SZ-1966,
SZ-1919, SZ-1959, SZ-1142 and SRX-274DL produced by Dow Corning
Toray Co., Ltd., L-5309, Y-10366, L-3622, L-598 and L-3150 produced
by Momentive Performance Materials Japan limited liability company.
The used amount of the surfactant is preferably 0.1 to 10 parts by
mass with respect to 100 parts by mass of the polyol composition,
and is more preferably 0.5 to 5 parts by mass.
<Auxiliary Agent>
[0076] When a flexible polyurethane foam is produced, a general
auxiliary agent or an additive for producing a flexible
polyurethane foam can be used with each above mentioned component
as long as the object of the present invention is not damaged.
Examples of the auxiliary agent and the additive include, for
example, chain extenders, crosslinkers, cell openers, flame
retardants, pigments, UV absorbers, and antioxidants. Specifically,
various auxiliary agents and additives, which are described in
Nobutaka Matsudaira and Tetsuro Maeda, "Polyurethane", eighth
edition, Maki Shoten, (1964) pp. 134-137 and in Hitoshi Matsuo,
Nobuaki Kunii, and Kiyoshi Tanabe, "Functional Polyurethane", first
edition, CMC Publishing CO., LTD., (1989) pp. 54-68, can be
used.
<Method for Producing Flexible Polyurethane Foam>
[0077] The method for producing flexible polyurethane foam is not
particularly limited and a well-known method can be adopted.
Specifically, any of a slab foam method, a hot cure mold foam
method, and a cold cure mold foam method can be adopted. In the
case of producing a seat pad for vehicles such as automobiles, a
cold cure mold foam method is preferable.
[0078] As the cold cure mold foam method, a well-known method can
be adopted. For example, there is a method in which each component
such as a polyol, a foaming agent, a catalyst, a surfactant,
another auxiliary agent, and a crosslinker is previously mixed to
prepare a resin premix, and this resin premix is mixed with an
isocyanate compound using a high pressure foaming machine or a low
pressure foaming machine so that it comes to have a predetermined
NCO index, and the mixture is injected into a mold and is reacted
and cured to obtain a flexible polyurethane foam in a certain
shape. Here, the NCO index is the value obtained by dividing the
mol number of the isocyanate group contained in the isocyanate
compound by the active hydrogen group contained in the resin
premix. The value of the NCO index is not limited as long as a foam
is formed, but it is preferably 0.70 to 1.50 and is more preferably
0.80 to 1.25.
[0079] The reaction curing time is usually 30 seconds to 30
minutes, the mold temperature is usually room temperature to
approximately 80.degree. C., and the curing temperature is
preferably approximately 150.degree. C. Further, after the curing,
the cured material may be heated at 80 to 180.degree. C. as long as
the object of the present invention is not damaged.
[0080] The resin premix is usually mixed with the isocyanate
compound by a high pressure foaming machine or a low pressure
foaming machine. However, in the case where a hydrolyzable compound
such as an organic tin catalyst is used as a catalyst and the
foaming agent contains water, in order to prevent a contact with
the water, the water component and the organic tin component are
injected to a foaming machine in a different path and they are
mixed at a mixing head of the foaming machine.
[0081] According to the present invention, a flexible polyurethane
foam having a high resilience, a moderate hardness and an excellent
durability in a good balance can be obtained. In general, the
resilience, the hardness and the durability required to the
flexible polyurethane foam are different by the purpose. However,
the flexible polyurethane foam of the present invention is
preferably used for the purpose of cushion materials requiring a
high resilience, in particular for the purpose of seat cushions,
seat backs, instrument panels, headrests and armrests for vehicles
such as automobiles, for the purpose of bedding or furniture, and
for the purpose of clothes.
[0082] For example, in general, for the purpose of seat cushions
for vehicles such as automobiles whose core density is 30 to 75
kg/m.sup.3, the hardness (25% ILD) required to the flexible
polyurethane foam is preferably 140 to 350 N/314 cm.sup.2, and is
more preferably 175 to 330 N/314 cm.sup.2. Also, the resilience is
preferably 50 to 80%, is more preferably 55 to 77%, and is
particularly preferably 60 to 75%. Also, the durability (humid aged
compression set) is preferably 25% or less and is more preferably
19% or less.
EXAMPLE
[0083] As follows, the present invention is explained in detail by
the Examples, but the present invention is not limited to these
Examples. "Part(s)" and "%" in the Examples respectively represent
"part(s) by mass" and "mass %". The analyses and the measurements
in the Examples and the Comparative Examples were carried out
according to the following methods.
[Analyses and Measurements Regarding Polyol]
(1) Hydroxyl Value (OHV):
[0084] The hydroxyl value (mgKOH/g) was measured according to the
method described in JIS K 1557-1.
(2) Total Unsaturation Degree:
[0085] The total unsaturation degree was measured according to the
method described in JIS K 1557-3.
(3) Viscosity:
[0086] The viscosity (mPas/25.degree. C.) was measured using a
cone-plane rotational viscometer (E-type viscometer).
(4) Molecular Weight (Mp, Mw and Mn):
[0087] The molecular weight of the polyol in TABLE 1 to TABLE 3 was
measured under the following conditions using a GPC system produced
by TOSOH CORPORATION, and the standard polystyrene converted
molecular weight was obtained.
Equipment: HLC-8320 GPC,
[0088] Column: two TSK-GEL .alpha.-M (7.8 mm.times.300 mm), Eluent:
0.01 mol-LiBr/1000 ml-DMAc, Flow rate: 0.6 ml/min, Detector: RI
detector, and Column temperature: 40.degree. C.
[0089] The molecular weight of the polyol in TABLE 11 was measured
under the following conditions using a GPC system produced by TOSOH
CORPORATION, and the standard polystyrene converted molecular
weight was obtained.
Equipment: HLC-8320 GPC,
[0090] Column: two TSK-GEL .alpha.-M (7.8 mm.times.300 mm), Eluent:
0.01 mol-LiBr/1000 ml-DMF, Flow rate: 0.6 ml/min, Detector: RI
detector, and Column temperature: 40.degree. C.
(5) Molecular Weight Distribution (Mw/Mn):
[0091] This was obtained by calculation from the molecular weights
Mw and Mn measured by the above-mentioned method.
(6) Area Ratio (S1) of Base Polyol, Area Ratio (S2) of High
Molecular Weight Side, and Area Ratio (S3) of Lower Molecular
Weight Side:
[0092] As for the polyol in TABLE 1 to TABLE 3, the peaks in the
higher molecular weight side and the lower molecular weight side
than the peak of the base polyol were identified from the
measurement result by GPC. The boundary between the peak of the
base polyol and the peak of the higher molecular weight side was
assumed to be a minimum point in the higher molecular weight side
than the peak of the base polyol which was nearest to the peak of
the base polyol, and the boundary between the peak of the base
polyol and the peak of the lower molecular weight side was assumed
to be a minimum point in the lower molecular weight side than the
peak of the base polyol which was nearest to the peak of the base
polyol. When the total area of the peaks of the base polyol, the
higher molecular weight side and the lower molecular weight side
were 100, the area ratios of the peaks were respectively S1, S2 and
S3.
