U.S. patent application number 09/402303 was filed with the patent office on 2002-05-02 for polyurethane foam, process for producing the same, and foam forming composition.
Invention is credited to AKIYAMA, HAJIME, KAKU, MOTONAO, KUBOTA, SADAO, KUMAGAI, YASUSHI, NAKANISHI, TORU, RYUGO, JIRO, SASATANI, YUICHI, TOMOSADA, TSUYOSHI, YANAGI, TATSUROH, YOSHIO, KUNIKIYO.
Application Number | 20020052425 09/402303 |
Document ID | / |
Family ID | 27552109 |
Filed Date | 2002-05-02 |
United States Patent
Application |
20020052425 |
Kind Code |
A1 |
KAKU, MOTONAO ; et
al. |
May 2, 2002 |
POLYURETHANE FOAM, PROCESS FOR PRODUCING THE SAME, AND FOAM FORMING
COMPOSITION
Abstract
A polyurethane foam which is obtained by reacting an
addition-polymerizable active hydrogen component comprising a
compound having a group containing active hydrogen and an
addition-polymerizable functional group or comprising both this
compound and a compound containing at least 2.5 groups (on the
average) containing active hydrogen and not containing
addition-polymerizable functional groups with an organic
polyisocyanate in the presence or absence of at least one auxiliary
selected from the group consisting of foaming agents and additives
to polymerize the addition-polymerizable functional group and
simultaneously form a polyurethane, and which has a structure in
which the chains formed by the addition polymerization have been
cross-linked to the polyurethane chains. The polyurethane foam is
useful as a rigid polyurethane foam excellent in hardness,
dimensional stability, etc. and usable as a heat insulator,
shock-absorbing material, synthetic wood, etc., or is useful as a
soft polyurethane foam reduced in compression set and usable as a
cushioning material, shock-absorbing material, sound
insulating/absorbing material, etc.
Inventors: |
KAKU, MOTONAO; (KYOTO,
JP) ; KUMAGAI, YASUSHI; (KYOTO, JP) ;
NAKANISHI, TORU; (KYOTO, JP) ; YANAGI, TATSUROH;
(KYOTO, JP) ; TOMOSADA, TSUYOSHI; (KYOTO, JP)
; YOSHIO, KUNIKIYO; (KYOTO, JP) ; AKIYAMA,
HAJIME; (KYOTO, JP) ; KUBOTA, SADAO; (KYOTO,
JP) ; RYUGO, JIRO; (KYOTO, JP) ; SASATANI,
YUICHI; (KYOTO, JP) |
Correspondence
Address: |
MERCHANT & GOULD PC
P.O. BOX 2903
MINNEAPOLIS
MN
55402-0903
US
|
Family ID: |
27552109 |
Appl. No.: |
09/402303 |
Filed: |
October 1, 1999 |
PCT Filed: |
March 26, 1998 |
PCT NO: |
PCT/JP98/01388 |
Current U.S.
Class: |
521/137 ;
521/163; 521/172; 521/173 |
Current CPC
Class: |
C08G 2101/0083 20130101;
C08G 2101/0008 20130101; C08G 18/4072 20130101; C08G 18/6705
20130101; C08G 18/6795 20130101; C08J 2205/10 20130101; C08G
2101/0025 20130101; C08G 18/67 20130101; C08G 18/673 20130101; C08G
2101/005 20130101 |
Class at
Publication: |
521/137 ;
521/163; 521/172; 521/173 |
International
Class: |
C08J 009/00 |
Foreign Application Data
Date |
Code |
Application Number |
Apr 2, 1997 |
JP |
9/100967 |
Jun 27, 1997 |
JP |
9/187497 |
Sep 29, 1997 |
JP |
9/283067 |
Sep 30, 1997 |
JP |
9/284557 |
Dec 1, 1997 |
JP |
9/347271 |
Dec 26, 1997 |
JP |
9/368855 |
Claims
1. (Amended) A polyurethane foam which is obtained by reacting an
addition-polymerizable active hydrogen component comprising a
compound (A1) below having an active hydrogen-containing group and
an addition-polymerizable functional group represented by a general
formula (1) below, or comprising this compound and a compound
having at least 2.5 groups (on the average) containing active
hydrogen and not having an addition-polymerizable functional group,
wherein the component may comprise not more than 80 mass % of a
compound (A0) containing an addition-polymerizable functional group
and not having an active hydrogen-containing group based on the
total mass of the compounds (A1) and (A0), with an organic
polyisocyanate in the presence or absence of at least one auxiliary
selected from the group consisting of blowing agents and additives
to polymerize the addition-polymerizable functional group and
simultaneously form a polyurethane, and which has a structure in
which addition-polymerization chains are cross-linked to
polyurethane chains 3wherein R denotes hydrogen, an alkyl group
having 1 to 15 carbon atoms, or an aryl group having 6 to 21 carbon
atoms; (A1): a compound selected from compounds (A1/1) to (A1/4)
below (A1/1) partial esters of unsaturated carboxylic acids with
polyols selected from polyols (i) to (vi) below (i) dihydric
alcohols (ii) alcohols with a value of 3 to 8 selected from
glycerol, trimethylolpropane, pentaerythritol, diglycerol,
.alpha.-methylglucoside, sorbitol, xylitol, mannitol, glucose,
fructose, and sucrose (iii) polyhydric phenols (iv) polyether
polyols in which alkylene oxides are added to polyhydric alcohols
or to polyhydric phenols (v) polyether polyols in which alkylene
oxides are added to amines (vi) polyester polyols derived from
polyhydric alcohols and polycarboxylic acids (A1/2) partially
amidated unsaturated carboxylic acids with amines (A1/3) partial
thioesters of unsaturated carboxylic acids with polythiols (A1/4)
vinyl monomers having a hydroxyl group selected from
p-hydroxylstyrene, (meth)allyl alcohol, cinnamyl alcohol, crotonyl
alcohol, and alkylene oxide adducts of these compounds.
2. (Amended) A polyurethane foam which is obtained by reacting an
addition-polymerizable active hydrogen component (A) comprising a
compound (A1) below having at least one group containing active
hydrogen (w) and at least one addition-polymerizable functional
group (x) represented by a general formula (1) below, or comprising
the compound (A1) and a compound (A2) having at least 2.5 groups
(w) (on the average) and not having the group (x), wherein the
component may comprise not more than 80 mass % of a compound (AO)
containing addition-polymerizable functional group and not having
an active hydrogen-containing group based on the total mass of the
compounds (A1) and (AO), with an organic polyisocyanate (B) in the
presence or absence of at least one auxiliary (C) selected from the
group consisting of blowing agents (C1) and additives (C2) to
polymerize the addition-polymerizable functional group and
simultaneously form a polyurethane, wherein in the case of using a
combination of the compounds (A1) and (A2) in the component (A) it
is selected from {circle over (1)} to {circle over (3)} below:
{circle over (1)} a compound (A11) having one group (w) as the
compound (A1), and a compound with a value of active
hydrogen-containing group of at least 40 as the compound (A2);
{circle over (2)} a compound (A12) having at least two groups (w)
as the compound (A1), and the compound (A2); {circle over (3)} the
compound (A11), the compound (A12), and the compound (A2); 4wherein
R denotes hydrogen, an alkyl group having 1 to 15 carbon atoms, or
an aryl group having 6 to 21 carbon atoms; (A1): a compound
selected from compounds (A1/1) to (A1/4) below (A1/1) partial
esters of unsaturated carboxylic acids with polyols selected from
polyols (i) to (vi) below (i) dihydric alcohols (ii) alcohols with
a value of 3 to 8 selected from glycerol, trimethylolpropane,
pentaerythritol, diglycerol, a -methylglucoside, sorbitol, xylitol,
mannitol, glucose, fructose, and sucrose (iii) polyhydric phenols
(iv) polyether polyols in which alkylene oxides are added to
polyhydric alcohols or to polyhydric phenols (v) polyether polyols
in which alkylene oxides are added to amines (vi) polyester polyols
derived from polyhydric alcohols and polycarboxylic acids (A1/2)
partially amidated unsaturated carboxylic acids with amines (A1/3)
partial thioesters of unsaturated carboxylic acids with polythiols
(A1/4) vinyl monomers having a hydroxyl group selected from
p-hydroxylstyrene, (meth)allyl alcohol, cinnamyl alcohol, crotonyl
alcohol, and alkylene oxide adducts of these compounds.
3. The polyurethane foam according to claim 2, wherein an amount of
the compound (A1) is from 1 to 100 mass % based on the total mass
of the compounds (A1) and (A2).
4. The polyurethane foam according to claim 2 or 3, wherein the
compound (A1) has from 1 to 10 addition-polymerizable functional
groups, and from 1 to 8 groups containing active hydrogen, which
are preferably hydroxyl groups.
5. The polyurethane foam according to claim 1 or 2, wherein the
compound (A1) is at least one active hydrogen compound having an
active hydrogen-containing group, and an acryloyl or methacryloyl
group.
6. The polyurethane foam according to claim 2 or 3, wherein a
reaction rate constant K1 between the active hydrogen-containing
group (w) in each of the compounds (A1) and (A2) and an isocyanate
group (z) in (B) at 120.degree. C. is not more than 1
(liter/mol/sec); a polymerization reaction rate constant K2 of the
addition-polymerizable functional group (x) in the compound (A1) is
not less than 10 (liter/mol/sec); and K2/K1 is not less than
100.
7. The polyurethane foam according to claim 2 or 3, wherein the
compound (A2) comprises a compound having from 3 to 8 groups
containing active hydrogen selected from hydroxyl, mercapto, and
amino groups, which is preferably at least one polyol selected from
the group consisting of polyether polyols and polyester
polyols.
8. (Amended) The polyurethane foam according to claim 2 or 3, which
is a rigid polyurethane foam, and in which the component (A)
satisfies a requirement that a M value expressed by a formula (2)
below is not more than 500, and in which in the case of containing
the compound (A2) in the component (A) a value of active
hydrogen-containing group of the compound (A2) is from 200 to 1000
M=J/(K+L.times.2-2) (2) wherein J denotes a (number average)
molecular weight of the component (A); K denotes an (average)
number of the active hydrogen-containing group per molecule of the
component (A); and L denotes an (average) number of the
addition-polymerizable functional group per molecule of the
component (A).
9. The polyurethane foam according to claim 8, which is obtained by
using as auxiliaries (C) a blowing agent (C1) and as needed a foam
stabilizer (C21) and/or an urethanation catalyst (C22) as additives
(C2), and which has a density of 5 to 900 kg/m.sup.3.
10. The polyurethane foam according to claim 8, which is obtained
by carrying out a polyurethane-forming reaction by mechanical froth
method without using as auxiliaries (C) a blowing agent (C1) but
using an inorganic powder (C23) and/or a hollow microsphere (C24),
a dehydrating agent (C25), and as needed a foam stabilizer (C21)
and/or an urethanation catalyst (C22) as additives (C2).
11. The polyurethane foam according to claim 8, which is obtained
by forming a syntactic foam without using as auxiliaries (C) a
blowing agent (C1) but using a hollow microsphere (C24), a
dehydrating agent (C25), and as needed an inorganic powder (C23) as
additives (C2).
12. The polyurethane foam according to claim 8, which is obtained
by further using a staple fiber (C26) as an additive (C2).
13. A thermal insulator comprising the polyurethane foam according
to claim 8.
14. A shock-absorbing material comprising the polyurethane foam
according to claim 8.
15. A synthetic wood comprising the polyurethane foam according to
claim 8.
16. The polyurethane foam according to claim 2 or 3, which is a
flexible polyurethane foam having a density of 10 to 500
kg/m.sup.3, and in which the component (A) satisfies a requirement
that a M value expressed by a formula (2) below is at least 500
M=J/(K+L.times.2-2) (2) wherein J denotes a (number average)
molecular weight of the component (A); K denotes an (average)
number of the active hydrogen-containing group per molecule of the
component (A); and L denotes an (average) number of the
addition-polymerizable functional group per molecule of the
component (A).
17. (Amended) An elastic polyurethane foam obtained by reacting an
addition-polymerizable active hydrogen component (A') below with an
organic polyisocyanate (B) in the presence or absence of at least
one auxiliary (C) selected from the group consisting of blowing
agents (C1) and additives (C2) to polymerize the
addition-polymerizable functional group and simultaneously form a
polyurethane: addition-polymerizable active hydrogen component
(A'): an addition-polymerizable active hydrogen component which
comprises an active hydrogen-containing group (w) and an
addition-polymerizable functional group (x) and which is selected
from (A31), (A32), and (A33) below; wherein a reaction rate
constant K1 between the active hydrogen-containing group (w) and an
isocyanate group (z) at 120.degree. C. is not more than 1
(liter/mol/sec); a polymerization reaction rate constant K2 of the
addition-polymerizable functional group (x) is not less than 10
(liter/mol/sec); and K2/K1 is not less than 100 (A31): an
addition-polymerizable active hydrogen compound which has an active
hydrogen-containing group (w) and an addition-polymerizable
functional group (x) and which may have a cyclic group (y) reactive
with the group (w); (A32): an active hydrogen compound (A321)
having at least three groups (w) or having the groups (w) and (y),
and an addition-polymerizable compound (A322) having the groups (x)
and (y), used in combination; (A33): the compound (A31), and the
compound (A321) and/or the compound (A322), used in combination;
wherein a compound (A311) having an active hydrogen-containing
group (w) and an addition-polymerizable functional group (x) among
the compound (A31) has a group (x) represented by a following
general formula (1) and is selected from (A1/1) to (A1/4) below 5
wherein R denotes hydrogen, an alkyl group having 1 to 15 carbon
atoms, or an aryl group having 6 to 21 carbon atoms (A1/1) partial
esters of unsaturated carboxylic acids with polyols selected from
polyols (i) to (vi) below (i) dihydric alcohols (ii) alcohols with
a value of 3 to 8 selected from glycerol, trimethylolpropane,
pentaerythritol, diglycerol, .alpha.-methylglucoside, sorbitol,
xylitol, mannitol, glucose, fructose, and sucrose (iii) polyhydric
phenols (iv) polyether polyols in which alkylene oxides are added
to polyhydric alcohols or to polyhydric phenols (v) polyether
polyols in which alkylene oxides are added to amines (vi) polyester
polyols derived from polyhydric alcohols and polycarboxylic acids
(A1/2) partially amidated unsaturated carboxylic acids with amines
(A1/3) partial thioesters of unsaturated carboxylic acids with
polythiols (A1/4) vinyl monomers having a hydroxyl group selected
from p-hydroxylstyrene, (meth)allyl alcohol, cinnamyl alcohol,
crotonyl alcohol, and alkylene oxide adducts of these
compounds.
18. A cushioning material comprising the polyurethane foam
according to claim 16.
19. A shock-absorbing material comprising the polyurethane foam
according to claim 16.
20. A sound insulating/absorbing material comprising the
polyurethane foam according to claim 16.
21. (Amended) A process for producing a polyurethane foam which
comprises reacting an addition-polymerizable active hydrogen
component (A) comprising a compound (A1) below having at least one
group containing active hydrogen (w) and at least one
addition-polymerizable functional group (x) represented by a
general formula (1) below, or comprising the compound (A1) and a
compound (A2) having at least 2.5 groups (w) (on the average) and
not having the group (x), wherein the component may comprise not
more than 80 mass % of a compound (A0) containing an
addition-polymerizable functional group and not having an active
hydrogen-containing group based on the total mass of the compounds
(A1) and (A0), with an organic polyisocyanate (B) in the presence
or absence of at least one auxiliary (C) selected from the group
consisting of blowing agents (C1) and additives (C2) to polymerize
the addition-polymerizable functional group and simultaneously form
a polyurethane, wherein in the case of using a combination of the
compounds (A1) and (A2) in the component (A) it is selected from
{circle over (1)} to {circle over (3)} below: {circle over (1)} a
compound (A11) having one group (w) as the compound (A1), and a
compound with a value of active hydrogen-containing group of at
least 40 as the compound (A2); {circle over (2)} a compound (A12)
having at least two groups (w) as the compound (A1), and the
compound (A2); {circle over (3)} the compound (A11), the compound
(A12), and the compound (A2); 6 wherein R denotes hydrogen, an
alkyl group having 1 to 15 carbon atoms, or an aryl group having 6
to 21 carbon atoms; (A1): a compound selected from compounds (A1/1)
to (A1/4) below (A1/1) partial esters of unsaturated carboxylic
acids with polyols selected from polyols (i) to (vi) below (i)
dihydric alcohols (ii) alcohols with a value of 3 to 8 selected
from glycerol, trimethylolpropane, pentaerythritol, diglycerol,
.alpha.-methylglucoside, sorbitol, xylitol, mannitol, glucose,
fructose, and sucrose (iii) polyhydric phenols (iv) polyether
polyols in which alkylene oxides are added to polyhydric alcohols
or to polyhydric phenols (v) polyether polyols in which alkylene
oxides are added to amines (vi) polyester polyols derived from
polyhydric alcohols and polycarboxylic acids (A1/2) partially
amidated unsaturated carboxylic acids with amines (A1/3) partial
thioesters of unsaturated carboxylic acids with polythiols (A1/4)
vinyl monomers having a hydroxyl group selected from
p-hydroxylstyrene, (meth)allyl alcohol, cinnamyl alcohol, crotonyl
alcohol, and alkylene oxide adducts of these compounds.