(7) Appearance:
[0093] The appearance of the polyether polyol was observed by
visual inspection at normal temperature, and the condition and
color were observed.
(8) Concentration of Residual Catalyst (mol %/Active Hydrogen):
[0094] The concentration of the residual catalyst is a
concentration of the residual cation in the polyol such as
tetrakis[tris(dimethylamino)phosphoranylideneamino]phosphonium
(hereinafter, referred to as PZN) or potassium to the active
hydrogen. If necessary, it was obtained as follow. In the case of
PZN, it was obtained by conducting a .sup.1H-NMR measurement using
a nuclear magnetic resonance apparatus AL-400 produced by JEOL data
Ltd. The chemical shift of the proton of the methyl group in PZN is
around 2.7 ppm, and the concentration can be calculated by a
comparison with a known concentration PZN and by a comparison with
the active hydrogen concentration of polyether polyol (A) and
polyol B-1. Also, in the case of a cation except PZN, the
concentration was obtained by conducting an analysis by a known
suitable method such as an ion chromatography, an ICP emission
analysis, or an elemental analysis.
(9) Primary Hydroxylate Ratio (Primary OH-Ate Ratio):
[0095] The primary hydroxylate ratio (%) was measured according to
the method described in JP 2000-344881 A.
(10) Moisture:
[0096] This was measured according to the method described in JIS K
1557-2.
(11) Charging Speed:
[0097] The charging speed of the alkylene oxide having a hydroxyl
group to the system was obtained as follows.
Charging speed=.gamma./(.alpha..times..beta.)
.gamma.: the charging speed of the alkylene oxide having a hydroxyl
group to the system (mol/Hrkg)=the mol number of the alkylene oxide
having a hydroxyl group which is charged in an hour in 1 kg of the
initiator which exists in the system .alpha.: the concentration of
the catalyst cation (mol/initiator OH)=the mol number of the cation
in 1 mol of OH contained in the polyol with a molecular weight of
2000 or more that is an initiator .beta.: the concentration of the
initiator OH (mol/kg)=the mol number of OH contained in 1 kg of the
initiator
[Analyses and Measurements Regarding Polyurethane Foam]
(12) Core Density (Density Core):
[0098] The surface skin was removed from the flexible polyurethane
foam sample to prepare a cuboid foam sample, and the core density
(kg/m.sup.3) was measured according to the method for measuring an
apparent density described in JIS K 7222.
(13) Hardness (25% ILD):
[0099] The hardness (N/314 cm.sup.2) of the flexible polyurethane
foam with a thickness of 100 mm was measured according to the D
method described in JIS K 6400-2.
(14) Tensile Strength:
[0100] The tensile strength [stress at the maximum point (kPa)] was
measured according to the method described in JIS K 6400-5.
(15) Elongation:
[0101] The elongation (%) was measured according to the method
described in JIS K 6400-5.
(16) Tear Strength:
[0102] The tear strength (N/cm) was measured according to the
method described in JIS K 6400-5.
(17) Humid Aged Compression Set (50% Wet Set):
[0103] The humid aged compression set (%) was measured according to
the method described in JIS K 6400-4. Specifically, a core part of
the flexible polyurethane foam molded was cut out to 50 mm.times.50
mm.times.25 mm to produce a specimen. This specimen was compressed
to the 50% thickness and was sandwiched between parallel plane
plates, and it was left as it was at 50.degree. C. under the
condition of the relative humidity of 95% for 22 hours. The
specimen was taken out and, 30 minutes later, the thickness was
measured and the distortion rate (%) was measured by comparing it
with the thickness before the test.
(18) Ball Rebound (Core):
[0104] The repulsion elastic modulus (%) was measured according to
the method described in JIS K 6400-3.
[0105] As follows, Example A of the first invention is
described.
Production of Polyol A
Examples A1 to A5
[0106] The base polyol (I) used for the present Example was
produced as follows. First, to an alcoholate obtained by adding
0.10 mol of KOH with respect to 1 mol of hydroxyl group in
propylene glycol (functional group number f=2), glycerin
(functional group number f=3) or pentaerythritol (functional group
number f=4) and by dehydrating it under a reduced pressure at
100.degree. C. for 6 hours, an addition polymerization of propylene
oxide (PO) was carried out in an autoclave at a reaction
temperature of 110.degree. C. under a maximum reaction pressure of
0.4 MPaG. Then, an addition polymerization of ethylene oxide (EO)
was carried out at a reaction temperature of 100.degree. C. under a
maximum reaction pressure of 0.4 MPaG so that the content of EO in
the whole came to be the value shown in TABLE 1, to obtain a crude
base polyol. 1.02 equivalents of phosphoric acid with respect to
potassium in this crude base polyol and 5 parts of water with
respect to 100 parts of the crude base polyol were added, and it
was neutralized at 90.degree. C. for 1 hour. Then, it was
dehydrated at 110.degree. C. under a reduced pressure so that the
water content came to be 500 ppm and the precipitated neutralized
salt was filtered to obtain the base polyol (I).
[0107] To an alcoholate which was obtained by supplying PZN so that
the catalyst cation concentration came to be .alpha. (mol/OH) with
respect to OH of this base polyol (I) and by dehydrating it under a
reduced pressure at 100.degree. C. for 6 hours, glycidol was
supplied under the conditions shown in TABLE 1 and an aging was
carried out to obtain polyols A1 to A5.
Examples A6 to A8
[0108] To an alcoholate which was obtained by adding 0.005 mol of
PZN with respect to 1 mol of glycerin and by dehydrating it under a
reduced pressure at 100.degree. C. for 6 hours, an addition
polymerization of PO was carried out in an autoclave at a reaction
temperature of 90.degree. C. under a maximum reaction pressure of
0.4 MPaG. Then, an addition polymerization of EO was carried out at
a reaction temperature of 100.degree. C. under a maximum reaction
pressure of 0.4 MPaG so that the content of EO in the whole came to
be the EO content in TABLE 1, to obtain polyol I-1 that was the
base polyol (I). The total unsaturation degree of this polyol I-1
was 0.020 meq/g, the hydroxyl value was 34 mgKOH/g, the residual
catalyst concentration was 0.18 mol %/active hydrogen. To this,
glycidol was supplied under the conditions shown in TABLE 1 and an
aging was carried out to obtain polyols A6 to A8.
Example A9
[0109] To an alcoholate which was obtained by supplying KOH so that
the catalyst cation concentration came to be .alpha. (mol/OH) with
respect to OH of the base polyol (I) shown in TABLE 2 and by
dehydrating it under a reduced pressure at 100.degree. C. for 6
hours, glycidol containing 1.68% of chlorohydrin as an impurity was
supplied and an aging was carried out to obtain polyol A9.