22. A composition for forming a polyurethane foam which comprises
an addition-polymerizable active hydrogen component (A) comprising
a compound (A1) below having at least one group containing active
hydrogen (w) and at least one addition-polymerizable functional
group (x) represented by a general formula (1) below, or comprising
the compound (A1) and a compound (A2) having at least 2.5 groups
(w) (on the average) and not having the group (x), wherein the
component may comprise not more than 80 mass % of a compound (AO)
containing an addition-polymerizable functional group and not
having an active hydrogen-containing group based on the total mass
of the compounds (A1) and (A0), and an organic polyisocyanate (B),
and which comprises or does not comprise at least one auxiliary (C)
selected from the group consisting of blowing agents (C1) and
additives (C2), wherein in the case of using a combination of the
compounds (A1) and (A2) in the component (A) it is selected from
{circle over (1)} to {circle over (3)} below: {circle over (1)} a
compound (A11) having one group (w) as the compound (A1), and a
compound with a value of active hydrogen-containing group of at
least 40 as the compound (A2); {circle over (2)} a compound (A12)
having at least two groups (w) as the compound (A1), and the
compound (A2); {circle over (3)} the compound (A11), the compound
(A12), and the compound (A2); 7 wherein R denotes hydrogen, an
alkyl group having 1 to 15 carbon atoms, or an aryl group having 6
to 21 carbon atoms; (A1): a compound selected from compounds (A1/1)
to (A1/4) below (A1/1) partial esters of unsaturated carboxylic
acids with polyols selected from polyols (i) to (vi) below (i)
dihydric alcohols (ii) alcohols with a value of 3 to 8 selected
from glycerol, trimethylolpropane, pentaerythritol, diglycerol,
.alpha.-methylglucoside, sorbitol, xylitol, mannitol, glucose,
fructose, and sucrose (iii) polyhydric phenols (iv) polyether
polyols in which alkylene oxides are added to polyhydric alcohols
or to polyhydric phenols (v) polyether polyols in which alkylene
oxides are added to amines (vi) polyester polyols derived from
polyhydric alcohols and polycarboxylic acids (A1/2) partially
amidated unsaturated carboxylic acids with amines (A1/3) partial
thioesters of unsaturated carboxylic acids with polythiols (A1/4)
vinyl monomers having a hydroxyl group selected from
p-hydroxylstyrene, (meth)allyl alcohol, cinnamyl alcohol, crotonyl
alcohol, and alkylene oxide adducts of these compounds.
23. (Amended) An addition-polymerizable active hydrogen component
for forming a polyurethane foam which comprises a compound (A1)
below having at least one group containing active hydrogen (w) and
at least one addition-polymerizable functional group (x)
represented by a general formula (1) below, or comprises the
compound (A1) and a compound (A2) having at least 2.5 groups (w)
(on the average) and not having the group (x), wherein the
component may comprise not more than 80 mass % of a compound (A0)
containing an addition-polymerizable functional group and not
having an active hydrogen-containing group based on the total mass
of the compounds (A1) and (A0), and wherein in the case of using a
combination of the compounds (A1) and (A2) it is selected from
{circle over (1)} to {circle over (3)} below: {circle over (1)} a
compound (A11) having one group (w) as the compound (A1), and a
compound with a value of active hydrogen-containing group of at
least 40 as the compound (A2); {circle over (2)} a compound (A12)
having at least two groups (w) as the compound (A1), and the
compound (A2); {circle over (3)} the compound (A11), the compound
(A12), and the compound (A2); 8 wherein R denotes hydrogen, an
alkyl group having 1 to 15 carbon atoms, or an aryl group having 6
to 21 carbon atoms; (A1): a compound selected from compounds (A1/1)
to (A1/4) below (A1/1) partial esters of unsaturated carboxylic
acids with polyols selected from polyols (i) to (vi) below (i)
dihydric alcohols (ii) alcohols with a value of 3 to 8 selected
from glycerol, trimethylolpropane, pentaerythritol, diglycerol,
.alpha.-methylglucoside, sorbitol, xylitol, mannitol, glucose,
fructose, and sucrose (iii) polyhydric phenols (iv) polyether
polyols in which alkylene oxides are added to polyhydric alcohols
or to polyhydric phenols (v) polyether polyols in which alkylene
oxides are added to amines (vi) polyester polyols derived from
polyhydric alcohols and polycarboxylic acids (A1/2) partially
amidated unsaturated carboxylic acids with amines (A1/3) partial
thioesters of unsaturated carboxylic acids with polythiols (A1/4)
vinyl monomers having a hydroxyl group selected from
p-hydroxylstyrene, (meth)allyl alcohol, cinnamyl alcohol, crotonyl
alcohol, and alkylene oxide adducts of these compounds.
Description
INDUSTRIAL FIELD
[0001] The present invention relates to a polyurethane foam
excellent in mechanical properties, a process for producing the
same, and a foam forming composition. More particularly, the
present invention relates to a polyurethane foam having a structure
in which polymer chains formed by an addition-polymerization
reaction (hereinafter abbreviated as addition-polymerization
chains) and polyurethane chains are cross-linked to each other,
which is excellent in mechanical properties such as hardness and
dimensional stability in the case of forming a rigid foam, and
which has mechanical properties such as reduced compression set in
the case of forming a flexible foam.
INDUSTRIAL BACKGROUND
[0002] Polyurethane foams having addition-polymerization chains and
polyurethane chains have been disclosed, for example, in Japanese
Publication of Unexamined Patent Application (Tokkai) No. HEI
3-244620 (Document 1), and Japanese Publication of Unexamined
Patent Application (Tokkai) No. SHO 63-23956 (Document 2).
[0003] The Japanese Publication of Unexamined Patent Application
(Tokkai) No. HEI 3-244620 (Document 1) discloses an elastic
polyurethane foam obtained by reacting a high molecular weight
polyol such as a polyoxyalkylene polyol having a hydroxyl value of
5 to 38 with a polyisocyanate compound in the presence of a low
viscosity compound having an addition-polymerizable unsaturated
group, a catalyst, and a blowing agent. Furthermore, Document 1
discloses that a compound having zero or one, particularly zero
functional group capable of reacting with an isocyanate may be used
as the low viscosity compound having an addition-polymerizable
unsaturated group, and indicates that if a compound having many
functional groups is used, it is incorporated in the polyurethane
chains and causes undesirable cross-linking.
[0004] Japanese Publication of Unexamined Patent Application
(Tokkai) No. SHO 63-23956 (Document 2) discloses a polyurethane
that is obtained by admixing a mixture of a long-chain polyol and a
short-chain diol with an ethylenic unsaturated esterol such as
alkyl hydroxy acrylate or alkyl hydroxy methacrylate to prepare a
polyol mixture having storage stability, and reacting the polyol
mixture with an organic polyisocyanate by a method such as RIM
(reaction injection molding). It is also disclosed in the Document
2 that a blowing agent may be included as an optional component in
the RIM.
[0005] It is a first object of the present invention to provide a
polyurethane foam excellent in mechanical properties.
[0006] It is another object of the present invention to provide a
rigid polyurethane foam excellent in mechanical properties such as
hardness and dimensional stability.
[0007] It is a further object of the present invention to provide a
flexible polyurethane foam which has mechanical properties such as
reduced compression set and in which ball rebound is not reduced
even when its density is decreased.
[0008] It is a still further object of the present invention to
obtain a rigid polyurethane foam that has equal dimensional
stability and equal or higher mechanical strength as compared to
the case of using conventional monochlorotrifluorocarbon (CFC-11),
and has good thermal insulation and flame resistance, when
producing a rigid polyurethane foam in the presence of at least one
blowing agent selected from hydrogen atom-containing halogenated
hydrocarbon, water, low boiling point hydrocarbon, and liquefied
carbon dioxide gas.
[0009] It is a still further object of the present invention to
provide a rigid polyurethane foam reinforced with staple fiber
having a high bending strength and a high bending modulus.
SUMMARY OF THE INVENTION
[0010] Other objects of the present invention, which will be
apparent from the above and below descriptions, are broadly
achieved by the following polyurethane foam:
[0011] A polyurethane foam which is obtained by reacting an
addition-polymerizable active hydrogen component comprising a
compound having an active hydrogen-containing group and an
addition-polymerizable functional group or comprising this compound
and a compound having at least 2.5 groups (on the average)
containing active hydrogen and not having an addition-polymerizable
functional group with an organic polyisocyanate in the presence or
absence of at least one auxiliary selected from the group
consisting of blowing agents and additives to polymerize the
addition-polymerizable functional group and simultaneously form a
polyurethane, and which has a structure in which the
addition-polymerization chains are cross-linked to the polyurethane
chains.
[0012] As the above-mentioned addition-polymerizable active
hydrogen component, an addition-polymerizable active hydrogen
component (A) comprising a compound (A1) having at least one group
containing active hydrogen (w) and at least one
addition-polymerizable functional group (x) or comprising the
compound (A1) and a compound (A2) having at least 2.5 groups (w)
(on the average) and not having the group (x) may be employed. When
using a combination of the compounds (A1) and (A2) in the component
(A), the combination is selected from {circle over (1)} to {circle
over (3)} below:
[0013] {circle over (1)} a compound (A11) having one group (w) as
the compound (A1), and a compound with a value of active
hydrogen-containing group of at least 40 as the compound (A2);
[0014] {circle over (2)} a compound (A12) having at least two
groups (w) as the compound (A1), and the compound (A2);
[0015] {circle over (3)} the compound (A11), the compound (A12),
and the compound (A2).
[0016] Hereinafter, a polyurethane foam obtained using an
addition-polymerizable active hydrogen component (A) is referred to
as a polyurethane foam [1].
[0017] Furthermore, the following addition-polymerizable active
hydrogen component (A') also may be used as the above-mentioned
addition-polymerizable active hydrogen component.
[0018] Addition-polymerizable active hydrogen component (A'): an
addition-polymerizable active hydrogen component that comprises the
active hydrogen-containing group (w) and an addition-polymerizable
functional group (x), and which is selected from (A31), (A32), and
(A33) below; wherein the reaction rate constant K1 between the
active hydrogen-containing group (w) and an isocyanate group (z) at
120.degree. C. is not more than 1 (liter/mol/sec); the
polymerization reaction rate constant K2 of the
addition-polymerizable functional group (x) is not less than 10
(liter/mol/sec); and K2/K1 is not less than 100.
[0019] (A31): an addition-polymerizable active hydrogen compound
which has the active hydrogen-containing group (w) and the
addition-polymerizable functional group (x), and which may have a
cyclic group (y) reactive with the group (w).
[0020] (A32): an active hydrogen compound (A321) having at least
three groups (w) or having the groups (w) and (y), and an
addition-polymerizable compound (A322) having the groups (x) and
(y), used in combination.
[0021] (A33): the compound (A31), the compound (A321) and/or the
compound (A322), used in combination.
[0022] Hereinafter, a polyurethane foam obtained using an
addition-polymerizable active hydrogen component (A') is referred
to as a polyurethane foam [2].
DETAILED DESCRIPTION OF THE INVENTION
[0023] In the polyurethane foam of the present invention, the
addition-polymerizable active hydrogen component (A) comprises at
least one compound (A1) having at least one group containing active
hydrogen (w) and at least one addition-polymerizable functional
group (x), or comprises the compound (A1) and at least one compound
(A2) having at least 2.5 groups (w) (on the average) and not having
the group (x).
[0024] The active hydrogen-containing group (w) in the compound
(A1) may be at least one group containing active hydrogen selected
from hydroxyl, mercapto, carboxyl, primary amino, and secondary
amino groups, etc., and preferably used is a hydroxyl group.
Examples of the addition-polymerizable functional group (x) in the
compound (A1) include radical-polymerizable functional groups of
the terminal olefin type or the internal olefin type,
cationic-polymerizable functional groups (e.g. vinyl ether group,
propenyl ether group), and anionic-polymerizable functional groups
(e.g. vinyl carboxyl group, cyano acryloyl group). Preferable are
radical-polymerizable functional groups, and particularly
preferable are radical-polymerizable functional groups of terminal
olefin type. The compound (A1) usually has from 1 to 10, preferably
from 1 to 5 addition-polymerizable functional groups (x), and
usually from 1 to 8, preferably from 1 to 5 groups containing
active hydrogen (w).
[0025] As the compound (A1) preferable is at least one active
hydrogen compound having an active hydrogen-containing group (w)
and also having a radical-polymerizable functional group of
terminal olefin type represented by the general formula (1) below
1
[0026] wherein R denotes hydrogen, an alkyl group having 1 to 15
carbon atoms, or an aryl group having 6 to 21 carbon atoms.
[0027] Particularly, active hydrogen compounds having an acryloyl
group or a methacryloyl group are preferably employed as the at
least one active hydrogen compound having a radical-polymerizable
functional group represented by the general formula (1).
[0028] As the compound (A1), more preferably used is a compound
represented by the general formula (3) below 2
[0029] wherein R denotes hydrogen, an alkyl group having 1 to 15
carbon atoms, or an aryl group having 6 to 21 carbon atoms; X
denotes O, S, or NH;
[0030] p and q denote positive integers; Q denotes an active
hydrogen-containing group; and Z denotes a residue of an active
hydrogen compound from which (p+q)groups containing active hydrogen
are removed, respectively. R is preferably hydrogen or an alkyl
group, particularly preferably hydrogen or methyl group; and X is
preferably O. The value of p is preferably from 1 to 7, more
preferably from 1 to 5. The value of q is preferably from 1 to 7,
more preferably from 1 to 4. In the case of the flexible foam
mentioned below, because the concentrations of the
addition-polymerizable functional group and the active
hydrogen-containing group are low, elongation or tear strength of
the obtained foam may be decreased if q is less than 2. Thus, the
value of q is particularly preferably from 2 to 4. Furthermore, the
value of (p+q) is preferably from 2 to 8, and in the case of a
flexible foam, more preferably it is from 3 to 8. Furthermore, it
is preferable to employ hydroxyl group as Q.
[0031] Examples of the compounds (A1) include (A1/1) to (A1/4) as
follows:
[0032] (A1/1): partial esters of unsaturated carboxylic acids with
polyols [polyhydric alcohols; polyhydric phenols; polyether polyols
in which alkylene oxides (AO) are added to polyhydric alcohols or
to polyhydric phenols; polyether polyols in which AO are added to
amines; polyester polyols derived from polyhydric alcohols and
polycarboxylic acids, and the like]
[0033] (A1/2): partially amidated unsaturated carboxylic acids with
amines
[0034] (A1/3): partial thioesters of unsaturated carboxylic acids
with polythiols
[0035] (A1/4): vinyl monomers having a hydroxyl group
[0036] The polyhydric alcohols among the polyols used in producing
the compounds (A1/1) include, for example, dihydric alcohols
[ethylene glycol, diethylene glycol, propylene glycol, dipropylene
glycol, 1,4-butanediol, 1,6-hexanediol, 1,3-butylene glycol,
neopentyl glycol, and the like], alcohols with a value of 3 to 8 or
more [glycerol, trimethylolpropane, pentaerythritol, diglycerol,
.alpha.-methylglucoside, sorbitol, xylitol, mannitol, glucose,
fructose, sucrose, and the like], and combinations of two or more
of these.
[0037] The polyhydric phenols among the polyols used in producing
the compounds (A1/1) include, for example, hydroquinone, bisphenols
(bisphenol A, bisphenol F, etc.), formalin low condensation
products of phenol compounds (novolac resin, intermediate of
resol), and combinations of two or more of these.
[0038] The amines in the polyether polyols in which AO are added to
amines among the polyols used in producing the compounds (A1/1)
include, for example, ammonia; alkanolamines [mono-, di-, or
triethanolamine, isopropanolamine, aminoethylethanolamine, and the
like]; alkylamines having 1 to 20 carbon atoms [methylamine,
ethylamine, n-butylamine, octylamine, and the like];
alkylenediamines having 2 to 6 carbon atoms [ethylenediamine,
hexamethylenediamine, and the like]; polyalkylene polyamines having
2 to 6 carbon atoms in the alkylene groups [diethylenetriamine,
triethylenetetramine, and the like]; aromatic amines having 6 to 20
carbon atoms [aniline, phenylenediamine, diaminotoluene,
xylylenediamine, methylenedianiline, diphenyl ether diamine, and
the like]; alicyclic amines having 4 to 15 carbon atoms
[isophoronediamine, cyclohexylenediamine, and the like];
heterocyclic amines having 4 to 15 carbon atoms [piperazine,
N-aminoethylpiperazine, 1,4-diaminoethylpiperaz- ine, and the
like], and combinations of two or more of these.
[0039] The alkylene oxides (AO) which are added to polyhydric
alcohols, polyhydric phenols, or amines include, for example,
ethylene oxide (hereinafter abbreviated as EO), propylene oxide
(hereinafter abbreviated as PO), 1,2-, 1,4- or 2,3-butylene oxide,
styrene oxide, and the like, and combinations of two or more of
these (when using combinations of two or more of these AO, either
random addition or block addition may be employed), but it is not
limited only to these examples. Among these examples, it is
preferable to use those containing PO and/or EO as main components
and containing not more than 20 mass % of other alkylene oxides.