Example A10
[0110] To an alcoholate which was obtained by supplying KOH so that
the catalyst cation concentration came to be .alpha. (mol/OH) with
respect to OH of the base polyol (I) shown in TABLE 2 and by
dehydrating it under a reduced pressure at 100.degree. C. for 6
hours, glycidol containing 0.5% of chlorohydrin as an impurity was
supplied and an aging was carried out to obtain polyol A10.
Example A11
[0111] An alcoholate which was obtained by supplying KOH so that
the catalyst cation concentration came to be .alpha. (mol/OH) with
respect to OH of the base polyol (I) shown in TABLE 2 and by
dehydrating it under a reduced pressure at 100.degree. C. for 6
hours was heated to 110.degree. C. With maintaining the
temperature, glycidol containing 1.68% of chlorohydrin as an
impurity was supplied for 1 hour so that the Cl derived from
chlorohydrin came to be equivalent to the first supplied K and an
aging was carried out for 3 hours. After that, 3.64-fold amount of
96% KOH with respect to the amount of the first supplied KOH was
supplied and was heated to 110.degree. C., and it was dehydrated
under a reduced pressure for 4 hours. Then, with maintaining the
temperature, glycidol containing 1.68% of chlorohydrin as an
impurity was supplied for 3 hours so that the concentration of the
components derived from glycidol came to be 49%. After that, an
aging was further carried out at 110.degree. C. for 15 hours to
obtain polyol A11.
Example A12
[0112] An alcoholate, which was obtained by supplying KOH so that
the catalyst cation concentration came to be .alpha. (mol/OH) with
respect to OH of the base polyol (I) shown in TABLE 2 and by
dehydrating it under a reduced pressure at 100.degree. C. for 6
hours, was heated to 110.degree. C. With maintaining the
temperature, glycidol containing 0.5% of chlorohydrin as an
impurity was supplied for 4 hours so that the Cl derived from
chlorohydrin came to be equivalent to the first supplied K. After
that, 4.85-fold amount of 96% KOH with respect to the amount of the
first supplied KOH was supplied and was heated to 130.degree. C.,
and it was dehydrated under a reduced pressure for 4 hours. Then,
with maintaining the temperature, glycidol containing 0.5% of
chlorohydrin as an impurity was supplied for 6.7 hours so that the
concentration of the components derived from glycidol came to be
80%. After that, an aging was further carried out at 130.degree. C.
for 17 hours to obtain polyol A12.
Example A13
[0113] Polyol A6 was supplied to an autoclave and was heated to
120.degree. C., and 5 parts of ethylene oxide with respect to 100
parts of the polyol was charged for 7.6 hours with maintaining
120.degree. C. After that, the internal pressured reaction was
carried out at 120.degree. C. for 4.3 hours to obtain polyol
A13.
Example A14
[0114] To a four-necked flask of 100 ml equipped with a
thermometer, a stirrer, a nitrogen introduction tube and a monomer
drip line, polyol I-1 as the base polyol (I) was charged. Then, it
was heated to 100.degree. C., and glycidol (produced by Wako Pure
Chemical Industries, Ltd., for chemical use, the same applied
hereinafter) as alkylene oxide (II) was charged using a
proportioning pump at a speed so that the reaction temperature
could be maintained at 100.degree. C. In this regard, the mol ratio
of base polyol (I) and alkylene oxide (II) was set to be 1/7. Also,
the average functional group number calculated by the supplied
composition was 10. After that, an aging was carried out at
100.degree. C. for 5 hours to obtain polyol A14.
Example A15
[0115] Polyol A15 was obtained in the same manner as in A14 except
that the mol ratio of base polyol (I) and glycidol that was
alkylene oxide (II) was 1/21.
Comparative Examples A1 and A2
[0116] The base polyol (I) shown in TABLE 3 was evaluated without
reacting glycidol.
Comparative Examples A3 to A5
[0117] PZN or KCl was supplied so that the catalyst cation
concentration came to be .alpha. (mol/OH) with respect to OH of the
base polyol (I) shown in TABLE 3. After that, glycidol was added in
the amount shown in TABLE 3 and the reaction was carried out at
130.degree. C. for a time shown in TABLE 3 to obtain a polyol. The
polyols of Comparative Examples A4 and A5 was divided into two
layers.
Production of Flexible Polyurethane Foam
Examples A16 to A38 and Comparative Examples A6 to A15
[0118] First, using a raw material shown in TABLE 4 to TABLE 10, a
resin premix was prepared.
[0119] Polyol B1 was produced as follows. To an alcoholate which
was obtained by adding potassium hydroxide to glycerin in an amount
of 10 mol % per hydroxyl group and by dehydrating it under a
reduced pressure at 100.degree. C. for 6 hours, an addition
polymerization of propylene oxide was carried out in an autoclave
at a reaction temperature of 110.degree. C. under a maximum
reaction pressure of 0.4 MPaG. Then, an addition polymerization of
ethylene oxide was carried out at a reaction temperature of
100.degree. C. under a maximum reaction pressure of 0.4 MPaG so
that the ethylene oxide came to be 15% of the whole amount, to
obtain a crude polyol. 1.02 equivalents of phosphoric acid with
respect to potassium in this crude polyol and 5 parts of water with
respect to 100 parts of the crude polyol were added, and it was
neutralized at 90.degree. C. for 1 hour. Then, it was dehydrated at
110.degree. C. under a reduced pressure so that the water content
came to be 500 ppm and the precipitated neutralized salt was
filtered to obtain polyol B1 with a hydroxyl value of 28 mgKOH/g
and a total unsaturation degree of 0.07 meq/g.
[0120] Polyol B2 was produced as follows. First, polyol B4 with a
hydroxyl value of 34 mgKOH/g was obtained in the same manner as in
above-mentioned polyol B1 except that ethylene oxide was reacted so
that the ethylene oxide came to be 14% of the whole amount. This
polyol B4 was supplied to a pressure-resistant autoclave of 1 liter
equipped with a thermometer, a stirring apparatus, a pressure gauge
and a liquid sending apparatus so that the autoclave was filled up
with the polyol, and it was heated to 120.degree. C. with stirring.
Further, a mixture liquid of 79.4 parts of polyol B4, 1 part of
2,2'-azobisisobutyronitrile that is a radical polymerization
initiator, and 16.5 parts of acrylonitrile and 4.1 parts styrene
(acrylonitrile/styrene=80/20 mass ratio, total amount of
acrylonitrile and styrene: 20.6 parts) was continuously charged to
this autoclave under the conditions of a reaction temperature of
120.degree. C., of a reaction pressure of 0.4 MPaG, and of a
staying time of 50 minutes, to polymerize the acrylonitrile and the
styrene in polyol B4. And, an initial fraction was removed so that
a polymer came to be uniformly dispersed in a reaction liquid which
was continuously exhausted from the outlet, to obtain the reaction
liquid exhausted. This reaction liquid was continuously heated
under a reduced pressure under the conditions of 120.degree. C. and
0.7 kPaG or less, and an unreacted acrylonitrile, styrene and a
decomposition material of the radical polymerization were removed
to obtain polyol B2 with a hydroxyl value of 28 mgKOH/g. When the
residual amount of acrylonitrile and styrene remaining in polyol B2
before heating under a reduced pressure was measured by gas
chromatography, the content of the vinyl polymer contained in
polyol B2 was 20%.
[0121] Polyol B3 was produced as follows. Polyol B4 was supplied to
a pressure-resistant autoclave of 1 liter equipped with a
thermometer, a stirring apparatus, a pressure gauge and a liquid
sending apparatus so that the autoclave was filled up with the
polyol, and it was heated to 120.degree. C. with stirring. Further,
a mixture liquid of 69.4 parts of polyol B4, 1 part of
2,2'-azobisisobutyronitrile that is a radical polymerization
initiator, and 30.6 parts of acrylonitrile was continuously charged
to this autoclave under the conditions of a reaction temperature of
120.degree. C., of a reaction pressure of 0.4 MPaG, and of a
staying time of 50 minutes, to polymerize the acrylonitrile in
polyol B4. An initial fraction was removed so that a polymer came
to be uniformly dispersed in a reaction liquid which was
continuously exhausted from the outlet, to obtain the reaction
liquid exhausted. This reaction liquid was continuously heated
under a reduced pressure under the conditions of 120.degree. C. and
0.7 kPaG or less, and an unreacted acrylonitrile and a
decomposition material of the radical polymerization were removed
to obtain polyol B3 with a hydroxyl value of 23 mgKOH/g. When the
residual amount of acrylonitrile remaining in polyol B3 before
heating under a reduced pressure was measured by gas
chromatography, the content of the vinyl polymer contained in
polyol B3 was 30%.
[0122] Cell opener-1 used was produced as follows. First, potassium
hydroxide was added in an amount of 0.1 mol per 1 mol of hydroxyl
group contained in glycerin and it was dehydrated under a reduced
pressure at 100.degree. C. for 6 hours. After that, an addition
polymerization of 14% of ethylene oxide was carried out in an
autoclave at a reaction temperature of 115.degree. C. under a
maximum reaction pressure of 0.4 MPaG. Then, an addition
polymerization of 30% of propylene oxide and 56% of ethylene oxide
was carried out at a reaction temperature of 115.degree. C. under a
maximum reaction pressure of 0.5 MPaG, and a neutralization,
dehydration and filtration steps were carried out by the same
operation as in polyol B1 to obtain cell opener-1. The hydroxyl
value of this cell opener-1 was 50 mgKOH/g, and the content of
ethylene oxide (EO) was 70% from the supplied ratio.
[0123] Crosslinker-1 used was produced as follows. First, potassium
hydroxide was added in an amount of 0.37 mol per 1.2 mol of
pentaerythritol and 1 mol of diglycerin and it was dehydrated under
a reduced pressure at 100.degree. C. for 6 hours. After that, an
addition polymerization of 100% of ethylene oxide was carried out
in an autoclave at a reaction temperature of 115.degree. C. under a
maximum reaction pressure of 0.4 MPaG. Then, a neutralization,
dehydration and filtration were carried out in the same manner as
in cell opener-1, and 25% of diethanolamine was mixed. The hydroxyl
value of this crosslinker-1 was 840 mgKOH/g.
[0124] The foaming agent used was water, catalyst-1 used was MINICO
TMDA (trade name) produced by Katsuzai-Chemical Corporation,
catalyst-2 used was MINICO L-1020 (trade name) produced by
Katsuzai-Chemical Corporation, surfactant-1 uses was SZ-1966 (trade
name) produced by Dow Corning Toray Co., Ltd., surfactant-2 uses
was L-5309 (trade name) produced by Momentive Performance Materials
Japan limited liability company, surfactant-3 uses was SZ-1966
(trade name) produced by Dow Corning Toray Co., Ltd., surfactant-4
uses was DABCO DC-2525 (trade name) produced by Air Products Japan,
Inc., and surfactant-5 uses was DABCO DC-6070 (trade name) produced
by Air Products Japan, Inc.
[0125] And, a resin premix of these was mixed with an isocyanate
compound (produced by Mitsui Chemicals, Inc., trade name:
COSMONATE.TM.-20) in an NCO index of 1.00. It was promptly injected
to a mold (inside size: 400 mm.times.400 mm.times.100 mm) at
63.degree. C., and the lid was closed to foam it. The curing
reaction proceeded for 6 minutes with keeping the mold temperature
of 63.degree. C. and the demolding from the mold was carried out to
obtain a flexible polyurethane foam.
[0126] From the results shown in TABLE 4 to TABLE 10, it is found
that the polyol (A) of each Example can maintain or improve the
hardness of the flexible polyurethane foam and can maintain the
ball rebound or the compression set that is an indicator of
durability in a good balance.
TABLE-US-00001 TABLE 1 Ex. A1 Ex. A2 Ex. A3 Ex. A4 Ex. A5 Ex. A6
Ex. A7 Ex. A8 Base Polyol f 2 2 3 4 4 3 3 3 (I) Calculated Mn 3000
3000 5000 6600 6600 5000 5000 5000 Content of EO (wt %) 20 20 15 15
15 14 14 14 Alkylene Calculated Functional Group 20 12.5 20 20 26.3
20 6.5 270 Oxide Number (II) Glycidol (wt %) 30.1 20 20.3 15.2 20
20 5 80 Ratio of Glycidol in Alkylene 100 100 100 100 100 100 100
100 Oxide (II) (wt %) AO/Glycidol Ratio in Polyol 75.3/24.7
84.0/16.0 83.8/16.2 88.0/12.0 84.0/16.0 84.2/15.8 96.2/3.8
24.7/75.3 Catalyst PZN PZN PZN PZN PZN PZN PZN PZN Reaction
Temperature 130 130 130 130 130 110 110 110 Charging Time of
Glycidol 2 2 2 2 2 2 0.5 8 Aging Time 4 4 4 4 4.4 8 6.5 20 Analyzed
OHV(mgKOH/g) 238.7 169.3 171.3 132.6 166.8 174.2 68.2 602.1 Values
Viscosity (mPa s/25.degree. C.) 1660 1180 1660 1610 1880 1990 1150
200000 Mw/Mn 12.3 11.5 10.9 14.6 9.6 10.3 11.0 12.0 High Molecular
Weight Side (S2) 29.00 22.34 21.03 19.90 19.84 6.69 1.10 0.00 Low
Molecular Weight Side (S3) 5.00 4.83 12.15 7.07 8.18 21.72 6.10
79.20 S1 66.00 72.83 66.82 73.03 71.98 71.59 92.80 20.80 S1/S2
69.5/30.5 76.5/23.5 76.1/23.9 78.6/21.4 78.4/21.6 91.5/8.5 98.8/1.2
100/0 Charging .alpha.: Concentration of Catalyst 0.0015 0.0013
0.0014 0.0013 0.0014 0.0018 0.0018 0.0018 Speed Cation
(mol/Initiator OH) .beta.: Concentration of Initiator OH 0.67 0.67
0.60 0.61 0.61 0.60 0.60 0.60 (mol/kg) .gamma.: Charging Speed of
Glycidol 3.00 1.69 1.72 1.21 1.69 1.72 1.42 13.51 (mol/Hr kg)
.gamma./(.alpha. * .beta.) 3000 1950 2048 1536 1992 1593 1315
12509
TABLE-US-00002 TABLE 2 Ex. A9 Ex. A10 Ex. A11 Ex. A12 Ex. A13 Ex.