The addition reaction may be performed by conventional methods.
[0040] The polyhydric alcohols used in the polyester polyols among
the polyols used in producing the compounds (A1/1) are same as
described above. The polycarboxylic acids include aliphatic
polycarboxylic acids [succinic acid, adipic acid, sebacic acid,
maleic acid, fumaric acid, and the like], aromatic polycarboxylic
acids [phthalic acid or its isomers, trimellitic acid, and the
like], ester-forming derivatives of these polycarboxylic acids
[acid anhydrides, lower alkyl esters having 1 to 4 carbon atoms in
the alkyl groups, and the like], and combinations of two or more of
these.
[0041] The compounds (A1/1) are obtained by partially esterifying
the polyols listed above with unsaturated carboxylic acids. The
unsaturated carboxylic acids include, for example, (meth)acrylic
acid, crotonic acid, maleic acid, fumaric acid, itaconic acid,
citraconic acid, mesaconic acid, aconitic acid, cinnamic acid,
vinylbenzoic acid, and the like, and combinations of two or more of
these [the (meth)acrylic acid herein refers to acrylic acid and/or
methacrylic acid, and hereinafter also is referred to in the same
way]; ester-forming derivatives of these unsaturated carboxylic
acids, for example, halides [e.g. (meth)acrylic acid chloride],
acid anhydrides [e.g. maleic acid anhydride, itaconic acid
anhydride, and citraconic acid anhydride]; and combinations of two
or more of these.
[0042] Examples of the compounds (A1/1) include 2-hydroxyethyl
(meth)acrylate, 2-hydroxypropyl (meth)acrylate, 4-hydroxybutyl
(meth)acrylate, 3-phenoxy-2-hydroxypropyl (meth)acrylate, glycerol
mono(meth)acrylate, glycerol di(meth)acrylate, diethylene glycol
mono(meth)acrylate, and the like, and combinations of two or more
of these.
[0043] The compounds (A1/2) are obtained by reacting the
above-mentioned unsaturated carboxylic acids with the polyamines or
alkanolamines among the above-mentioned amines. Examples include
(meth)acrylamido ethyl amine, (meth)acrylamido hexyl amine, and the
like, and combinations of two or more of these.
[0044] The polythiols used in producing the compounds (A1/3)
include, for example, ethanedithiol, 1,2-propanedithiol,
1,3-propanedithiol, 1,4-butanedithiol, 1,4-benzenedithiol,
1,2-benzenedithiol, bis(4-mercaptophenyl) sulfide,
4-t-butyl-1,2-benzenedithiol, ethylene glycol dithioglycolate,
trimethylolpropanetris(thioglycolate) thiocyanuric acid,
di(2-mercaptoethyl) sulfide, di(2-mercaptoethyl) ether, and
combinations of two or more of these. The compounds (A1/3) are
obtained by reacting these polythiols with the above-mentioned
unsaturated carboxylic acids. Examples of the compounds (A1/3)
include acryloyl thioethyl mercaptan, acryloyl thiobutyl mercaptan,
and the like, and combinations of two or more of these.
[0045] Examples of the compounds (A1/4) include p-hydroxylstyrene,
(meth)allyl alcohol, cinnamyl alcohol, crotonyl alcohol, adducts of
the above-mentioned alkylene oxides (AO) to these compounds, and
combinations of two or more of these.
[0046] Preferable among these are partial esters of unsaturated
carboxylic acids with polyols among the compounds (A1/1),
particularly preferably partial esters of unsaturated carboxylic
acids with polyhydric alcohols or their AO adducts, most preferably
diethylene glycol mono(meth)acrylate, because they have low
viscosity and this also lowers the viscosity of a
polyurethane-forming composition when used.
[0047] Considering its viscosity-reducing effect in a
polyurethane-forming composition, the molecular weight of the
compound (A1) per an active hydrogen-containing group is preferably
from 40 to 2,500. For the rigid foams described below, it is more
preferably from 40 to 500, particularly preferably from 45 to
300.
[0048] The compound (A2) is at least one compound having at least
2.5 (on the average), preferably 3 to 8 groups containing active
hydrogen (w), and not having an addition-polymerizable functional
group (x).
[0049] If the number of active hydrogen-containing groups is less
than 2.5 (on the average), in the case of forming a rigid foam,
mechanical properties such as hardness and dimensional stability
are reduced, and in the case of forming a flexible foam,
compression set increases.
[0050] The active hydrogen-containing group (w) in the compound
(A2) may be at least one group containing active hydrogen selected
from hydroxyl, mercapto, and amino groups.
[0051] Suitable examples of the compounds (A2) are those having 3
to 8 active hydrogen-containing groups selected from hydroxyl,
mercapto, and amino groups, preferably hydroxyl group. Examples
include the above-mentioned polyhydric alcohols, polyhydric
phenols, amines [diamines, polyamines, alkanolamines], polyether
polyols, polyester polyols, and the like, particularly preferably
at least one polyol selected from the group consisting of polyether
polyols and polyester polyols.
[0052] The polyether polyols may be known polyether polyols
commonly used in polyurethane foams, e.g. adducts of the
above-mentioned alkylene oxides (AO) to the above-mentioned
polyhydric alcohols, polyhydric phenols, polycarboxylic acids,
amines, and the like. It is preferable to use those containing PO
and/or EO as main components and containing not more than 20 mass %
of other alkylene oxides as the AO, particularly preferably PO
and/or EO. The polyester polyols may be known polyester polyols
commonly used in polyurethane foams, e.g. polyester polyols derived
from the above-mentioned polyhydric alcohols or polyhydric phenols
and the above-mentioned polycarboxylic acids. Among these compounds
(A2) particularly preferable are polyether polyols in which AO is
added to polyhydric alcohols. Moreover, the number average
molecular weight of the compound (A2) is preferably from 50 to
10,000, particularly preferably from 60 to 8,000.
[0053] In the present invention, a vinyl polymer (F) also may be
further dispersed in the compound (A2) as needed. The vinyl polymer
(F) may be dispersed in the (A2) after it is polymerized, but
preferably it is dispersed by polymerizing a vinyl monomer (f) in
the (A2) to be stabilized. Examples of the vinyl monomer (f)
include acrylonitrile, styrene, vinylidene chloride, alkyl
(meth)acrylate, and the like, and preferable are acrylonitrile and
styrene. The amount of the (F) is usually from 5 to 50 mass parts,
preferably from 15 to 45 mass parts per 100 mass parts of the
(A2).
[0054] It is preferable that the reaction rate constant K1 between
the active hydrogen-containing group (w) in each of the compounds
(A1) and (A2) and an isocyanate group (z) in (B) at 120.degree. C.
is not more than 1 (liter/mol/sec); the polymerization reaction
rate constant K2 of the addition-polymerizable functional group (x)
in (A1) is not less than 10 (liter/mol/sec); and K2/K1 is not less
than 100.
[0055] The ratio of the (A1) contained in the component (A) based
on the total mass of the compounds (A1) and (A2) is usually from 1
to 100 mass %, more preferably from 2 to 100 mass %. For the rigid
foams described below, it is more preferably from 5 to 100 mass %,
particularly preferably from 10 to 95 mass %.
[0056] An essential component in the component (A) is a compound
(A1) or a combination of compounds (A1) and (A2). When a
combination is used, it is selected from {circle over (1)} to
{circle over (3)} below:
[0057] {circle over (1)} a compound (All) having one group
containing active hydrogen (w) as the compound (A1), and a compound
having a value of active hydrogen-containing group of at least 40
as the compound (A2),
[0058] wherein the value of active hydrogen-containing group refers
to "56100/(equivalent of active hydrogen)", i.e. "56100/(molecular
weight per an active hydrogen-containing group)";
[0059] {circle over (2)} a compound (A12) having at least two
groups containing active hydrogen (w) as the compound (A1), and the
compound (A2);
[0060] {circle over (3)} the compound (A11), the compound (A12),
and the compound (A2).
[0061] That is, when the compound (A2) used in the combination has
a value of active hydrogen-containing group of 40 or more, the
compound (A1) may be either the compound (A11) having one group
containing active hydrogen (w) or the compound (A12) having at
least two groups (w). However, when the compound (A2) used in the
combination has a value of active hydrogen-containing group of less
than 40, it is necessary to use at least partially the compound
(A12) having at least two groups containing active hydrogen (w) as
the compound (A1). This is because, when the compound (A2) is a
long chain compound with a value of active hydrogen-containing
group of less than 40, which is considerably low, one group
containing active hydrogen (w) that is contained in the compound
(A1) is not enough to keep a sufficient degree of cross-linking of
the addition-polymerization chains per a length of the polyurethane
chains formed. On the other hand, when the compound (A2) has a
relatively short chain with a value of active hydrogen-containing
group of 40 or more, a sufficient degree of crosslinking of the
addition-polymerization chains per a length of the polyurethane
chains formed is ensured, even when the compound (A1) has only one
group containing active hydrogen (w). Because sufficient
crosslinking is ensured, when forming a rigid foam, polyurethane
foams excellent in mechanical properties such as hardness and
dimensional stability can be obtained, and when forming a flexible
foam, polyurethane foams having mechanical properties such as small
compression set can be obtained. Also, because of the same reason,
when using only the compound (A11) as the (A1) in a combination of
the (A1) and (A2), it is preferable to use a compound having a
value of active hydrogen-containing group of at least 60,
particularly preferably at least 100, as the compound (A2). In each
case of the above {circle over (1)} to {circle over (3)}, the
amount of the compound (A1) based on the total mass of the
compounds (A1) and (A2) is preferably from 1 to 99 mass %, more
preferably from 2 to 95 mass %. In the case of {circle over (3)},
the amount of the compound (A12) based on the total mass of the
compounds (A11) and (A12) is preferably at least 5 mass %, more
preferably at least 20 mass %.
[0062] In the present invention, at least one compound (A0)
containing an addition-polymerizable functional group and not
having an active hydrogen-containing group also can be used in the
component (A) as needed. As the addition-polymerizable functional
group in the (A0), the same groups as in the compound (A1) may be
employed, and preferable are radical-polymerizable functional
groups. Examples of the radical-polymerizable functional groups
include acryloyl, methacryloyl, vinyl, vinylbenzyl, vinylphenyl,
and allyl ether groups, and the like. A preferable
radical-polymerizable functional group is an acryloyl or
methacryloyl group.
[0063] The number of the addition-polymerizable functional groups
in the compound (A0) is usually from 1 to 10, preferably from 1 to
8. When increase of the mechanical strength is significant, the
number of the addition-polymerizable functional groups in the (A0)
is preferably from 2 to 8, particularly preferably from 4 to 8.
Considering to lower the viscosity of the polyurethane-forming
composition, the viscosity of the compound (A0) is preferably not
more than 1,000 mPa.multidot.s (at 25.degree. C.), particularly
preferably not more than 500 mPa.multidot.s (at 25.degree. C.).
Furthermore, the (A0) also may be contained in the component (A)
along with the (A1) as a by-product which is simultaneously formed
when producing the (A1). The amount of the (A0) is usually not more
than 80 mass %, preferably not more than 60 mass %, particularly
preferably not more than 40 mass % based on the total mass of the
(A1) and (A0).
[0064] As the compound (A0), aromatic hydrocarbon monomers
[styrene, .alpha.-methyl styrene, etc.], unsaturated nitriles
[(meth)acrylonitrile etc.], and the like may be employed, but
preferable examples of the (A0) are the (A01) to (A03) as
follows:
[0065] (A01) esters of unsaturated carboxylic acids with polyols
[polyhydric alcohols; polyhydric phenols; polyether polyols in
which alkylene oxides (AO) are added to these compounds; polyether
polyols in which AO are added to amines; polyester polyols derived
from polyhydric alcohols and polycarboxylic acids; and the
like]
[0066] (A02) amidated unsaturated carboxylic acids with amines
[0067] (A03) thioesters of unsaturated carboxylic acids with
polythiols
[0068] The compound (A01) is obtained by reacting the polyols and
unsaturated carboxylic acids used in producing the above-mentioned
compound (A11) in a molar ratio different from that in the (A11).
The compound (A02) is obtained by reacting the polyamines or
alkanolamines and the unsaturated carboxylic acids used in
producing the above-mentioned compound (A12) in a molar ratio
different from that in the (A12). The compound (A03) is obtained by
reacting the polythiols and the unsaturated carboxylic acids used
in producing the above-mentioned compound (A13) in a molar ratio
different from that in the (A13).
[0069] The polyurethane foam [1] of the present invention is
obtained by reacting the component (A) with an organic
polyisocyanate (B) in the presence or absence of at least one
auxiliary (C) selected from the group consisting of blowing agents
(C1) and additives (C2) to polymerize the addition-polymerizable
functional group and simultaneously form a polyurethane.
[0070] In the present invention, it is understood that to
polymerize the addition-polymerizable functional group and
simultaneously form a polyurethane means that the polymerization of
the addition-polymerizable functional group and the
polyurethane-forming reaction are carried out simultaneously at
least partially during the reaction period. In order to improve the
mechanical properties of the polyurethane with increased
crosslinking density, it is preferable that the other reaction is
initiated before a resin is formed through a curing in one
reaction, so that the two reactions are carried out
simultaneously.
[0071] As the organic polyisocyanate (B), conventional materials
used in producing polyurethane foams may be employed. Examples of
such isocyanates include aromatic polyisocyanates (B1), aliphatic
polyisocyanates (B2), alicyclic polyisocyanates (B3), araliphatic
polyisocyanates (B4), modified polyisocyanates (B5), and mixtures
of two or more of these.
[0072] The aromatic polyisocyanates (B1) include aromatic
diisocyanates having 6 to 16 carbon atoms (not including the carbon
atoms in the NCO group; this also applies to the isocyanates
mentioned below), aromatic triisocyanates having 6 to 20 carbon
atoms, crude materials of these isocyanates, and the like. Examples
of (B1) are 1,3- and 1,4-phenylene diisocyanates, 2,4- and
2,6-tolylene diisocyanates (TDI), crude TDI, 2,4'- and
4,4'-diphenylmethane diisocyanates (MDI), crude MDI, polymethylene
polyphenyl isocyanate (polymeric MDI),
naphthylene-1,5-diisocyanate,
triphenylmethane-4,4',4"-triisocyanate, and the like.
[0073] The aliphatic polyisocyanates (B2) include aliphatic
diisocyanates having 6 to 10 carbon atoms and the like. Examples of
(B2) are 1,6-hexamethylene diisocyanate (HDI),
2,2,4-trimethylhexamethylene diisocyanate, lysine diisocyanate, and
the like.
[0074] The alicyclic polyisocyanates (B3) include alicyclic
diisocyanates having 6 to 16 carbon atoms and the like. Examples of
(B3) are isophorone diisocyanate (IPDI), 4,4'-dicyclohexylmethane
diisocyanate, 1,4-cyclohexane diisocyanate, norbornane
diisocyanate, and the like.
[0075] The araliphatic polyisocyanates (B4) include araliphatic
diisocyanates having 8 to 12 carbon atoms and the like. Examples of
(B4) are xylylene diisocyanate,
.alpha.,.alpha.,.alpha.',.alpha.'-tetramethylx- ylylene
diisocyanate, and the like.
[0076] The modified polyisocyanates (B5) include modified materials
of the (B1) to (B4) (carbodiimide modified materials, allophanate
modified materials, urea modified materials, biuret modified
materials, isocyanurate modified materials, oxazolidone modified
materials, and the like). Examples of (B5) are urethane modified
MDI, carbodiimide modified MDI, urethane modified TDI, biuret
modified HDI, isocyanurate modified IPDI, and the like.
[0077] Among these listed as the organic polyisocyanates (B),
preferable are at least one organic polyisocyanate selected from
TDI, MDI, crude TDI, crude MDI, urethane modified TDI, urethane
modified MDI, and carbodiimide modified MDI.
[0078] The blowing agents (C1) as optional components may be at
least one selected from hydrogen atom-containing halogenated
hydrocarbons, water, low boiling point hydrocarbons, and liquefied
carbon dioxide gas. These are used when foaming with blowing
agents.
[0079] Examples of the hydrogen atom-containing halogenated
hydrocarbons include HCFC types (hydrochlorofluorocarbon types)
(e.g. HCFC-123, HCFC-141b, HCFC-22, and HCFC-142b), HFC types
(hydrofluorocarbon types) (e.g. HFC-134a, HFC-152a, HFC-356mff,
HFC-236ea, HFC-245ca, HFC-245fa, and HFC-365mcf), and the like.
Among these, preferable are HCFC-141b, HFC-134a, HFC-356mff,
HFC-236ea, HFC-245ca, HFC-245fa, and HFC-365mcf, and combinations
of two or more of these.