A14 Ex. A15 Base f 3 3 3 3 3 3 3 Polyol Calculated Mn 6000 6000
6000 6000 5000 5000 5000 (I) Content of EO (wt %) 15 15 15 15 14 14
14 Alkylene Calculated Functional Group 23 51 51 328 20 10 24 Oxide
Number (II) Glycidol (wt %) 20 49 49 80 19.2 9.5 23.7 Ratio of
Glycidol in Alkylene 100 100 100 100 80.9 100 100 Oxide (II) (wt %)
AO/Glycidol Ratio in Polyol 84.1/15.9 58.3/41.7 58.3/41.7 24.8/75.2
85.1/14.9 92.7/7.3 84.2/15.8 Catalyst K K K K PZN PZN PZN Reaction
Temperature 130 110 110 110 130 120 100 100 Charging Time of
Glycidol 2 4 4 4 8 7.5 2 2 Aging Time 6.5 30 15 17 4 5 5 Analyzed
OHV(mgKOH/g) 166.2 356.4 361.2 563.2 158.2 102.9 178 Values
Viscosity (mPa s/25.degree. C.) 3240 10300 9410 200000 1880 1240
1800 Mw/Mn 25.7 13.9 14.4 378.0 28.4 15.6 10.3 High Molecular 22.69
42.98 45.76 57.40 23.13 2.94 9.21 Weight Side (S2) Low Molecular
8.48 8.57 5.36 20.00 11.63 9.80 20.34 Weight Side (S3) S1 68.83
48.46 48.88 22.60 65.24 87.26 70.45 S1/S2 75.2/24.8 53.0/47.0
51.6/48.4 28.3/71.7 73.8/26.2 96.7/3.3 88.4/11.6 Charging .alpha.:
Concentration of Catalyst 0.0829 0.0829 0.0829 0.0829 0.0018 0.0018
0.0018 Speed Cation (mol/Initiator OH) .beta.: Concentration of
0.50 0.50 0.50 0.50 0.60 0.60 0.60 Initiator OH (mol/kg) .gamma.:
Charging Speed of 1.66 3.18 3.18 3.18 1.72 1.41 2.04 Glycidol
(mol/Hr kg) .gamma./(.alpha. * .beta.) 40 77 77 77 1593 1306 1889
The charging speeds in the first 1 Hr and in the following 3 Hr are
different.
TABLE-US-00003 TABLE 3 Comp. Comp. Comp. Comp. Comp. Ex. A1 Ex. A2
Ex. A3 Ex. A4 Ex. A5 Base Polyol f 3 3 3 3 3 (I) Calculated Mn 5000
6000 92 6000 6000 Content of EO (wt %) 14 15 0 15 15 Calculated
Functional Group Number 3 3 20 23 23 Alkylene Oxide Glycidol (wt %)
0 0 41.3 20 20 (II) Ratio of Glycidol in Alkylene Oxide -- -- 42.7
100 100 (II) (wt %) AO/Glycidol Ratio in Polyol 100/0 100/0
69.6/30.4 84.1/15.9 84.1/15.9 Catalyst PZN K PZN KCI KCI Reaction
Temperature -- -- 120 130 130 Charging Time of Glycidol -- -- 4 at
once at once Aging Time -- -- 6 6.5 17 Analyzed Values OHV(mgKOH/g)
34 28 382 167.3 165.8 Viscosity (mPa s/25.degree. C.) 900 1200 6600
unmeasurable unmeasurable Mw/Mn 1.4 1.7 2.1 3.3 2.9 High Molecular
Weight Side (S2) 0.00 0.00 0.00 0.00 0.00 Low Molecular Weight Side
(S3) 0.87 7.73 0.00 15.89 12.98 S1 99.13 92.27 100.00 84.11 87.02
S1/S2 100/0 100/0 100/0 100/0 100/0 Charging Speed .alpha.:
Concentration of Catalyst Cation 0.0018 0.0829 0.0028 0.0829 0.0083
(mol/Initiator OH) .beta.: Concentration of Initiator OH (mol/kg)
0.60 0.50 32.61 0.50 0.50 .gamma.: Charging Speed of Glycidol
(mol/Hr kg) -- -- 184.50 at once at once .gamma./(.alpha. *
(.beta.) 2050
TABLE-US-00004 TABLE 4 comp. Ex. A16 Ex. A17 Ex. A18 Ex. A19 Ex.
A20 Ex. A6 Polyol B1 60 60 60 60 60 70 Polyol B3 30 30 30 30 30 30
Polyol (Ex. A1) 10 Polyol (Ex. A2) 10 Polyol (Ex. A3) 10 Polyol
(Ex. A4) 10 Polyol (Ex. A5) 10 Crosslinker-1 3.0 3.0 3.0 3.0 3.0
3.0 H2O 4.1 4.1 4.1 4.1 4.1 4.1 Catalyst-1 0.1 0.1 0.1 0.1 0.1 0.1
Catalyst-2 0.4 0.4 0.4 0.4 0.4 0.4 Surfactant-3 0.6 0.6 0.6 0.6 0.6
0.6 TOTAL 108.2 108.2 108.2 108.2 108.2 108.2 Mass % of Polyol A
11.1 11.1 11.1 11.1 11.1 0.0 with respect to 100 of Polyol B
Density: Core (kg/m3) 37.2 37.2 37.1 36.9 37.2 37.5 25% ILD(N/314
cm2) 211 196 189 184 192 160 Tensile Strength (kPa) 151 139 141 121
124 145 Elongation ( % ) 94 94 98 93 91 113 Tear Strength (N/cm)
4.6 5.1 4.9 4.5 5.2 4.8 50% Wet Set (%) 13.0 13.2 13.2 13.1 13.5
14.7 Ball Rebound: Core (%) 66 67 67 69 68 69
TABLE-US-00005 TABLE 5 Comp. Comp. Comp. Ex. A21 Ex. A22 Ex. A23
Ex. A7 Ex. A8 Ex. A9 Polyol B1 60 66 66 50 70 66 Polyol B3 30 30 30
50 30 30 Polyol (Ex. A9) 10 Polyol (Ex. A10) 4 Polyol (Ex. A11) 4
Polyol (Comp. Ex. A4) . 4 Cell Opener-1 1 Crosslinker-1 1.5 1.5 1.5
1.5 1.5 1.5 H2O 4.1 4.1 4.1 4.1 4.1 4.1 Catalyst -1 0.1 0.1 0.1 0.1
0.1 0.1 Catalyst-2 0.4 0.4 0.4 0.4 0.4 0.4 Surfactant-3 0.6 0.6 0.6
0.6 0.6 Surfactant-4 0.2 Surfactant-5 0.8 TOTAL 106.7 106.7 106.7
108.1 106.7 106.7 Mass % of Polyol A 11.1 4.2 4.2 0.0 0.0 4.2 with
respect to 100 of Polyol B Density: Core (kg/m3) 36.9 37.2 37.2
37.1 37.0 The polyol 25% ILD(N/314 cm2) 197 187 185 196 162 was
separated Tensile Strength (kPa) 182 166 150 200 173 and a foam
Elongation ( % ) 114 110 100 120 124 body was not Tear Strength
(N/cm) 5.2 5.3 5.2 6.8 6.5 obtained. 50% Wet Set (%) 18.4 21.2 17.6
23.6 25.9 Ball Rebound: Core (%) 68 67 67 65 66
TABLE-US-00006 TABLE 6 Comp. Ex. A24 Ex. A25 Ex. A26 Ex. A27 Ex.
A10 Polyol B1 66 30 67.5 67.5 70 Polyol B3 30 30 30 30 30 Polyol
(Ex. A11) 4 Polyol (Ex. A7) 40 Polyol (Ex. A12) 2.5 Polyol (Ex. A8)
2.5 Crosslinker-1 1.5 1.5 1.5 1.5 1.5 H2O 4.1 4.1 4.1 4.1 4.1
Catalyst-1 0.1 0.1 0.1 0.1 0.1 Catalyst-2 0.4 0.4 0.4 0.4 0.4
Surfactant-3 0.6 0.6 0.6 0.6 0.6 TOTAL 106.7 106.7 106.7 106.7
106.7 Mass % of Polyol A 4.2 66.7 2.6 2.6 0.0 with respect to 100
of Polyol B Density: Core (kg/m3) 37.2 38.2 37.4 37.8 40.1 25%
ILD(N/314 cm2) 185 193 181 165 158 Tensile Strength (kPa) 150 161
165 152 162 Elongation (%) 100 94 109 101 119 Tear Strength (N/cm)
5.2 6.3 6.2 6.0 7.2 50% Wet Set (%) 17.6 16.9 18.1 14.8 21.8 Ball
Rebound: Core (%) 67 66 66 67 66
TABLE-US-00007 TABLE 7 Comp. Ex. A28 Ex. A29 Ex. A11 Polyol B1 60
59.5 70 Polyol B3 30 30 30 Polyol (Ex. A6) 10 Polyol (Ex. A13) 10.5
Cross linker-1 1.5 1.5 1.5 H2O 4.1 4.1 4.1 Catalyst-1 0.1 0.1 0.1
Catalyst-2 0.4 0.4 0.4 Surfactant-3 0.6 0.6 0.6 TOTAL 106.7 106.7
106.7 Mass % of Polyol A 11.1 11.7 0.0 with respect to 100 of
Polyol B Density: Core (kg/m3) 38.2 40.0 40.1 25% ILD(N/314 cm2)
189 183 158 Tensile Strength (kPa) 163 159 162 Elongation (%) 98
105 119 Tear Strength (N/cm) 5.4 5.1 7.2 50% Wet Set (%) 16.9 16.5
21.8 Ball Rebound: Core (%) 65 66 66
TABLE-US-00008 TABLE 8 Comp. Ex. A30 Ex. A31 Ex. A32 Ex. A33 Ex.
A12 Polyol B1 60 45 66 60 70 Polyol B3 30 30 30 30 30 Polyol (Ex.
A6) 10 25 Polyol (Ex. A10) 4 10 Crosslinker-1 1.5 1.5 1.5 1.5 1.5
H2O 4.1 4.1 4.1 4.1 4.1 Catalyst-1 0.1 0.1 0.1 0.1 0.1 Catalyst-2
0.4 0.4 0.4 0.4 0.4 Surfactant-3 0.6 1.0 0.6 1.0 0.6 TOTAL 106.7
107.1 106.7 107.1 106.7 Concentration of 2.0 5.0 2.0 5.0 0.0
Glycidol Body in Polyol Density: Core (kg/m3) 37.2 36.8 37.3 36.7
40.1 25% ILD(N/314 cm2) 183 209 194 217 158 Tensile Strength (kPa)
170 181 160 146 162 Elongation (%) 111 99 106 91 119 Tear Strength
(N/cm) 5.9 5.8 6.1 4.5 7.2 50% Wet Set (%) 16.5 15.2 18.8 18.1 21.8
Ball Rebound: Core (%) 66 65 66 65 66
TABLE-US-00009 TABLE 9 Comp. Comp. Ex. A34 Ex. A35 Ex. A36 Ex. A13
Ex. A14 Polyol B1 30 45 60 30 30 Polyol B2 60 45 30 70 70 Polyol
(Ex. A15) 10 10 10 Polyol (Comp. Ex. A3) 2 Cell Opener-1 1.0 1.0
1.0 1.0 1.0 Crosslinker-1 2.0 2.0 2.0 2.0 2.0 H2O 3.5 3.5 3.5 3.5
3.5 Catalyst-1 0.1 0.1 0.1 0.1 0.1 Catalyst-2 0.4 0.4 0.4 0.4 0.4
Surfactant-1 1.0 Surfactant-2 1.0 1.0 1.0 1.0 TOTAL 108.0 108.0
108.0 108.0 110.0 Mass % of Polyol A 11.1 11.1 11.1 0.0 0.0 with
respect to 100 of Polyol B Density: Core (kg/m3) 46.9 47.1 46.4
44.5 45.0 25% ILD(N/314 cm2) 243 220 192 212 174 Tensile Strength
(kPa) 190 160 153 209 181 Elongation (%) 103 101 105 112 111 Tear
Strength (N/cm) 6.2 5.5 4.9 7.2 6.6 50% Wet Set (%) 15.8 12.0 11.3
16.9 16.5 Ball Rebound: Core (%) 69 70 73 67 67
TABLE-US-00010 TABLE 10 Comp. Ex. A37 Ex. A38 Ex. A15 Polyol B1 50
65 50 Polyol B3 30 15 50 Polyol (Ex. A15) 20 Polyol (Ex. A14) 20
Cell Opener-1 2 1 1 Crosslinker-1 2 2 3 H2O 4.1 4.1 4.1 Catalyst-1
0.05 0.05 0.1 Catalyst-2 0.45 0.45 0.4 Surfactant-3 0.7 0.7
Surfactant-4 0.2 Surfactant-5 0.8 TOTAL 109.3 108.3 109.6 Mass % of
Polyol A 25 25 0 with respect to 100 of Polyol B Density: Core
(kg/m3) 37.8 38.0 37.5 25% ILD(N/314 cm2) 181 176 185 Tensile
Strength (kPa) 92 88 132 Elongation (%) 80 88 104 Tear Strength
(N/cm) 4.0 3.7 5.2 50% Wet Set (%) 15.1 12.1 17.1 Ball Rebound:
Core (%) 70 70 67
[0127] Next, Example a of the second invention is described.