[0080] The low boiling point hydrocarbons usually have a boiling
point of -5 to 70.degree. C., and examples include butane, pentane,
cyclopentane, and mixtures thereof. When a usual rigid urethane
foam is formed by a foaming method with a blowing agent, the
compound (A2) is used as a polyol component. However, because the
solubility of the low boiling point hydrocarbons to the compound
(A2) is low, if the low boiling hydrocarbons are used as blowing
agents, problems may result. For example, the expansion ratio of
the obtained foam may be decreased, or the cells easily become
non-uniform. On the other hand, in the present invention, a
polyurethane foam is formed using the component (A), and the
solubility of the low boiling point hydrocarbons to the component
(A) is increased by using the compound (A1) as an essential
component. Therefore, when the low boiling point hydrocarbons are
used as the blowing agents (C1) in producing the foam [1] of the
present invention, they can be used in large amounts because of
their high solubility to the component (A), and moreover, the
premix of the component (A) and the blowing agents has good
stability. Therefore, it is free of problems such as that the
expansion ratio of the foam may be decreased or non-uniform cells
are easily formed, and thus is beneficial. When using a hydrogen
atom-containing halogenated hydrocarbon compound as the blowing
agent in producing the foam [1] of the present invention, the
amount used is usually not more than 50 mass parts, preferably from
5 to 45 mass parts per 100 mass parts of the component (A). When
using a low boiling point hydrocarbon as the blowing agent in
producing the foam [1] of the present invention, the amount used is
usually not more than 45 mass parts, preferably from 5 to 40 mass
parts per 100 mass parts of the component (A). When using liquefied
carbon dioxide gas as the blowing agent in producing the foam [1]
of the present invention, the amount used is usually not more than
30 mass parts, preferably from 2 to 25 mass parts per 100 mass
parts of the component (A). When using a combination of a hydrogen
atom-containing halogenated hydrocarbon compound and water as the
blowing agent in producing the foam [1] of the present invention,
the amount of the hydrogen atom-containing halogenated hydrocarbon
compound used is usually not more than 45 mass parts, preferably
from 5 to 40 mass parts per 100 mass parts of the component (A),
and the amount of the water used is usually not more than 10 mass
parts, preferably from 0.5 to 8 mass parts per 100 mass parts of
the component (A). When using a combination of a low boiling point
hydrocarbon and water as the blowing agent in producing the foam
[1] of the present invention, the amount of the low boiling point
hydrocarbon used is usually not more than 40 mass parts, preferably
from 2 to 35 mass parts per 100 mass parts of the component (A),
and the amount of the water used is usually not more than 10 mass
parts, preferably from 0.5 to 8 mass parts per 100 mass parts of
the component (A). When using a combination of liquefied carbon
dioxide gas and water as the blowing agent in producing the foam
[1] of the present invention, the amount of the liquefied carbon
dioxide gas used is usually not more than 25 mass parts, preferably
from 0.1 to 20 mass parts per 100 mass parts of the component (A),
and the amount of the water used is usually not more than 10 mass
parts, preferably from 0.5 to 8 mass parts per 100 mass parts of
the component (A). When using water alone as the blowing agent in
producing the foam [1] of the present invention, the amount of the
water used is usually from 0.1 to 30 mass parts, preferably from 1
to 20 mass parts per 100 mass parts of the component (A).
[0081] Examples of the additives (C2) as optional components are
foam stabilizers (C21), urethanation catalysts (C22), inorganic
powders (C23), hollow microspheres (C24), dehydrating agents (C25),
staple fibers (C26), radical-polymerization initiators (C27), chain
transfer agents (C28), dust-scattering reducers (C29), and the
like. The use of these additives is at least partially different
depending on the respective embodiments of foams blown with blowing
agents, mechanical froth foam, and syntactic foam as described
below. Other examples of the additives (C2) as optional components
are polymerization inhibitors, organic lubricants (e.g. calcium
stearate, ethylenediamine stearyl amide, oleic acid monoethanol
amide, etc.), plasticizers (e.g. dioctyl phthalate, dioctyl
adipate, etc.), thixotropy adding agents (e.g. particulate silica),
ultraviolet ray absorbing agents, age resistants, antioxidants,
colorants (dyes, pigments), flame retardants, antifungal agents,
antibacterial agents, and the like.
[0082] The foam stabilizers (C21) may be any materials used in
usual production of polyurethane foams, e.g. dimethyl
siloxane-based foam stabilizer, polyether modified dimethyl
siloxane-based foam stabilizer, phenyl methyl siloxane-based foam
stabilizer, and the like. Examples of the foam stabilizers (C21)
include "SH-193" and "SH-195" (produced by TORAY DOW CORNING
SILICONE CO., Ltd.), "SZ-1627", "SZ-1931", "SZ-1923", and "SZ-1932"
(produced by NIPPON UNICAR COMPANY LTD.", and the like. Among these
preferable are "SZ-1931", "SZ-1923", and "SZ-1932". The amount of
the foam stabilizer (C21) as an optional component is usually not
more than 3%, preferably from 0.1 to 3%, particularly preferably
from 0.2 to 2%, based on the total mass of the polyurethane
foam-forming composition. For example, in the case of a mechanical
froth foam, when using not less than 0.1% of a foam stabilizer
(C21), the effects of finely dispersing and maintaining an inert
gas, which is blown in during the production of the foam, is
improved, so that a molded product with desired density and cell
size is easily obtained. When using not more than 3% of a foam
stabilizer (C21), bleed-out of the foam stabilizer onto the surface
of the molded product is unlikely to occur.
[0083] Examples of the urethanation catalysts (C22) include
amine-based catalysts (e.g. triethylenediamine, N-ethylmorpholine,
diethylethanolamine, bis(dimethylaminoethyl) ether,
N,N,N',N'-tetramethylhexamethylenediamine,
1-isobutyl-2-methylimidazole, 1,8-diazabicyclo-[5,4,0]-undecene-7,
etc.), metal catalysts (e.g. stannous octylate, stannic dibutyl
dilaurate, lead octylate, etc.), and the like. Preferable among
these are triethylenediamine, bis(dimethylaminoethyl) ether,
N,N,N',N'-tetramethylhexamethylenediamine, and stannic dibutyl
dilaurate.
[0084] The amount of the urethanation catalyst (C22) as an optional
component is usually not more than 5%, preferably from 0.001 to
3.5%, particularly preferably from 0.01 to 3% based on the total
mass of the polyurethane foam-forming composition. When the amount
of the catalyst is not less than 0.001%, the speed of the curing
rises, and also the size of the cells in the molded product does
not become large, and the texture of the molded product does not
become coarse. The foam tends to have a finer texture as the amount
of the catalyst increases. However, if the amount of the catalyst
exceeds 5%, the speed of the curing may become too fast, and thus
problems may be caused in the production of the foam.
[0085] The inorganic powders (C23) are used to increase the
dimensional stability or mechanical strength of the molded product,
or to provide flame resistance. The average particle size of the
inorganic powder is preferably not more than 50 .mu.m, particularly
preferably not more than 10 .mu.m when it is intended to improve
the dimensional stability or mechanical strength. Examples of the
inorganic powders (C23) include calcium carbonate, silica, kaoline,
talc, aluminum hydroxide, calcium sulfate, barium sulfate, zinc
white, titanium oxide, crushed stone, alumina, mica, fly ash,
bentonite, ceramic powder, milled fiber, and the like. Preferable
among these are calcium carbonate, aluminum hydroxide, silica, and
talc.
[0086] Because the hollow microspheres (C24) have a cavity inside,
they serve as a factor of forming foam layers, and also are used to
lighten the weight and improve the processability of the molded
product. Examples of such hollow microspheres (C24) include hollow
microspheres comprising thermoplastic resins such as polyvinylidene
chloride, polymethyl methacrylate, and polyacrylonitrile, hollow
microspheres comprising thermosetting resins such as phenol resin,
epoxy resin, and urea resin, microspheres comprising inorganic
materials such as glass, alumina, shirasu, and carbon. Preferable
among these are hollow microspheres comprising thermoplastic resins
or thermosetting resins in view of their processability. The
diameters of the hollow microspheres (C24) are usually from 10 to
200 .mu.m on the average, and the bulk density is usually from 0.01
to 0.5. Examples of the hollow microspheres (C24) include
"Matsumoto Microsphere F-80ED" and "MFL" series (produced by
MATSUMOTO YUSHI-SEIYAKU CO., Ltd.", "phenolic microballoon
BJO-0930" (produced by UNION CARBIDE), "Glass Bubbles K-15" and
"Glass Bubbles K-37" (produced by Scotchlite), and the like.
[0087] The dehydrating agents (C25) are used when forming a
mechanical froth foam or syntactic foam. They are used to prevent
water or moisture from being mixed in the foam-forming composition
and acting as a blowing agent in the urethanation reaction, so that
a fine surface may be provided when the obtained molded product is
processed by cutting. As the dehydrating agents (C25), common
compounds having dehydrating effect may be used, but preferable are
dehydrating agents which are neutral or alkaline and have a
particle diameter of 0.1 to 50 .mu.m. Examples of suitable
dehydrating agents (C25) include calcium oxide, calcium sulfate
(hemihydrate gypsum), calcium chloride, molecular sieve, and the
like. Preferable among these are calcium sulfate (hemihydrate
gypsum) and molecular sieve.
[0088] As the staple fibers (C26), conventional materials used for
reinforcing thermosetting resins may be employed. The staple fibers
(C26) have effects, for example, of improving the dimensional
stability, bending strength, and bending modulus of the molded
product. Furthermore, inorganic materials as the (C26) provide
flame resistance. Examples of the materials of the staple fibers
(C26) include fiber materials, for example, inorganic staple fibers
(C261) such as glass fiber, ceramic fiber, carbon fiber, and rock
wool; natural fibers; and synthetic fibers. Among these preferable
is glass fiber in view of its effectiveness in reinforcing resins.
The thickness of the staple fibers (C26) is preferably from 1 to
10,000 denier, particularly preferably from 10 to 2,000 denier. The
length of the staple fibers (C26) is preferably from 0.1 to 50 mm,
particularly preferably from 0.5 to 20 mm.
[0089] When compounds having a radical-polymerizable functional
group are used as the compound (A1) and as needed as the compound
(A0) to form the foam [1] of the present invention, these compounds
can be brought into reaction in the presence of a
radical-polymerization initiator (C27) as needed. Examples of the
radical-polymerization initiator (C27) include common
radical-polymerization initiators, for example, oil-soluble
radical-polymerization initiators such as azo compounds [e.g.
2,2'-azobisisobutyronitrile,
2,2'-azobis-(2,4-dimethylvaleronitrile),
1,1'-azobis-(1-acetoxy-1-phenylethane), etc.], peroxides [e.g.
dibenzoyl peroxide, benzoyl peroxide, dicumyl peroxide, t-butyl
peroxy benzoate, etc.], and combinations of peroxides and
dimethylaniline (redox catalysts), and water-soluble
radical-polymerization initiators such as azobiscyano valeric acid,
azobisamidinopropane salt, potassium persulfate, and combinations
of sodium persulfate and sodium bisulfite (redox catalysts).
Preferable among these are oil-soluble radical-polymerization
initiators. The amount of the radical-polymerization initiator
(C27) is preferably from 0.0001 to 10 mass parts, more preferably
from 0.0005 to 1 mass parts per 100 mass parts of the total amount
of the (A1) and the (A0) used as needed.
[0090] Furthermore, in the case of radical polymerization, a chain
transfer agent (C28) may be used as needed. Examples of the (C28)
include alkyl mercaptans (e.g. dodecyl mercaptan, mercaptoethanol,
etc.), enol ethers described in Japanese Publication of Unexamined
Patent Application (Tokkai) No. SHO 55-31880, and the like.
Preferable among these are alkyl mercaptans. The amount of the
chain transfer agent (C28) is preferably from 0.0001 to 10 mass
parts, more preferably from 0.0005 to 1 mass parts per 100 mass
parts of the total amount of the (A1) and the (A0) used as
needed.
[0091] In the case of a rigid polyurethane foam that is processed
by cutting, a dust-scattering reducer (C29) may be added as needed.
Because a dust-scattering reducer (C29) contained in the foam
inhibits the scattering in the air of dust generated when the foam
is cut, it is preferable that the foam contains the (C29) when its
density is low. Examples of the dust-scattering reducer (C29)
include esterified materials and etherified materials in which the
hydroxyl groups at both ends of a polyalkylene glycol are enclosed
by a fatty acid or a higher alcohol. Examples of the polyalkylene
glycols are homopolymers of EO or PO, and block or random
copolymers comprising EO and PO. Preferable among these are
homopolymer of EO and block copolymers comprising EO and PO. The
molecular weight of the polyalkylene glycol is: in the case of
polyethylene glycol (hereinafter abbreviated as PEG), usually from
200 to 1000, preferably from 200 to 600; in the case of
polypropylene glycol (hereinafter abbreviated as PPG), usually from
200 to 4000, preferably from 200 to 1000; and in the case of a
copolymer comprising EO and PO (hereinafter abbreviated as PEPG),
usually from 400 to 5000, preferably from 1000 to 3000. Examples of
the above-mentioned fatty acids include saturated or unsaturated
fatty acids having 8 to 18 carbon atoms. Examples of the saturated
fatty acids include caprylic acid, capric acid, lauric acid,
myristic acid, palmitic acid, stearic acid, and the like. Examples
of the unsaturated fatty acids include oleic acid, linoleic acid,
linolenic acid, and the like. Preferable among these are lauric
acid and oleic acid. Examples of the above-mentioned higher alcohol
are saturated or unsaturated alcohols having 8 to 18 carbon atoms.
Examples of the saturated alcohols include lauryl alcohol, myristyl
alcohol, cetyl alcohol, stearyl alcohol, and the like. Examples of
the unsaturated alcohols include oleyl alcohol and the like.
Preferable among these are lauryl alcohol, stearyl alcohol, and
oleyl alcohol. The dust-scattering reducers (C29) may be used
either alone or in combination of two or more types. The (C29) may
be a solid form, but it is desirable to be either a liquid or paste
form at 20.degree. C., so that its effect of inhibiting
dust-scattering may be increased. A combination of two or more
types of the dust-scattering reducers (C29), in which at least one
in the combination is a liquid or paste form also may be employed.
Among these dust-scattering reducers (C29) particularly preferable
are dilauric acid ester and dioleic acid ester of PEG (molecular
weight of 200 to 600).
[0092] One embodiment of the polyurethane foam [1] of the present
invention is a rigid polyurethane foam [I] in which the component
(A) satisfies the requirement that the M value expressed by the
formula (2) below is not more than 500
M=J/(K+L.times.2-2) (2)
[0093] wherein J denotes the (number average) molecular weight of
the component (A); K denotes the (average) number of the active
hydrogen-containing group per molecule of the (A); and L denotes
the (average) number of the addition-polymerizable functional group
per molecule of the (A).
[0094] The M value of the (A) used in the foam [I] is preferably
not more than 300, more preferably not more than 250, particularly
preferably from 50 to 200. If the M value exceeds 500, the
mechanical strength becomes low as a rigid foam.
[0095] As the compound (A2) that is used in the rigid polyurethane
foam [I] as needed, those comprising at least one selected from
polyether polyols, polyester polyols, polyhydric alcohols, and
amines [e.g. diamines, polyamines, and alkanolamines] are
preferably used. The value (on the average) of the active
hydrogen-containing groups (hydroxyl value in the case of polyols)
in the compound (A2) used in the foam [I] is preferably from 200 to
1000, more preferably from 250 to 700, particularly preferably from
300 to 650. In the case of the foam [I], when the value (on the
average) of the active hydrogen-containing groups in the compound
(A2) is not less than 200, the heat resistance and the strength of
the obtained foam becomes high. When the value is not more than
1000, the molded product does not become too hard and brittle, and
also scorch due to reaction heat may not be generated in the
foam.
[0096] Furthermore, one embodiment of the rigid polyurethane foam
[I] is a rigid polyurethane foam [Ia] having a density of 5 to 900
kg/m.sup.3, which is formed using as auxiliaries (C) a blowing
agent (C1) and as needed a foam stabilizer (C21) and/or an
urethanation catalyst (C22) as additives (C2). The density of the
foam [Ia] is preferably from 10 to 500 kg/m.sup.3, particularly
preferably from 20 to 200 kg/m.sup.3.
[0097] By further using an inorganic powder (C23) and/or an
inorganic staple fiber (C261) as additives (C2) in the foam [Ia], a
flame-resistant rigid polyurethane foam can be obtained. The amount
of the (C23) and/or the (C261) used to provide the foam with flame
resistance is preferably from 9 to 40%, particularly preferably
from 20 to 35% based on the total mass of the foam-forming
composition. When the amount of the (C23) and/or the (C261) is not
less than 9%, flame resistance is improved. When the amount is not
more than 40%, the mechanical strength of the foam is not
decreased.
[0098] Another embodiment of the foam [I] is a rigid polyurethane
foam [Ib] which obtained by carrying out a polyurethane-forming
reaction by a mechanical froth method without using as auxiliaries
(C) a blowing agent (C1) but using inorganic powder (C23) and/or
hollow microsphere (C24), a dehydrating agent (C25), and as needed
a foam stabilizer (C21) and/or an urethanation catalyst (C22) as
additives (C2).
[0099] In the mechanical froth foaming method, the inorganic powder
(C23) and/or hollow microsphere (C24) serve as nucleating agents
when an inert gas is made into fine bubbles and dispersed in the
polyurethane foam-forming composition by mechanical stirring, and
play a role in keeping the bubbles stabilized. The density of the
foam [Ib] is usually from 100 to 1800 kg/m.sup.3, preferably from
200 to 1200 kg/m.sup.3, particularly preferably from 300 to 1000
kg/m.sup.3.
[0100] Still another embodiment of the foam [I] is a rigid
polyurethane foam [Ic] produced by forming a syntactic foam without
using as auxiliaries (C) a blowing agent (C1) but using a hollow
microsphere (C24), a dehydrating agent (C25), and as needed an
inorganic powder (C23) as additives (C2).
[0101] The density of the foam [Ic] is usually from 100 to 1800
kg/m.sup.8, preferably from 200 to 1200 kg/m.sup.3, particularly
preferably from 300 to 1000 kg/m.sup.3.
[0102] The rigid polyurethane foams [Ib] and [Ic] have advantages
in that they are of light weight and have an even density
distribution, and exhibit a fine surface when cut, and that
reduction in the mechanical properties is small when their density
is decreased.
[0103] In the foams [Ib] and [Ic], the inorganic powder (C23) and
hollow microsphere (C24) are used as fillers. The inorganic powder
is useful to increase the dimensional stability and material
strength of the foam and to improve the flame resistance. The
hollow microsphere is useful for lightening the weight or improving
the processability of the molded product. Therefore, the amounts
should be chosen depending on the use of the foam. For example, to
improve the strength or dimensional stability of the foam, the
amount of the inorganic powder may be increased. And to obtain a
molded product that has a low density and is easy to cut, the
amount of the hollow microsphere may be increased. The amount of
the filler comprising the inorganic powder (C23) and hollow
microsphere (C24) is usually from 2 to 60%, particularly preferably
from 5 to 40% based on the total mass of the foam-forming
composition. When the amount of the filler is not less than 2%, the
bubbles generated in the mechanical froth foaming method are
sufficiently maintained. When the amount of the filler is not more
than 50%, the viscosity of the foam-forming composition does not
become too high, so that production become easy.
[0104] In the foams [Ib] and [Ic], because the dehydrating agent
(C25) is added to prevent blowing caused by moisture in the
foam-forming composition, e.g. moisture in the fillers, during the
urethanation reaction, its amount should be adjusted depending on
the content of the moisture in the composition. It is also
necessary to increase the amount of the dehydrating agent (C25)
when the amount of the fillers is large. The amount of the
dehydrating agent (C25) is usually from 0.5 to 8%, preferably from
0.8 to 6% based on the total mass of the foam-forming composition.
When the amount of the dehydrating agent is not less than 0.5%,
blowing is not caused by the absorbed moisture during the curing
reaction, so that the obtained molded product exhibits a fine
texture. Furthermore, when the amount of the dehydrating agents is
not more than 8%, the molded product has good cutting
workability.
[0105] In the foams [Ib] and [Ic], a dust-scattering reducer (C29)
may be optionally added. The (C29) reduces the amount of the dust
scattering when the molded product is cut. There is a tendency that
the amount of the scattering dust increases as the density of the
molded product decreases. Therefore, when the molded product has a
low density, it is desirable that the (C29) is contained in a
relatively large amount. The amount of the (C29) is usually from 3
to 30%, preferably from 5 to 20% based on the total mass of the
foam-forming composition. When the amount of the (C29) is not less
than 3%, the amount of the scattering dust decreases sufficiently.
When the amount is not more than 30%, hardness and heat resistance
of the molded product are not affected.
[0106] The foams [Ib] and [Ic] can be processed by cutting into
desired shapes to produce cut moldings. The methods of the cutting
include hand working using chisel, saw, plane or the like, and
machine working using a CNC machine or the like.
[0107] The foams [Ia] to [Ic] may be rigid polyurethane foams that
further contain staple fiber (C26) as an additive (C2). By using
the staple fiber (C26), a rigid foam with high bending strength and
high bending modulus can be obtained.
[0108] Particularly, because in the present invention the component
(A) contains the compound (A1) and as needed the compound (A0),
which reduce the viscosity of the composition, a staple
fiber-reinforced foam having stronger mechanical strength may be
produced by increasing the content of the staple fiber than in a
conventional case. For example, when producing a mechanical froth
foam [Ib], even if the amount of the staple fiber used in the
composition is increased, the viscosity of the composition does not
become as high as in a conventional case. Thus, mechanical stirring
can be conducted sufficiently, so that inert gas is uniformly
dispersed. Therefore, the obtained foam has high mechanical
strength. Accordingly, a mechanical froth foam that can be applied
to repeated uses such as materials of molds or to uses subject to a
bending stress can be provided. When the foam is reinforced with
staple fiber, the amount of the staple fiber (C26) is usually not
more than 50 mass %, preferably from 10 to 50 mass %, particularly
preferably from 20 to 40 mass % based on the total mass of the
foam-forming composition. When the amount of the (C26) is not less
than 10 mass %, its effect of reinforcing the resin is increased.
When the amount is not more than 50 mass %, defects are not
generated in the foam and a homogeneous foam can be obtained.
Furthermore, when the foams [Ib] and [Ic] are reinforced with
staple fiber, in order not to make the viscosity of the composition
too high, the total amount of the staple fiber (C26), inorganic
powder (C23), and hollow microsphere (C24) is usually not more than
60 mass %, preferably from 10 to 60 mass %, particularly from 20 to
50 mass % based on the total mass of the foam-forming composition.
When the staple fiber (C26) is contained in the foams [Ib] and [Ic]
as their components, staple fiber-reinforced rigid polyurethane
foams, which have an even density distribution, which are of light
weight and excellent in dimensional stability, and which exhibit
fine surfaces when cut, and have high bending strength and high
bending modulus, can be obtained.
[0109] Because the rigid polyurethane foam [I] has high strength,
good thermal insulation and flame resistance, and particularly
excellent dimensional stability, it can be used in a wide range of
applications utilizing these characteristics. The uses of the rigid
polyurethane foam [I] include refrigerators, freezers, thermal
insulators for construction etc., shock-absorbing materials,
synthetic woods (including for structural materials, materials for
models, etc.), and the like.
[0110] Another embodiment of the polyurethane foam [1] of the
present invention is a flexible polyurethane foam [II] that has a
density of 10 to 500 kg/m.sup.3 and in which the component (A)
satisfies the requirement that the M value expressed by the above
formula (2) is at least 500.
[0111] The M value of the component (A) used in the foam [II] is
preferably at least 800, more preferably at least 1,000,
particularly preferably from 1,100 to 15,000. If the M value is
less than 500, the flexibility becomes inadequate as a flexible
foam. Furthermore, the density of the foam [II] is preferably from
15 to 200 kg/m.sup.3, particularly preferably from 20 to 100
kg/m.sup.3.
[0112] The value (on the average) of the active hydrogen-containing
groups (hydroxyl value in the case of polyols) in the compound (A2)
used in the foam [II] as needed is preferably from 4 to 200, more
preferably from 10 to 150, particularly preferably from 15 to 120.
When the value (on the average) of the active hydrogen-containing
groups is within the above-mentioned range, a foam that has
flexibility and in which the compression set is small enough can be
obtained. Moreover, those preferable as the compound (A2) are the
same as in the case of the foam [I].
[0113] One embodiment of the flexible polyurethane foam [II] is a
flexible polyurethane foam that is formed using as auxiliaries (C)
a blowing agent (C1) and as needed a foam stabilizer (C21) and/or
an urethanation catalyst (C22) as additives (C2). Moreover, by
further using inorganic powder (C23) and/or inorganic staple fiber
(C261) as additives (C2), a flame-resistant flexible polyurethane
foam can be obtained. The amounts of the (C23) and/or the (C261)
used are the same as in the case of the above-mentioned foam
[Ia].
[0114] The flexible polyurethane foam [II] is advantageous because
it has good hardness so that its density may be lowered, and also
it has small compression set. Therefore, it can be used in a wide
variety of applications utilizing these characteristics. The
flexible polyurethane foam [II] can be used as a cushioning
material, shock-absorbing material, sound insulating/absorbing
material, etc.
[0115] One example of the method for producing the polyurethane
foam [Ia] by blowing with a blowing agent according to the present
invention is as follows: First, a component (A), a blowing agent
(C1), and as needed at least one additive (C2) are mixed in
predetermined amounts. Then, using a polyurethane foaming machine
or an agitator, the mixture is mixed with an organic polyisocyanate
(B) rapidly. The obtained mixture solution (a foam base solution)
is poured into a mold. After curing for a predetermined period, it
is removed from the mold to obtain a polyurethane foam.
[0116] Furthermore, a polyurethane foam can be obtained by spray
foaming or continuous foaming. Moreover, in a prepolymer method,
the viscosity of the foam base solution in which individual
components are mixed becomes high in the urethanation reaction.
Therefore, a one shot process is preferably employed.
[0117] Moreover, the NCO index (equivalent number of isocyanate
group per one equivalent of active hydrogen-containing
group.times.100) when producing the foam [Ia] is preferably from 40
to 500, particularly preferably from 60 to 250. If the NCO index is
less than 40, the calorific value become low during the blowing.
Thus, the expansion ratio may become small, the mechanical strength
of the foam may be decreased, or the dimensional stability of the
foam may be deteriorated. On the other hand, if the NCO index is
more than 500, the foam may become brittle. Moreover, in a common
process of forming a polyurethane foam, only the compound (A2) is
employed as the polyol component, and the NCO index is usually at
least 80. This is because, if the NCO index is decreased,
mechanical strength is reduced, or dimensional stability is
deteriorated. In the process of the present invention, however,
because of the use of the self-polymerizable compound (A1), even
when the NCO index is small, the crosslinking density becomes
higher than in common urethane foams, and the decrease in the
mechanical strength of the foam is small. Thus, even when only
water is used as a blowing agent, if the NCO index is decreased,
the amount of the organic isocyanate with respect to the polyol
does not become large, so that a mixing deficiency is unlikely to
occur during the blowing.
[0118] One example of the process for forming the mechanical froth
foam [Ib] or syntactic foam [Ic] of the present invention is as
follows: A foam-forming composition is usually produced by
preparing two components separately, i.e. a component comprising
the component (A) (hereinafter referred to as an active hydrogen
component in the description of this process) and a component
comprising the organic polyisocyanate (B) (hereinafter referred to
as the NCO component in the description of this process). The
active hydrogen component and the NCO component are prepared by
mixing respective raw materials using a mixing vessel having a
mixing blade such as of a propeller or paddle type, or using a
planetary mixer, Hobart mixer, or the like. In the foams [Ib] and
[Ic], fillers such as inorganic powder and hollow microsphere,
dehydrating agents, dust-scattering reducers, foam stabilizers,
urethanation catalysts, and the like are usually contained in the
active hydrogen component, but they also may be contained in the
NCO component. Particularly, when a large amount of fillers is
contained, it is preferable that a portion of the fillers is
contained in the NCO component. In such a case, by adding a
dehydrating agent in the NCO component depending on the content of
the fillers in the NCO component, deterioration with age (increased
viscosity) of the NCO component can be prevented. Materials such as
colorants or catalysts that are used in small amounts may be added
preliminarily to the active hydrogen component, but they also may
be added into the mixing machine at the same time when the active
hydrogen component and the NCO component are mixed and molded
through curing. The foams [Ib] and [Ic] are obtained by causing
reaction in a composition comprising the active hydrogen component
and the NCO component to polymerize the addition-polymerizable
functional group and simultaneously form a polyurethane in the
absence of a blowing agent.
[0119] Furthermore, when producing the foams [Ib] and [Ic], the NCO
index is preferably from 40 to 500, more preferably from 60 to 250,
particularly preferably from 85 to 120. If the NCO index is less
than 40, the mechanical strength of the foams may be decreased, or
the coefficient of linear expansion may be increased. On the other
hand, if the NCO index is more than 500, the foams may become hard
and brittle.
[0120] The process for producing the mechanical froth foam [Ib] in
which an inert gas is mixed and the process for producing the
syntactic foam [Ic] in which an inert gas is not mixed according to
the present invention are, for example, the procedures as follows,
respectively.
[0121] In the process in which an inert gas is mixed:
[0122] (1) An active hydrogen component and a NCO component are
prepared according to the above-mentioned processes.
[0123] (2) The active hydrogen component, the NCO component, and an
inert gas are mixed uniformly in a certain ratio, and the mixture
liquid is poured into a mold.
[0124] (3) After curing the mixture liquid in the mold, it is
removed from the mold to obtain a mechanical froth foam [Ib].
[0125] In this process, it is preferable to use, for example, a
mechanical froth method, i.e. a method in which a mixer with a high
shearing force such as an Oakes mixer is used, to mix the active
hydrogen component, the NCO component, and the inert gas uniformly.
The mechanical froth method is suitable for continuously mixing a
gas into a liquid ingredient.
[0126] Examples of the inert gas mixed are those that will not
react with the active hydrogen component or with the NCO component,
and that are not in a liquid state under the atmospheric pressure
at a temperature of -30.degree. C. Preferable are air, nitrogen,
and carbon dioxide gas. The amount of the inert gas mixed is
usually from 10 to 70%, preferably from 20 to 60% based on the
total volume of the inert gas and the entire composition.
[0127] In the process in which an inert gas is not mixed:
[0128] (1) An active hydrogen component and a NCO component are
prepared according to the above-mentioned processes.
[0129] (2) The active hydrogen component and the NCO component are
mixed uniformly in a certain ratio, and the mixture liquid is
poured into a mold.
[0130] (3) Defoaming under a reduced pressure is performed, and the
bubbles contained in the mixture liquid in the mold are
removed.
[0131] (4) After curing the mixture liquid in the mold, it is
removed from the mold to obtain a syntactic foam [Ic].
[0132] In this process, the mixing is performed by stirring with a
mixing blade such as a propeller type, flat blade type, curved
blade type, Pfaudler type, paddle type, or the like in a mixing
vessel, or by using a mixing machine such as a screw type, kneader
type, universal type, etc. Usually, a mixing machine of either
screw or kneader type is employed.
[0133] The polyurethane foam [2] of the present invention is an
elastic polyurethane foam obtained by reacting an
addition-polymerizable active hydrogen component (A') mentioned
below with an organic polyisocyanate (B) in the presence or absence
of at least one auxiliary (C) selected from the group consisting of
blowing agents (C1) and additives (C2) to polymerize the
addition-polymerizable functional group and simultaneously form a
polyurethane.
[0134] Addition-polymerizable active hydrogen component (A'): an
addition-polymerizable active hydrogen component, which comprises
an active hydrogen-containing group (w) and an
addition-polymerizable functional group (x), and which is selected
from the (A31), (A32), and (A33) below; wherein the reaction rate
constant K1 between the active hydrogen-containing group (w) and an
isocyanate group (z) at 120.degree. C is not more than 1
(liter/mol/sec); polymerization reaction rate constant K2 of the
addition-polymerizable functional group (x) is not less than 10
(liter/mol/sec); and K2/K1 is not less than 100.
[0135] (A31): an addition-polymerizable active hydrogen compound
that has an active hydrogen-containing group (w) and an
addition-polymerizable functional group (x), and which may have a
cyclic group (y) reactive with the group (w).
[0136] (A32): an active hydrogen compound (A321) having at least
three groups (w) or having the groups (w) and (y), and an
addition-polymerizable compound (A322) having the groups (x) and
(y), used in combination.
[0137] (A33): the compound (A31), and the compound (A321) and/or
the compound (A322), used in combination.
[0138] In producing the foam [2] of the present invention, the
addition polymerization of the addition-polymerizable functional
group (x) and the urethanation reaction between the isocyanate
group in the organic polyisocyanate (B) and the active
hydrogen-containing group (w) are carried out in the same reaction
system. Moreover, in the present invention, it is understood that
to polymerize the addition-polymerizable functional group and
simultaneously form a polyurethane means that the polymerization of
the addition-polymerizable functional group and the
polyurethane-forming reaction are carried out simultaneously at
least partially during the reaction period. In order to improve the
mechanical properties with increased crosslinking density, it is
preferable that the other reaction is initiated before a resin is
formed through curing in one reaction, so that the two reactions
are carried out at the same time.
[0139] The active hydrogen-containing group (w) used in the foam
[2] of the present invention has a reaction rate constant K1
between the group (w) and isocyanate group of not more than 1
(liter/mol/sec) at 120.degree. C. Examples of such an active
hydrogen-containing group (w) are hydroxyl, mercapto, carboxyl,
primary amino, and secondary amino groups, and the like. Preferable
among these are hydroxyl or mercapto group, particularly preferably
hydroxyl group.
[0140] As the addition-polymerizable functional group (x) used in
the present invention, an addition-polymerizable functional group
which has a polymerization reaction rate constant K2 of not less
than 10 (liter/mol/sec) at 120.degree. C., K2/K1 being not less
than 100, may be employed. Examples of such an
addition-polymerizable functional group (x) are
radical-polymerizable groups, cationic-polymerizable groups, and
anionic-polymerizable groups. Preferable among these are
radical-polymerizable groups.