Example a1
[0128] To an alcoholate obtained by adding 0.005 mol of PZN with
respect to 1 mol of glycerin and by dehydrating it under a reduced
pressure at 100.degree. C. for 6 hours, an addition polymerization
of propylene oxide was carried out in an autoclave at a reaction
temperature of 90.degree. C. under a maximum reaction pressure of
0.4 MPaG. Then, an addition polymerization of ethylene oxide was
carried out at a reaction temperature of 100.degree. C. under a
maximum reaction pressure of 0.4 MPaG so that ethylene oxide in the
whole came to be 14%, to obtain polyol i-1. The total unsaturation
degree of this polyol i-1 was 0.020 meq/g, the hydroxyl value was
34 mgKOH/g, and the residual catalyst concentration was 0.18 mol
%/active hydrogen.
[0129] To a four-necked flask of 100 ml equipped with a
thermometer, a stirrer, a nitrogen introduction tube and a monomer
drip line, 76.0 parts of polyol i-1 as active hydrogen compound (i)
was charged. Then, it was heated to 100.degree. C., and 24.1 parts
of glycidol (produced by Wako Pure Chemical Industries, Ltd., for
chemical use, the same applied hereinafter) as alkylene oxide (ii)
was charged using a proportioning pump at a speed so that the
reaction temperature could be maintained at 100.degree. C. In this
alkylene oxide (ii), the mol ratio of glycidol and alkylene oxide
except for glycidol was 100/0, and the mol ratio of active hydrogen
compound (i) and alkylene oxide (ii) was 1/21, and the average
functional group number calculated by the supplied composition was
24. After that, an aging was carried out at 100.degree. C. for 5
hours to obtain polyol a1.
Examples a2 to a11
[0130] Polyols a2 to all were obtained by changing active hydrogen
compound (i) and alkylene oxide (ii) as shown in TABLE 11.
[0131] Example a2 is an example which is the same as Example A14 of
the first invention. In Examples a3 to a6, a7 and a9, the whole
amount of the prepared glycerin and the prepared catalyst were
charged to the four-necked flask of 100 ml and it was dehydrated
under a reduced pressure at 100.degree. C. for 5 hours, and
glycidol was then charged. After that, the reaction was carried out
in the same operation as that of polyol a1. Also, in the production
in Examples a1 to a6, a phosphazenium salt compound was used as a
basic compound, but was used for the production of a flexible
polyurethane foam without carrying out the decatalyst step.
[0132] Example a8 is an example in which glycidol uses as alkylene
oxide (ii) was also used as active hydrogen compound (i). Also,
Example a10 is an example in which alkylene oxide (ii) and
propylene oxide (PO) were copolymerized, and Example all is an
example in which alkylene oxide (ii) and ethylene oxide (EO) were
copolymerized.
Comparative Examples a1 to a4
[0133] As shown in TABLE 11, properties of polyglycerins 06, 10 and
X produced by Daicel Corporation are shown for comparison. These
have a primary hydroxylate ratio that is too high.
Production of Flexible Polyurethane Foam
Examples a12 to a25 and Comparative Examples a5 to a12
[0134] First, using a raw material shown in TABLE 12 to TABLE 14, a
resin premix was prepared. Each component used such as the cell
opener was the same as that of Example A. Polyols b1, b2 and b3
used were the same as polyols B1, B2 and B3.
[0135] Polyol a4 is the same as that of Comparative Example A3.
[0136] And, a resin premix of these was mixed with an isocyanate
compound (produced by Mitsui Chemicals, Inc., trade name:
COSMONATE.TM.-20) in an NCO index of 1.00. It was promptly injected
to a mold (inside size: 400 mm.times.400 mm.times.100 mm) at
60.degree. C., and the lid was closed to foam it. The curing
reaction proceeded for 8 minutes with keeping the mold temperature
of 60.degree. C. and the demolding from the mold was carried out to
obtain a flexible polyurethane foam.
[0137] From the results shown in TABLE 12 to TABLE 14, it is found
that the polyol (a) of each Example can improve the hardness of the
flexible polyurethane foam without lowering the durability and the
ball rebound. In particular, when compared to each Comparative
Example where the primary OH-ate ratio is larger than 60%, the
effect of improving the hardness developing and the Wet Set is
large in each Example. Also, it is found that the effect of
improving the hardness and the Wet Set is large if the primary
OH-ate ratio is 25 to 60% even if EO and PO are copolymerized.
[0138] On the other hand, the flexible polyurethane polyol of
Comparative Example a5 is known as a prior art. Herein, although
the used amount of the polymer dispersed polyol as an polyol is
adjusted to improve the hardness of the flexible polyurethane foam,
the balance with the 50% Wet Set and the ball rebound core is not
sufficient. Also, Comparative Examples a9 to all are a prior art
which intends to improve the hardness by a crosslinker described in
BACKGROUND ART. Herein, it is found not only that the foam hardness
is not largely improved, but also that 50% Wet Set was largely
reduced.
TABLE-US-00011 TABLE 11 Ex. a1 Ex. a2 Ex. a3 Ex. a4 Ex. a5 Ex. a6
Ex. a7 Ex. a8 Active Kind Polyol Polyol Glycerin Glycerin Glycerin
Glycerin Glycerin non Hydrogen i-1 i-1 Compound Average Functional
Group (i) Number of Active Hydrogen 3 3 3 3 3 3 3 0 Compound
Alkylene Added Mol Number of Glycidol 21 7 5 30 154 671 9 1 Oxide
with respect to Active Hydrogen (ii) Compound (x) Alkylene Oxide
other than -- -- -- -- -- -- -- -- Glycidol Added Mol Number of the
above -- -- -- -- -- -- -- -- (y) (x)/(x) + (y) (mol %) 100 100 100
100 100 100 100 100 Average Number of Functional Groups 24 10 8 33
157 674 12 2 OHV(mgKOH/g) 178 103 962 795 738 735 862 743 Viscosity
(mPa s/25.degree. C.) 1,800 1,200 no flow- no flow- no flow- no
flow- no flow- no flow- ability ability ability ability ability
ability Molecular Weight Mp 7,080 6,880 440 1,580 9,060 23,000 752
956 Molecular Weight Mn 910 1,490 140 380 940 600 248 256 Molecular
Weight Mw 8,230 7,460 470 1,480 7,340 15,500 769 1,240 Molecular
Weight Distribution Mw/Mn 9.0 5.0 3.4 3.9 7.8 25.8 3.1 4.8 Average
Number of Functional Groups 22.5 12.6 8 22 119 301 12 13 Calculated
by HOV and Mp Appearance white white pale slightly slightly liquid
liquid yellow turbid turbid trans- liquid liquid parent liquid
Primary OH-ate Ratio (%) 50.8 56.4 48.8 46.4 46.4 46.2 47.4 45.5
Comp. Comp. Comp. Comp. Ex. a9 Ex. a10 Ex. a11 Ex. a1 Ex. a2 Ex. a3
Ex. a4 Active Kind Glycerin Glycerin Glycerin Polygly- Polygly-
Polygly- Glycerin Hydrogen cerin 06 cerin 10 cerin X Compound
Average Functional Group (i) Number of Active Hydrogen 3 3 3 3 3 3
3 Compound Alkylene Added Mol Number of Glycidol 17 17 17 -- -- --
17 Oxide with respect to Active Hydrogen (ii) Compound (x) Alkylene
Oxide other than -- PO EO EO Glycidol Added Mol Number of the above
-- 8.8 11.2 -- -- -- 39.0 (y) (x)/(x) + (y) (mol %) 100 65.9 60.3
-- -- -- 30.4 Average Number of Functional Groups 20 20 20 8 12 22
20 OHV(mgKOH/g) 815 626 649 951 867 756 382 Viscosity (mPa
s/25.degree. C.) no flow- no flow- 94,800 no flow- no flow- no
flow- 6,600 ability ability ability ability ability Molecular
Weight Mp 1,250 1,930 1,690 530 830 3,140 2,860 Molecular Weight Mn
421 332 598 200 280 580 1,290 Molecular Weight Mw 1,210 1,750 1,650
530 850 3,210 2,610 Molecular Weight Distribution Mw/Mn 2.9 5.3 2.8
2.7 3.0 5.5 2.0 Average Number of Functional Groups 18 22 20 9 13
42 20 Calculated by HOV and Mp Appearance pale slightly slightly
white trans- trans- pale yellow turbid turbid parent parent yellow
trans- liquid liquid viscous trans- parent liquid parent liquid
Primary OH-ate Ratio (%) 46.7 29.2 59.3 64.8 64.7 65.1 82.7 Average
functional group number is the number of the active hydrogen group
in the molecule, and is represented by an intege value by rounding
off the number. 1The value cannot be calculated because glycidol pe
se is (i). 2It cannot be calculated because there is not a mol
ratio of (i)/glycidol.