[0141] Examples of the radical-polymerizable groups include
acryloyl, methacryloyl, vinyl ester, vinylbenzyl, vinylphenyl,
vinylidene, and allyl ether groups, and the like. Preferable among
these are acryloyl or methacryloyl group. Examples of the
cationic-polymerizable groups include vinyl ether group, propenyl
ether group, and the like. Examples of the anionic-polymerizable
groups include vinylcarboxyl group, cyanoacryloyl group, and the
like. Examples of the cyclic group (y) reactive with the group (w)
include epoxy group, anhydrous maleyl group, and the like.
Preferable among these is an epoxy group.
[0142] The number of the active hydrogen-containing groups (w) in
the above-mentioned addition-polymerizable active hydrogen compound
(A31) is usually from 1 to 10, preferably from 2 to 5. Furthermore,
the number of the addition-polymerizable functional groups (x) in
the compound (A31) is usually from 1 to 10, preferably from 1 to 5.
Furthermore, the number of the cyclic groups (y) in the compound
(A31) is usually 0 or from 1 to 5, preferably from 0 to 2.
[0143] Examples of a compound (A311) having an active
hydrogen-containing group (w) and addition-polymerizable functional
group (x) in one molecule among the compounds (A31) include the
same compounds as the compound (A1) used in the above-mentioned
foam [1].
[0144] Examples of a compound (A312) having the groups (w), (x),
and (y) in one molecule among the compounds (A31) include partially
glycidyl-etherified partial esters of unsaturated carboxylic acids
with polyols. Examples of the partial esters of unsaturated
carboxylic acids with polyols include the same compounds as the
compound (A1/1) used in the above-mentioned foam [1]. The partially
glycidyl-etherified materials mentioned above as examples of the
compound (A312) are obtained by partial esterification and partial
glycidyl-etherification of polyols, which are performed either
sequentially or simultaneously, using unsaturated carboxylic acids
and epichlorohydrin.
[0145] It is preferable that the relationship between the (number
average) molecular weight W and the total number F of the groups
(w), (x) and (y) in one molecule is W/F>-1000 in the compound
(A31), so that the elasticity of the urethane foam is easily
maintained when the amount of the (A31) used is increased. It is
particularly preferable that W/F is from 1200 to 5000.
[0146] A compound (A321) is either a compound (A321/0) having at
least three groups (w) and not having the group (y), or an active
hydrogen compound having the groups (w) and (y). The number of the
group (w) in the (A321/0) is usually from 3 to 10, preferably from
3 to 6. Moreover, in the compounds (A321) other than the (A321/0),
the number of the group (w) is usually from 1 to 10, preferably
from 2 to 6, and the number of the group (y) is usually from 1 to
5, preferably from 1 to 2. The group (y) reacts with the group (w)
contained in the compound (A31) or (A32) rapidly to form a bond
therebetween as well as to form a new active hydrogen-containing
group (w'). Therefore, in the case of the active hydrogen compound
having the groups (w) and (y), the number of the group (w) may be
from 1 to 10 but in the case of the compound (A321/0) not having
the group (y), it is necessary that the number of the group (w) is
from 3 to 10.
[0147] The compound (A321/0) among the compounds (A321) may be at
least one selected from known polyether polyols, polyester polyols,
polyhydric alcohols, and amines [polyamines and alkanolamines]
commonly used in polyurethane foams as listed above in the
description of the foam [1], in which the number of the active
hydrogen-containing groups is within the above-mentioned range.
[0148] Examples of an active hydrogen compound having the groups
(w) and (y) among the compounds (A321) include the (A321/1) to
(A321/4) as follows:
[0149] (A321/1) Partially glycidyl-etherified polyols
[0150] (A321/2) Partially glycidyl-thioetherified polythiols
[0151] (A321/3) Epoxides having hydroxyl groups
[0152] (A321/4) Substituted maleic anhydrides having hydroxyl
groups
[0153] The compounds (A321/1) can be obtained by reacting the
above-mentioned polyols with compounds containing epoxy groups such
as glycidol or epichlorohydrin.
[0154] The compounds (A321/2) can be obtained by reacting the
above-mentioned polythiols with compounds containing epoxy groups
such as glycidol or epichlorohydrin.
[0155] Examples of the compounds (A321/3) include glycidol and the
like.
[0156] Examples of the compounds (A321/4) include hydroxyethyl
maleic anhydride and the like.
[0157] In the present invention, a vinyl polymer (F) may be
dispersed in the compound (A321) as needed. The polymer (F) may be
dispersed in the compound (A321) after it is polymerized, but
preferably it is dispersed and stabilized by polymerizing a
vinyl-based monomer (f) in the (A321). Examples of the monomer (i)
include acrylonitrile, styrene, vinylidene chloride, alkyl
(meth)acrylate, and the like. Preferable among these are
acrylonitrile and styrene. The amount of the polymer (F) is usually
from 5 to 50 mass parts, preferably from 15 to 45 mass parts per
100 mass parts of the compound (A321).
[0158] The compound (A322) is an addition-polymerizable compound
having an addition-polymerizable functional group (x) and a cyclic
group (y). The number of the group (x) in the compound (A322) is
usually from 1 to 10, preferably from 1 to 5. Furthermore, the
number of the cyclic group (y) in the compound (A322) is usually
from 1 to 5, preferably from 1 to 2.
[0159] Examples of the compound (A322) include glycidyl acrylate,
glycidyl methacrylate, maleic anhydride, and the like. The groups
(y) in the compound (A322) are suitable for increasing the reaction
rate because they react with the groups (w) contained in the
compound (A31) or (A32) rapidly to form a bond therebetween as well
as to form a new active hydrogen-containing group (w'). However,
because the group (w') has a large steric hindrance, unreacted
active hydrogen-containing groups may remain, or its ring may open
independently by reacting with water due to the effect of an amine
catalyst, which may be used as a catalyst of urethanation reaction,
and deteriorates the properties of the foam without contributing to
the crosslinking. Therefore, it is preferable that the
addition-polymerizable active hydrogen component (A') comprises the
addition-polymerizable active hydrogen compound (A31) or comprises
the compound (A31) and the active hydrogen compound (A321).
[0160] When the component (A') comprises the above-mentioned (A31)
or (A33), it is preferable that the (A31) is from 1 to 100 mass %,
the (A321) is from 0 to 99 mass %, and the (A322) is from 0 to 50
mass % based on the total mass of the (A31), (A321) and (A322). It
is particularly preferable that the (A31) is from 5 to 100 mass %,
the (A321) is from 0 to 95 mass %, and the (A322) is from 0 to 30
mass %.
[0161] When the component (A') comprises the above-mentioned (A32),
it is preferable that the (A321) is from 50 to 99 mass %, and the
(A322) is from 1 to 50 mass % based on the total mass of the (A321)
and (A322). It is particularly preferable that the (A321) is from
70 to 98 mass % and the (A322) is from 2 to 30 mass %.
[0162] In the present invention, an elastic urethane foam that is
produced by reacting a component comprising the compound (A31) used
as the component (A') [including the case in which a compound other
than the (A31) is also contained] and a polyisocyanate component as
essential components has a M' value expressed by the formula below
of usually at least 500, preferably at least 800, more preferably
at least 1000, particularly preferably from 1,100 to 15,000:
M' value=J'/(K'+L'.times.2-2)
[0163] wherein J' denotes the (number average) molecular weight of
the addition-polymerizable active hydrogen component comprising the
compound (A31), K' denotes the (average) number of the group (w)
per molecule, and L' denotes the (average) number of the group (x)
per molecule.
[0164] If the M' value is less than 500, the flexibility of the
elastic polyurethane foam is reduced.
[0165] Examples of the organic polyisocyanate (B) used in the foam
[2] of the present invention include the same compounds as in the
above-mentioned foam [1], and those preferable are also the same as
in the above-mentioned foam [1].
[0166] When producing the foam [2] of the present invention, in the
case of using a compound having a radical-polymerizable unsaturated
group as the addition-polymerizable functional group, reaction can
be carried out in the presence or absence of a
radical-polymerization initiator or a chain transfer agent as in
the process for producing the foam [1]. Also, the types of the
radical-polymerization initiator or the chain transfer agent that
may be employed, their amounts used, or those preferable are the
same as in the process for producing the foam [1].
[0167] At least one selected from the group consisting of water,
hydrogen atom-containing halogenated hydrocarbon, low boiling point
hydrocarbon, and carbon dioxide may be used as a blowing agent as
needed. In terms of preventing harmful effects to the earth
environment and maintaining the working environment, water or
carbon dioxide is preferably used. There has been a conventional
problem that hardness is more difficult to develop when using
carbon dioxide as a blowing agent than when using water. However,
because hardness can be improved in the present invention, carbon
dioxide also may be preferably employed as a blowing agent.
[0168] In the same way as in the process for producing the foam
[1], urethanation catalysts and foam stabilizers may be used as
needed, and the types and the amounts used thereof are also the
same.
[0169] Furthermore, in the same way as in the foam [1], various
known additives and auxiliaries, e.g. surfactants such as
emulsifiers and foam stabilizers, age resistors such as antioxiants
and ultraviolet ray absorbing agents, inorganic powders such as
calcium carbonate and barium sulfate, staple fibers such as glass
fiber, carbon fiber, and potassium titanate whisker, flame
retardants, plasticizers, polymerization inhibitors, colorants,
antibacterial agents, antifungal agent, and the like may be used as
needed.
[0170] One example of the process for producing the polyurethane
foam [2] of the present invention is as follows: First, an
addition-polymerizable active hydrogen component (A') is mixed with
a blowing agent, foam stabilizer, catalyst, radical-polymerization
initiator, and other additives in predetermined amounts as needed.
Then, using a polyurethane foaming machine or an agitator, this
mixture is admixed with an organic polyisocyanate (B) rapidly. The
obtained mixture solution (foam base solution) is poured into a
mold, and after curing for a predetermined period, it is removed
from the mold to obtain a polyurethane foam. Furthermore, a
polyurethane foam may be obtained by spray foaming or continuous
foaming. Moreover, in a prepolymer method, the viscosity of the
foam base solution in which individual components are mixed becomes
high in the urethanation reaction. Therefore, a one shot process is
preferably employed. Furthermore, the polyurethane foam also may be
obtained by a mechanical froth method without using a blowing
agent.
[0171] Moreover, the NCO index in the case of producing the foam
[2] is preferably from 40 to 500, particularly preferably from 60
to 250. If the NCO index is less than 40, the expansion ratio may
become small due to the small calorific value during the blowing,
or the mechanical strength of the foam may be decreased. On the
other hand, if the NCO index exceeds 500, the foam may become
brittle.
[0172] The polyurethane foam [2] of the present invention can be
used as a cushioning material, shock-absorbing material, sound
insulating/absorbing material, etc.
BEST MODES FOR CARRYING OUT THE INVENTION
[0173] The present invention will be further described by referring
to the following non-limiting Examples and Comparative
Examples.
[0174] In the following Examples and Comparative Examples, the
"part" means "mass part" unless specified otherwise.
[0175] Evaluations of the Polyurethane Foams [Ia] and [II]
PRODUCTION EXAMPLE 1
Production of Glycerol Monoacrylate
[0176] Using 0.3 g (0.003 mole) of sulfuric acid as a catalyst, 72
g (1 mole) of acrylic acid was reacted with 92 g (1 mole) of
glycerol. The reaction mixture was neutralized with 0.34 g (0.006
mole) of potassium hydroxide, and 0.15 g (0.1 mass %) of
hydroquinon was added as a stabilizer. Thus, glycerol monoacrylate
(A1-1) was obtained.
PRODUCTION EXAMPLE 2
Production of Glycerol Diacrylate
[0177] Using 0.6 g (0.006 mole) of sulfuric acid as a catalyst, 144
g (2 moles) of acrylic acid was reacted with 92 g (1 mole) of
glycerol. The reaction mixture was neutralized with 0.68 g (0.012
mole) of potassium hydroxide, and 0.20 g (0.1 mass %) of
hydroquinon was added as a stabilizer. Thus, glycerol diacrylate
(A1-2) was obtained.
PRODUCTION EXAMPLE 3
Production of Pentaerythritol PO 4-molar Adduct Triacrylate)
[0178] Using 0.9 g (0.009 mole) of sulfuric acid as a catalyst, 216
g (3 moles) of acrylic acid was reacted with 368 g (1 mole) of a
polyol (hydroxyl value of 610) in which 4 moles of PO was added to
1 mole of pentaerythritol. The reaction mixture was neutralized
with 1.01 g (0.018 mole) of potassium hydroxide, and 0.53 g (0.1
mass %) of hydroquinon was added as a stabilizer. Thus,
pentaerythritol PO 4-molar adduct triacrylate (A1-3) was
obtained.
PRODUCTION EXAMPLE 4
Production of Sorbitol EO 6-molar Adduct Tetraacrylate)
[0179] Using 1.2 g (0.012 mole) of sulfuric acid as a catalyst, 288
g (4 moles) of acrylic acid was reacted with 446 g (1 mole) of a
polyol (hydroxyl value of 755) in which 6 moles of EO was added to
1 mole of sorbitol. The reaction mixture was neutralized with 1.35
g (0.024 mole) of potassium hydroxide, and 0.60 g (0.1 mass %) of
hydroquinon was added as a stabilizer. Thus, sorbitol EO 6-molar
adduct tetraacrylate (A1-4) was obtained.
PRODUCTION EXAMPLE 5
Production of Diethylene Glycol Monoacrylate
[0180] Using 0.3 g (0.003 mole) of sulfuric acid as a catalyst, 72
g (1 mole) of acrylic acid was reacted with 106 g (1 mole) of
diethylene glycol. The reaction mixture was neutralized with 0.34 g
(0.006 mole) of potassium hydroxide, and 0.16 g (0.1 mass %) of
hydroquinon was added as a stabilizer. Thus, diethylene glycol
monoacrylate (A1-5) was obtained.
EXAMPLE 1
Production of a Rigid Urethane Foam by Blowing with Water Alone
[0181] 100 parts of glycerol monoacrylate (Al-1), 1.5 parts of
"SILICONE SH-193" (a silicone-based foam stabilizer produced by
TORAY DOW CORNING SILICONE CO., Ltd.), 7 parts of water, 10 parts
of "FYROL CEF" (organic phosphorus-based flame retardant produced
by AKZO JAPAN CO., Ltd.), and 2.0 parts of "Ucat-1000" (a
N,N,N',N'-tetramethylhexamethylenediamine-bas- ed amine catalyst
produced by SAN APRO CO., Ltd.) were mixed, and controlled at a
temperature of 25.degree. C. To this mixture liquid, 203.7 parts of
crude MDI (NCO index of 70) controlled at 25.degree. C. was added
and stirred by "Homodisper" (an agitator manufactured by TOKUSHU
KIKA INDUSTRIES Ltd.) at 4000 rpm for 10 seconds. Then, it was
poured into an aluminum mold of 1000 mm (length).times.100 mm
(width).times.50 mm (height) controlled at 60.degree. C. After 10
minutes, it was removed from the mold to obtain a rigid
polyurethane foam.
EXAMPLE 2
Production of a Rigid Urethane Foam by Blowing with a Low Boiling
Point Hydrocarbon and Water Used in Combination
[0182] 30 parts of diethylene glycol monoacrylate (Al-5) was mixed
with 70 parts of a polyol (A2-1) obtained by adding PO (4.55 mole)
to pentaerythritol (1 mole). The mixture was further admixed with
3.0 parts of "SILICONE SH-193", 2 parts of water, 18 parts of
cyclopentane, 10 parts of "FYROL CEF", 0.01 part of
t-butylperoxybenzoate, and 2 parts of "Ucat-1000", and controlled
at a temperature of 25.degree. C. To this mixture liquid, 150.3
parts of crude MDI (NCO index of 100) controlled at 25.degree. C.
was added, and the same procedures as in Example 1 were carried
out. Thus, a rigid polyurethane foam was obtained.
EXAMPLE 3
Production of a Rigid Urethane Foam by Blowing with Water Alone
[0183] 100 parts of sorbitol EO 6-molar adduct tetraacrylate
(A1-4), 1.5 parts of "SILICONE SH-193", 7 parts of water, 10 parts
of "FYROL CEF", and 2 parts of "Ucat-1000" were mixed, and
controlled at a temperature of 25.degree. C. To this mixture
liquid, 146.3 parts of crude MDI (NCO index of 100) controlled at
25.degree. C. was added, and the same procedures as in Example 1
were carried out. Thus, a rigid polyurethane foam was obtained.
EXAMPLE 4
Production of a Rigid Urethane Foam by Blowing with Water Alone
[0184] 50 parts of pentaerythritol PO 4-molar adduct triacrylate
(A1-3) was mixed with 50 parts of a polyol (A2-1) obtained by
adding PO (4.55 moles) to pentaerythritol (1 mole). The mixture was
further admixed with 1.5 parts of "SILICONE SH-193", 7 parts of
water, 10 parts of "FYROL CEF", 0.01 part of t-butylperoxybenzoate,
and 2 parts of "Ucat-1000", and controlled at a temperature of
25.degree. C. To this mixture liquid, 167.3 parts of crude MDI (NCO
index of 90) controlled at 25.degree. C. was added, and the same
procedures as in Example 1 were carried out. Thus, a rigid
polyurethane foam was obtained.
EXAMPLE 5
Production of a Rigid Urethane Foam by Blowing with Substitute for
Freon and Water Used in Combination
[0185] 80 parts of glycerol diacrylate (A1-2) was mixed with 20
parts of a polyol (A2-2) obtained by adding PO (2.7 moles) to
glycerol (1 mole). The mixture was further admixed with 1.5 parts
of "SILICONE SH-193", 2 parts of water, 25 parts of "HCFC-141b", 10
parts of "FYROL CEF", 0.01 part of t-butylperoxybenzoate, and 2
parts of "Ucat-1000", and controlled at a temperature of 25.degree.
C. To this mixture liquid, 116.8 parts of crude MDI (NCO index of
100) controlled at 25.degree. C. was added, and the same procedures
as in Example 1 were carried out. Thus, a rigid polyurethane foam
was obtained.
EXAMPLE 6
Production of a Rigid Urethane Foam by Blowing with Liquefied
Carbon Dioxide Gas and Water Used in Combination
[0186] 50 parts of glycerol diacrylate (A1-2) was mixed with 50
parts of a polyol (A2-1) obtained by adding PO (4.55 moles) to
pentaerythritol (1 mole). The mixture was further admixed with 1.5
parts of "SILICONE SH-193", 2 parts of water, 10 parts of "FYROL
CEF", and 2 parts of "Ucat-1000". The mixture liquid was put into a
raw material tank of a high-pressure foaming machine. In the
mixture liquid, 18 parts of liquefied carbon dioxide gas was
injected and mixed at a back pressure of 1 MPa of the tank, and it
was controlled at a temperature of 25.degree. C. This was mixed
with 131.7 parts of crude MDI (NCO index of 100) controlled at a
temperature of 25.degree. C. by colliding at 15 MPa, and poured
into an aluminum mold of 1000 mm (length).times.100 mm
(width).times.50 mm (height) controlled at 60.degree. C. After 10
minutes, it was removed from the mold to obtain a rigid
polyurethane foam.
EXAMPLE 7
Production of a Rigid Urethane Foam by Blowing with Substitute for
Freon and Water Used in Combination
[0187] 30 parts of diethylene glycol monoacrylate (A1-5) was mixed
with 70 parts of a polyol (A2-1) obtained by adding PO (4.55 moles)
to pentaerythritol (1 mole). The mixture was further admixed with
1.5 parts of "SILICONE SH-193", 1.5 parts of water, 25 parts of
"HCFC-141b", 10 parts of "FYROL CEF", and 2 parts of "Ucat-1000",
and controlled at a temperature of 25.degree. C. To the mixture
liquid, 150.3 parts of crude MDI (NCO index of 100) controlled at
25.degree. C. was added, and the same procedures as in Example 1
were carried out. Thus, a rigid polyurethane foam was obtained.
EXAMPLE 8
Production of a Rigid Urethane Foam by Blowing with a Low Boiling
Point Hydrocarbon and Water Used in Combination
[0188] 70 parts of diethylene glycol monoacrylate (A1-5), 30 parts
of diethylene glycol diacrylate (A0-1), 3.0 parts of "SILICONE
SH-193", 2 parts of water, 18 parts of cyclopentane, 10 parts of
"FYROL CEF", 0.01 part of t-butylperoxybenzoate, and 2 parts of
"Ucat-1000" were mixed, and controlled at a temperature of
25.degree. C. To this mixture liquid, 89.4 parts of crude MDI (NCO
index of 100) controlled at 25.degree. C. was added, and the same
procedures as in Example 1 were carried out. Thus, a rigid
polyurethane foam was obtained.
EXAMPLE 9
Production of a Rigid Urethane Foam by Blowing with Water Alone
[0189] 30 parts of glycerol monoacrylate (A1-1), 70 parts of
pentaerythritol PO 4-molar adduct triacrylate (A1-3), 1.5 parts of
"SILICONE SH-193", 7 parts of water, 10 parts of "FYROL CEF", 0.01
part of t-butylperoxybenzoate, and 2 parts of "Ucat-1000" were
mixed, and controlled at a temperature of 25.degree. C. To this
mixture liquid, 125.3 parts of crude MDI (NCO index of 70)
controlled at 25.degree. C. was added, and the same procedures as
in Example 1 were carried out. Thus, a rigid polyurethane foam was
obtained.
EXAMPLE 10
Production of a Flame-resistant Rigid Urethane Foam
[0190] 100 parts of glycerol diacrylate (A1-2), 80 parts of
aluminum hydroxide (produced by NIPPON LIGHT METAL CO., Ltd.), 2.5
parts of "SILICONE SH-193", 9 parts of water, 10 parts of "FYROL
CEF", and 2 parts of "Ucat-1000" were mixed, and controlled at a
temperature of 25.degree. C. To this mixture liquid, 203.2 parts of
crude MDI (NCO index of 100) controlled at 25.degree. C. was added,
and the same procedures as in Example 1 were carried out. Thus, a
flame-resistant rigid polyurethane foam was obtained.
EXAMPLE 11
Production of a Flexible Urethane Foam by Blowing with Water
Alone
[0191] 3 parts of glycerol monoacrylate (A1-1), 60 parts of a
polyol (A2-3) obtained by adding PO (73 moles) and further EO (16
moles) to glycerol (1 mole), 40 parts of a polymer polyol (20 mass
% polyacrylonitrile) (A2-4) obtained by polymerizing acrylonitrile
in the polyol (A2-3), 1 part of diethanolamine, 1 part of "SILICONE
SRX-253" (a silicone-based foam stabilizer produced by TORAY DOW
CORNING SILICONE CO., Ltd.), 3.7 parts of water, 0.4 part of "TEDA
L33" (a triethylenediamine-based amine catalyst produced by TOSOH
CO., Ltd.), and further 0.07 part of "TOYOCAT ET" (a
bis(dimethylaminoethyl) ether-based amine catalyst produced by
TOSOH CO., Ltd.) were mixed, and controlled at a temperature of
25.degree. C. To this mixture liquid, 50.4 parts of a mixture of
TDI/crude MDI (=80/20 mass %) (NCO index of 100) controlled at
25.degree. C. was added and stirred by "Homodisper" (an agitator
manufactured by TOKUSHU KIKA INDUSTRIES Ltd.) at 4000 rpm for 10
seconds. Then, the mixture liquid was poured into an aluminum mold
of 300 mm (length).times.300 mm (width).times.100 mm (height)
controlled at 60.degree. C. After 10 minutes, it was removed from
the mold to obtain a flexible polyurethane foam.
COMPARATIVE EXAMPLE 1
Production of a Rigid Urethane Foam by Blowing with Water Alone
[0192] 100 parts of a polyol (A2-2) obtained by adding PO (2.7
moles) to glycerol (1 mole), 1.5 parts of "SILICONE SH-193", 7
parts of water, 10 parts of "FYROL CEF", and 2 parts of "Ucat-1000"
were mixed, and controlled at a temperature of 25.degree. C. To the
mixture liquid, 268.0 parts of crude MDI (NCO index of 100)
controlled at 25.degree. C. was added, and the same procedures as
in Example 1 were carried out. Thus, a rigid polyurethane foam was
obtained.
COMPARATIVE EXAMPLE 2
Production of a Rigid Urethane Foam by Blowing with a Low Boiling
Point Hydrocarbon and Water Used in Combination
[0193] 100 parts of a polyol (A2-1) obtained by adding PO (4.55
moles) to pentaerythritol (1 mole), 1.5 parts of "SILICONE SH-193",
2 parts of water, 18 parts of cyclopentane, 10 parts of "FYROL CEF"
and 2 parts of "Ucat-1000" were mixed, and controlled at a
temperature of 25.degree. C. To this mixture liquid, 165.6 parts of
crude MDI (NCO index of 100) controlled at 25.degree. C. was added,
and the same procedures as in Example 1 were carried out. Thus, a
rigid polyurethane foam was obtained.
COMPARATIVE EXAMPLE 3
Production of a Rigid Urethane Foam by Blowing with Water Alone
[0194] 100 parts of a polyol (A2-1) obtained by adding PO (4.55
moles) to pentaerythritol (1 mole), 1.5 parts of "SILICONE SH-193",
7 parts of water, 10 parts of "FYROL CEF", and 2 parts of
"Ucat-1000" were mixed, and controlled at a temperature of
25.degree. C. To this mixture liquid, 168.6 parts of crude MDI (NCO
index of 70) controlled at 25.degree. C. was added, and the same
procedures as in Example 1 were carried out. Thus, a rigid
polyurethane foam was obtained.
COMPARATIVE EXAMPLE 4
Production of a Rigid Urethane Foam by Blowing with Water Alone
[0195] 100 parts of a polyol (A2-5) obtained by adding PO (3 moles)
to sorbitol (1 mole), 1.5 parts of "SILICONE SH-193", 7 parts of
water, 10 parts of "FYROL CEF", and 2 parts of "Ucat-1000" were
mixed, and controlled at a temperature of 25.degree. C. To this
mixture liquid, 333.7 parts of crude MDI (NCO index of 100)
controlled at 25.degree. C. was added, and the same procedures as
in Example 1 were carried out. Thus, a rigid polyurethane foam was
obtained.
COMPARATIVE EXAMPLE 5
Production of a Rigid Urethane Foam by Blowing with Substitute for
Freon and Water Used in Combination
[0196] 100 parts of a polyol (A2-1) obtained by adding PO (4.55
moles) to pentaerythritol (1 mole), 1.5 parts of "SILICONE SH-193",
2 parts of water, 32 parts of "HCFC-141b", 10 parts of "FYROL CEF",
and 2 parts of "Ucat-1000" were mixed, and controlled at a
temperature of 25.degree. C. To this mixture liquid, 165.6 parts of
crude MDI (NCO index of 100) controlled at 25.degree. C. was added,
and the same procedures as in Example 1 were carried out. Thus, a
rigid polyurethane foam was obtained.
COMPARATIVE EXAMPLE 6
Production of a Flame-resistant Rigid Urethane Foam
[0197] 100 parts of a polyol (A2-2) obtained by adding PO (2.7
moles) to glycerol (1 mole), 118 parts of aluminum hydroxide
(produced by NIPPON LIGHT METAL CO., Ltd.), 2.5 parts of "SILICONE
SH-193", 9 parts of water, 10 parts of "FYROL CEF", and 2 parts of
"Ucat-1000" were mixed, and controlled at a temperature of
25.degree. C. To this mixture liquid, 298.0 parts of crude MDI (NCO
index of 100) controlled at 25.degree. C. was added, and the same
procedures as in Example 1 were carried out. Thus, a
flame-resistant rigid polyurethane foam was obtained.
COMPARATIVE EXAMPLE 7
Production of a Flexible Urethane Foam by Blowing with Water
Alone
[0198] 40 parts of a polyol (A2-3) obtained by adding PO (73 moles)
and further EO (16 mole) to glycerol (1 mole), 60 parts of a
polymer polyol (20 mass % of polyacrylonitrile) (A2-4) obtained by
polymerizing acrylonitrile in the polyol (A2-3), 1 part of
diethanolamine, 1 part of "SILICONE SRX-253" (a silicone-based foam
stabilizer produced by TORAY DOW CORNING SILICONE CO., Ltd.), 3.7
parts of water, 0.4 part of "TEDA L33" (an amine catalyst produced
by TOSOH CO., Ltd.), and further 0.07 part of "TOYOCAT ET" (an
amine catalyst produced by TOSOH CO., Ltd.) were mixed, and
controlled at a temperature of 25.degree. C. To this mixture
liquid, 46.3 parts of a mixture of TDI/crude MDI (=80/20 mass %)
(NCO index of 100) controlled at 25.degree. C. was added, and the
same procedures as in Example 11 were carried out. Thus, a flexible
polyurethane foam was obtained.
TEST EXAMPLES
[0199] Tests for Rigid Urethane Foam:
[0200] Dimensional stability was evaluated by cutting out a foam
with dimensions of 100 mm.times.100 mm.times.50 mm, measuring the
dimensions of the foam one day after it was molded and two days
after it was allowed to stand at a temperature of 70.degree. C. and
at a relative humidity of 95%, and calculating the rate of change
in volume. The compressive strength was measured in accordance with
the test method of compressive strength of JIS A 9514, and the
flame resistance was measured in accordance with the test method of
flame resistance of JIS A 9514. The ratio of closed cells was
measured by the air-comparative aerometer 1000 manufactured by
TOKYO SCIENCE CO., Ltd. Tables 1 to 3 show the M value and the
measurement results of the compressive strength, rate of change in
volume, thermal conductivity, test of flame resistance, and ratio
of closed cells for the foams obtained in each of Examples 1 to 10
and Comparative Examples 1 to 6.
[0201] Tests for Flexible Urethane Foam:
[0202] Hardness, elongation, tear strength, and compression set
were respectively measured in accordance with JIS K 6401 and JIS K
6301. Tables 4 and 5 show the M value and the measurement results
of the hardness, elongation, tear strength, and compression set of
the foams obtained in each of Example 11 and Comparative Example
7.
1TABLE 1 Example 1 2 3 4 5 M value 73 185 83 139 78 Condition of
Cell Uniform Uniform Uniform Uniform Uniform Mass of Foam (g) 175
177 177 176 176 Density of Foam (kg/m.sup.3) 33.0 30.2 33.4 33.0
33.4 Rate of Change in Volume -1.7 +12.0 -3.5 -3.9 +11.5 (dv %)
Compressive Strength 1.5 1.4 1.8 1.6 1.5 (kgf/cm.sup.2) Thermal
Conductivity 0.0210 0.0169 0.0225 0.0218 0.0162 (kcal/m .multidot.
hr .multidot..degree. C.) Flame Resistance: Distance of Burning
(cm) -- -- -- -- -- Time of Burning (sec) -- -- -- -- -- Ratio of
Closed Cells (%) 96 97 97 97 95
[0203]
2TABLE 2 Example 6 7 8 9 10 M value 100 185 161 84 67 Condition of
Cell Uniform Uniform Uniform Uniform Uniform Mass of Foam (g) 175
175 176 175 175 Density of Foam (kg/m.sup.3) 33.2 32.9 33.5 33.1
33.8 Rate of Change in Volume -2.8 +4.8 +11.0 -4.5 -2.2 (dv %)
Compressive Strength 1.4 1.3 1.5 1.3 1.6 (kgf/cm.sup.2) Thermal
Conductivity (kcal/m .multidot. hr .multidot..degree. C.) 0.0205
0.0169 0.0170 0.0215 0.0220 Flame Resistance: Distance of Burning
(cm) -- -- -- -- 2.0 Time of Burning (sec) -- -- -- -- 19 Ratio of
Closed Cells (%) 98 94 98 96 92
[0204]
3TABLE 3 Comparative Example 1 2 3 4 5 6 M value 250 200 200 89 200
250 Condition of Cell Uniform Non- Uniform * Uniform * Uniform Mass
of Foam (g) 175 175 176 -- 175 -- Density of Foam (kg/m.sup.3) 33.8
33.9 33.2 -- 33.0 -- Rate of Change in Volume (dv %) -58.5 -- 50.2
-- +20.3 -- Compressive Strength (kgf/cm.sup.2) 0.8 -- 0.7 -- 0.8
-- Thermal Conductivity (kcal/m .multidot. hr .multidot..degree.
C.) 0.0225 -- 0.0229 -- 0.0190 -- Flame Resistance: Distance of
Burning (cm) -- -- -- -- -- -- Time of Burning (sec) -- -- -- -- --
-- Ratio of Closed Cells (%) 96 -- 96 -- 97 -- Note) * Blowing was
difficult because of high viscosity.
[0205]
4 TABLE 4 Example 11 M value 1392 Mass of Foam (g) 342 Density of
Foam (kg/m.sup.3) 38.0 Hardness (kgf) 14.5 Elongation (%) 117 Tear
Strength (kgf/cm) 0.58 Compression Set (%) 13
[0206]
5 TABLE 5 Comparative Example 7 M value 3296 Mass of Foam (g) 342
Density of Foam (kg/m.sup.3) 38.0 Hardness (kgf) 14.4 Elongation
(%) 100 Tear Strength (kgf/cm) 0.45 Compression Set (%) 25
[0207] Considerations of Tables 1 to 5
[0208] 1) Comparing the Examples 1, 3, 4 and 9 with the Comparative
Examples 1 and 3, in which water alone is used as a blowing agent,
each of the Examples provided a rigid foam having high mechanical
strength and low rate of change in volume.
[0209] 2) Comparing the Example 5 with the Comparative Example 5,
in which substitute for freon and water were used in combination as
blowing agents, the Example provided a rigid foam having high
mechanical strength and low rate of change in volume.
[0210] 3) Comparing the Examples 2 and 8 with the Comparative
Example 2, in which a low boiling point hydrocarbon and water were
used in combination as blowing agents, while the cells were uniform
in the Examples, the cells were non-uniform in the Comparative
Example. This is because the compound (A1) having an active
hydrogen-containing group and an addition-polymerizable functional
group used in the process of the present invention has a good
compatibility with hydrocarbon.