TABLE-US-00012 TABLE 12 Comp. Comp. Ex. a12 Ex. a13 Ex. a14 Ex. a5
Ex. a6 Polyol b1 30 45 60 30 30 Polyol b2 60 45 30 70 70 Polyol
(Ex. a1) 10 10 10 Polyol (Comp. Ex. a4) 2 Cell Opener-1 1.0 1.0 1.0
1.0 1.0 Crosslinker-1 2.0 2.0 2.0 2.0 2.0 H2O 3.5 3.5 3.5 3.5 3.5
Catalyst-1 0.1 0.1 0.1 0.1 0.1 Catalyst-2 0.4 0.4 0.4 0.4 0.4
Surfactant-1 1.0 Surfactant-2 1.0 1.0 1.0 1.0 TOTAL 108.0 108.0
108.0 108.0 110.0 Mass % of Polyol a 11.1 11.1 11.1 0.0 0.0 with
respect to 100 of Polyol b Density: Core (kg/m3) 46.9 47.1 46.4
44.5 45.0 25% ILD(N/314 cm2) 243 220 192 212 174 Tensile Strength
(kPa) 190 160 153 209 181 Elongation (%) 103 101 105 112 111 Tear
Strength (N/cm) 6.2 5.5 4.9 7.2 6.6 50% Wet Set (%) 15.8 12.0 11.3
16.9 16.5 Ball Rebound: Core (%) 69 70 73 67 67
TABLE-US-00013 TABLE 13 Comp. Ex. a15 Ex. a16 Ex. a7 Polyol b1 50
65 50 Polyol b3 30 15 50 Polyol (Ex. a1) 20 Polyol (Ex. a2) 20 Cell
Opener-1 2 1 1 Crosslinker-1 2 2 3 H2O 4.1 4.1 4.1 Catalyst-1 0.05
0.05 0.1 Catalyst-2 0.45 0.45 0.4 Surfactant-3 0.7 0.7 Surfactant-4
0.2 Surfactant-5 0.8 TOTAL 109.3 108.3 109.6 Mass % of Polyol a 25
25 0 with respect to 100 of Polyol b Density: Core (kg/m3) 37.8
38.0 37.5 25% ILD(N/314 cm2) 181 176 185 Tensile Strength (kPa) 92
88 132 Elongation (%) 80 88 104 Tear Strength (N/cm) 4.0 3.7 5.2
50% Wet Set (%) 15.1 12.1 17.1 Ball Rebound: Core (%) 70 70 67
TABLE-US-00014 TABLE 14 Ex. Ex. Ex. Ex. Ex. Ex. Ex. Ex. Ex. Comp.
Comp. Comp. Comp. Comp. a17 a18 a19 a20 a21 a22 a23 a24 a25 Ex. a8
Ex. a9 Ex. a10 Ex. a11 Ex. a12 Polyol b1 50 50 50 50 70 70 70 70 70
50 50 50 50 70 Polyol b3 50 50 50 50 30 30 30 30 30 50 50 50 50 30
Polyol (Ex. a3) 4 Polyol (Ex. a4) 4 Polyol (Ex. a5) 4 Polyol (Ex.
a6) 4 Polyol (Ex. a7) 2 Polyol (Ex. a8) 2 Polyol (Ex. a9) 2 Polyol
(Ex. a10) 2 Polyol (Ex. a11) 2 Polyglycerin 06 4 (Comp. Ex. a1)
Polyglycerin 10 4 (Comp. Ex. a2) Polyglycerin X 4 (Comp. Ex. a3)
Cell Openert-1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 Crosslinker-1 3 3 3 3
1.5 1.5 1.5 1.5 1.5 3 3 3 3 1.5 H2O 4.1 4.1 4.1 4.1 4.1 4.1 4.1 4.1
4.1 4.1 4.1 4.1 4.1 4.1 Catalyst-1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1
0.1 0.1 0.1 0.1 0.1 0.1 Catalyst-2 0.4 0.4 0.4 0.4 0.4 0.4 0.4 0.4
0.4 0.4 0.4 0.4 0.4 0.4 Surfactant-3 0.7 0.7 0.7 0.7 0.6 0.6 0.6
0.6 0.6 0.7 1.2 1.2 1.2 0.6 TOTAL 113.3 113.3 113.3 113.3 109.7
109.7 109.7 109.7 109.7 109.3 113.8 113.8 113.8 107.7 Mass % of
Polyol 4 4 4 4 2 2 2 2 2 0 4 4 4 0 a with respect to 100 of Polyol
b Density: Core 39.0 38.8 38.5 38.8 36.8 38.4 38.3 38.3 38.5 38.8
38.5 38.9 38.6 37.4 (kg/m3) 25% ILD(N/314 248 226 226 229 192 194
181 175 179 206 214 214 218 158 cm2) Tensile Strength 117 135 140
121 159 156 158 146 136 146 122 143 136 162 (kPa) Elongation ( % )
59 73 74 66 109 109 104 103 95 96 67 77 74 119 Tear Strength 4.3
4.5 4.6 4.8 5.1 4.7 6.0 5.5 5.3 4.5 4.0 4.5 5.3 7.2 (N/cm) 50% Wet
Set (%) 18.9 18.6 18.3 18.3 16.2 15.6 15.6 13.6 13.0 16.9 22.8 20.4
20.1 20.7 Ball Rebound: 66 67 66 66 67 68 67 68 68 68 66 67 67 66
Core (%)
* * * * *