[0211] 4) Comparing the Examples 1 and 9 with the Comparative
Example 3, each of the Examples provided a rigid foam having high
mechanical strength and low rate of change in volume, even though
the NCO index has not more than 80. This is because the compound
(A1) having an active hydrogen-containing group and an
addition-polymerizable functional group used in the process of the
present invention is self-polymerizable.
[0212] 5) Comparing the Example 10 with the Comparative Example 6,
in which inorganic powder was mixed, while the cells were uniform
in the Example because the viscosity of the material in which
inorganic powder was dispersed in an active hydrogen component was
low, blowing was difficult in the Comparative Example because the
viscosity of the material in which inorganic powder was dispersed
in an active hydrogen component was high.
[0213] 6) Comparing the Example 11 with the Comparative Example 7,
a flexible foam having large elongation, high tear strength, and
small compression set was obtained in the Example.
[0214] Evaluations of Polyurethane Foams [Ib] and [Ic]
[0215] [Raw Materials Used]
[0216] Compounds (A1) having an active hydrogen-containing group
and an addition-polymerizable functional group
[0217] (A1-5): diethylene glycol monoacrylate
[0218] (A1-1): glycerol monoacrylate
[0219] Compounds (A2) having at least 2.5 (on the average) active
hydrogen-containing groups and not having an addition-polymerizable
functional group
[0220] (A2-6): polyether polyols having a hydroxyl value of 400 in
which PO is added to pentaerythritol
[0221] (A2-7): polyether polyols having a hydroxyl value of 400 in
which PO is added to glycerol
[0222] Organic polyisocyanate (B)
[0223] (B-1): polymethylene polyphenyl isocyanate ("Lupranate
M-20S" produced by BASF Corporation)
[0224] Auxiliaries (C)
[0225] Hollow Microsphere (C24-1): acrylonitrile-based
thermoplastic resin hollow microsphere ("Matsumoto Microsphere
MFL-80GCA" produced by MATSUMOTO YUSHI-SEIYAKU CO., Ltd.)
[0226] Inorganic Powder (C23-1): talc (Soap Stone C produced by
NIHON MISTRON CO., Ltd.)
[0227] Dehydrating Agent (C25-1): molecular sieve ("Molecular Sieve
3A-B powder" produced by UNION SHOWA K.K.)
[0228] Dust-Scattering Reducer (C29-1): PEG (molecular weight 600)
dioleic acid ester ("Ionet DL200" produced by Sanyo Chemical
Industries, Ltd.; in liquid state)
[0229] Foam Stabilizer (C21-1): silicone-based foam stabilizer
("SZ-1932" produced by NIPPON UNICAR COMPANY LTD.)
[0230] Urethanation Catalyst (C22-1): stannic dibutyl dilaurate
("Stann BL" produced by SANKYO ORGANIC CHEMICALS CORPORATION)
[0231] Radical-Polymerization Initiator (C27-1):
t-butylperoxybenzoate
[0232] [Test Methods]
[0233] Hardness: hardness was measured by "D-type hardness gauge"
manufactured by KOBUNSHI KEIKI CO., Ltd. in accordance with the
conditions under ASTM D2240.
[0234] Bending Strength: bending strength was measured by the
"Instron type universal tester" manufactured by Shimadzu
Corporation in accordance with the conditions under JIS K6911.
[0235] Impact Strength: Izod impact strength (no notch) was
measured in accordance with the conditions under JIS K6911.
[0236] Scorch Resistance: the active hydrogen component was mixed
with the NCO component with the amount of the catalyst being
controlled to cause curing for 2 minutes under the condition of
temperature controlled at 30.degree. C. The mixture was poured into
a thermal insulating mold having dimensions of 100 mm.times.100
mm.times.150 mm to a thickness of 100 mm, cured for one hour, and
then removed from the mold to obtain a molded product. The molded
product was cut half with a saw, and the scorch resistance was
determined as .times. when scorching was found in the cross
section, and determined as .smallcircle. when no scorching was
found in the cross section.
EXAMPLES 12 to 14
[0237] Each of the raw materials was put into a planetary mixer in
amounts by mass parts as shown in Table 6, and stirred at from 130
to 200 rpm for 10 minutes to obtain an active hydrogen component
and a NCO component. Then, while rotating the rotor of a mechanical
froth machine (MF-350 type mechanical froth foaming apparatus
manufactured by TOHO MACHINERY CO., Ltd.) at 300 rpm, continuously
supplied to the inlet of the mixing head were the active hydrogen
component and the NCO component at a rate of 10 to 20 L/min in
total and dry air in the proportion as shown in Table 1. Then, the
mixture liquid in which fine bubbles were uniformly dispersed,
which was continuously discharged from the outlet, was poured into
an aluminum mold having dimensions of 500 mm.times.500 mm.times.200
mm to a thickness of 100 mm, and heated and cured at 80.degree. C.
for two hours. Then, it was allowed to stand and cooled for 8
hours, and removed from the mold to obtain a molded product. Table
6 shows the evaluation results of the molded product.
COMPARATIVE EXAMPLES 8 AND 9
[0238] A molded product was obtained according to the same
procedures as in Examples 12 to 14 using raw materials in the
amounts by mass parts as shown in Table 6. Table 6 shows the
evaluation results of the molded product.
6 TABLE 6 Comparative Example Example 12 13 14 8 9 Active Compound
(A1-5) 15.3 13.6 Hydrogen Compound (A1-1) 13.4 Component Compound
(A2-6) 15.3 13.6 13.4 29.6 26.5 Hollow Microsphere 8.1 7.3 7.1 7.9
7.1 (C24-1) Inorganic Powder 5.4 5.3 (C23-1) Dehydrating Agent 1.5
1.4 1.3 1.5 1.3 (C25-1) Dust-Scattering 20.4 18.1 17.9 19.7 17.6
Reducer (C29-1) Foam Stabilizer 1.0 0.9 0.9 1.0 0.9 (C21-1)
Urethanation Catalyst 0.04 0.04 0.04 0.04 0.04 (C22-1)
Polymerization 0.01 0.01 0.01 Initiator (C27-1) NCO Polyisocyanate
28.7 25.6 37.5 30.9 27.6 Component (B-1) Hollow Microsphere 8.1 7.3
7.1 7.9 7.1 (C24-1) Inorganic Powder 5.4 5.3 (C23-1) Dehydrating
Agent 1.5 1.4 1.3 1.5 1.3 (C25-1) Amount of Air (volume %*) 60.5
49.0 62.7 61.0 49.5 Evaluation Density (g/cm.sup.3) 0.25 0.35 0.25
0.25 0.35 Results Hardness (Shore D) 22 45 23 12 39 of Molded
Bending Strength 0.5 1.2 0.5 0.2 0.8 Product (kgf/mm.sup.2) Impact
Strength 2.0 3.5 2.1 0.8 2.0 Scorch Resistance .largecircle.
.largecircle. .largecircle. X X Note) *volume % = {Volume of
Air/(Volume of Air + Total Volume of the Composition)} .times. 100,
wherein the Volume of Air indicates the volume at 25.degree. C. and
at 1 atm.
EXAMPLES 15 TO 17
[0239] Each of the raw materials was put into a planetary mixer in
the amounts by mass parts as shown in Table 7, and stirred at 130
rpm for 10 minutes to obtain an active hydrogen component. Mixing
was also performed in the same way when incorporating auxiliaries
in a NCO component. Then, the active hydrogen component and the NCO
component were put into a vessel of 1 L in the proportions as shown
in Table 7 so that their total mass may become about 400 g, and
mixed by a propeller blade for about 1 minute. The mixture liquid
was poured into a metallic mold having dimensions of 50 mm X 50 mm
X 200 mm, and after it was defoamed under a reduced pressure for
about 30 seconds, it was heated and cured at 80.degree. C. for two
hours. Then, it was allowed to stand and cooled for 8 hours, and
removed from the mold to obtain a molded product. Table 7 shows the
evaluation results of the molded product.
COMPARATIVE EXAMPLES 10 AND 11
[0240] A molded product was obtained according to the same
procedures as in Examples 15 to 17 using the raw materials in the
amounts by mass parts as shown in Table 7. Table 7 shows the
evaluation results of the molded product.
7 TABLE 7 Comparative Example Example 15 16 17 10 11 Active
Compound (A1-5) 15.0 13.6 Hydrogen Compound (A1-1) 12.7 Component
Compound (A2-6) Compound (A2-7) 15.0 13.6 12.7 29.1 25.2 Hollow
Microsphere 9.0 8.2 9.3 9.3 8.4 (C24-1) Inorganic Powder 4.5 5.9
(C23-1) Dehydrating Agent 1.5 1.4 1.3 1.4 1.3 (C25-1)
Dust-Scattering 20.0 18.2 17.0 18.6 16.8 Reducer (C29-1) Foam
Stabilizer 1.0 0.9 0.8 0.9 0.8 (C21-1) Urethanation Catalyst 0.04
0.04 0.03 0.04 0.03 (C22-1) Polymerization 0.01 0.01 0.01 Initiator
(C27-1) NCO Polyisocyanate (B-1) 28.0 25.5 35.5 30.0 26.0 Component
Hollow Microsphere 9.0 8.2 9.3 9.3 8.4 (C24-1) Inorganic Powder 4.5
5.9 (C23-1) Dehydrating Agent 1.5 1.4 1.3 1.4 1.3 (C25-1) Density
(g/cm.sup.3) 0.60 0.65 0.60 0.60 0.65 Evaluation Hardness (Shore D)
60 62 60 51 56 Results Bending Strength 2.5 2.7 2.5 1.8 2.0 of
Molded (kgf/mm.sup.2) Product Impact Strength 5.4 6.0 5.6 4.4 5.0
Scorch Resistance .largecircle. .largecircle. .largecircle. X X
EXAMPLE 18
[0241] 80 parts of diethylene glycol monoacrylate (A1-5), 18 parts
of hollow microsphere (C24-1), and 2 parts of dehydrating agent
(C25-1) were put into a planetary mixer and stirred at 130 rpm for
10 minutes to obtain an active hydrogen component. 80 parts of
organic polyisocyanate (B-1), 18 parts of hollow microsphere
(C24-1), and 2 parts of dehydrating agent (C25-1) were put into a
planetary mixer and stirred at 130 rpm for 10 minutes to obtain a
NCO component. Then, 195 parts of the active hydrogen component,
165 parts of the NCO component, 40 parts of staple fiber of glass
fiber roving ("ER 4630" produced by ASAHI FIBER GLASS CO., Ltd.)
cut to a length of 6 mm (C26-1), 0.16 part of urethanation catalyst
(C22-1), and 0.02 part of radical-polymerization initiator (C27-1)
were put into a vessel of 1 L, and mixed by a propeller blade for
about 1 minute. The mixture liquid was poured into a metallic mold
having dimensions of 50 mm.times.50 mm.times.200 mm, and after it
was defoamed under a reduced pressure for about 30 seconds, it was
heated and cured at 80.degree. C. for two hours. Then, it was
allowed to stand and cooled for 8 hours, and removed from the mold
to obtain a molded product.
EXAMPLE 19
[0242] 74 parts of diethylene glycol monoacrylate (A1-5), 24 parts
of hollow microsphere (C24-1), and 2 parts of dehydrating agent
(C25-1) were put into a planetary mixer and stirred at 130 rpm for
10 minutes to obtain an active hydrogen component. 74 parts of
organic polyisocyanate (B-1), 24 parts of hollow microsphere
(C24-1), and 2 parts of dehydrating agent (C25-1) were put into a
planetary mixer and stirred at 130 rpm for 10 minutes to obtain a
NCO component. Then, 173 parts of the active hydrogen component,
147 parts of the NCO component, 80 parts of staple fiber (C26-1),
0.14 part of urethanation catalyst (C22-1), and 0.02 part of
radical-polymerization initiator (C27-1) were put into a vessel of
1 L, and mixed by a propeller blade for about 1 minute. The mixture
liquid was poured into a metallic mold having dimensions of 50
mm.times.50 mm.times.200 mm, and after it was defoamed under a
reduced pressure for about 30 seconds, it was heated and cured at
80.degree. C. for two hours. Then, it was allowed to stand and
cooled for 8 hours, and removed from the mold to obtain a molded
product.
EXAMPLE 20
[0243] 80 parts of glycerol monoacrylate (A1-1), 18 parts of hollow
microsphere (C24-1), and 2 parts of dehydrating agent (C25-1) were
put into a planetary mixer and stirred at 130 rpm for 10 minutes to
obtain an active hydrogen component. 80 parts of organic
polyisocyanate (B-1), 18 parts of hollow microsphere (C24-1), and 2
parts of dehydrating agent (C25-1) were put into a planetary mixer
and stirred at 130 rpm for 10 minutes to obtain a NCO component.
Then, 126 parts of the active hydrogen component, 234 parts of the
NCO component, 40 parts of staple fiber (C26-1), 0.16 part of
urethanation catalyst (C22-1), and 0.01 part of
radical-polymerization initiator (C27-1) were put into a vessel of
1 L, and mixed by a propeller blade for about 1 minute. The mixture
liquid was poured into a metallic mold having dimensions of 50
mm.times.50 mm.times.200 mm, and after it was defoamed under a
reduced pressure for about 30 seconds, it was heated and cured at
80.degree. C. for two hours. Then, it was allowed to stand and
cooled for 8 hours, and removed from the mold to obtain a molded
product.
EXAMPLE 21
[0244] 80 parts of glycerol diacrylate (A1-2), 18 parts of hollow
microsphere (C24-1), and 2 parts of dehydrating agent (C25-1) were
put into a planetary mixer and stirred at 130 rpm for 10 minutes to
obtain an active hydrogen component. 80 parts of organic
polyisocyanate (B-1), 18 parts of hollow microsphere (C24-1), and 2
parts of dehydrating agent (C25-1) were put into a planetary mixer
and stirred at 130 rpm for 10 minutes to obtain a NCO component.
Then, 214 parts of the active hydrogen component, 146 parts of the
NCO component, 40 parts of staple fiber (C26-1), 0.16 part of
urethanation catalyst (C22-1), and 0.04 part of
radical-polymerization initiator (C27-1) were put into a vessel of
1 L, and mixed by a propeller blade for about 1 minute. The mixture
liquid was poured into a metallic mold having dimensions of 50
mm.times.50 mm.times.200 mm, and after it was defoamed under a
reduced pressure for about 30 seconds, it was heated and cured at
80.degree. C. for two hours. Then, it was allowed to stand and
cooled for 8 hours, and removed from the mold to obtain a molded
product.
EXAMPLE 22
[0245] 80 parts of diethylene glycol monoacrylate (A1-5), 20 parts
of staple fiber of glass chopped strand ("RES015-BM38" produced by
NIPPON SHEET GLASS CO., LTD.) (C26-2), 18 parts of hollow
microsphere (C24-1), 2 parts of dehydrating agent (C25-1), 1 part
of foam stabilizer (C21-1), 0.16 part of urethanation catalyst
(C22-1), and 0.01 part of radical-polymerization initiator (C27-1)
were put into a planetary mixer and stirred at 130 rpm for 10
minutes to obtain an active hydrogen component. 80 parts of organic
polyisocyanate (B-1), 20 parts of staple fiber (C26-2), 18 parts of
hollow microsphere (C24-1) and 2 parts of dehydrating agent (C25-1)
were put into a planetary mixer and stirred at 130 rpm for 10
minutes to obtain a NCO component. Then, while rotating the rotor
of a mechanical froth machine (MF-350 type mechanical froth foaming
apparatus manufactured by TOHO MACHINERY CO., Ltd.) at 300 rpm,
continuously supplied to the inlet of the mixing head were the
active hydrogen component and the NCO component with a mass ratio
of 100:70 at 18.6 L/min in total and dry air at 1.4 L/min. Then,
the mixture liquid in which fine bubbles were uniformly dispersed,
which was continuously discharged from the outlet, was poured into
an aluminum mold having dimensions of 500 mm.times.500 mm.times.200
mm to a thickness of 100 mm, and heated and cured at 80.degree. C.
for two hours. Then, it was allowed to stand and cooled for 8
hours, and removed from the mold to obtain a molded product.
COMPARATIVE EXAMPLE 12
[0246] 80 parts of a compound containing an active
hydrogen-containing group (A2-7), 18 parts of hollow microsphere
(C24-1), and 2 parts of dehydrating agent (C25-1) were put into a
planetary mixer and stirred at 130 rpm for 10 minutes to obtain an
active hydrogen component. 80 parts of organic polyisocyanate
(B-1), 18 parts of hollow microsphere (C24-1), and 2 parts of
dehydrating agent (C25-1) were put into a planetary mixer and
stirred at 130 rpm for 10 minutes to obtain a NCO component. Then,
180 parts of the active hydrogen component, 180 parts of the NCO
component, 40 parts of staple fiber (C26-1), and 0.16 part of
urethanation catalyst (C22-1) were put into a vessel of 1 L, and
mixed by a propeller blade for about 1 minute. The mixture liquid
was poured into a metallic mold having dimensions of 50 mm.times.50
mm.times.200 mm, and after it was defoamed under a reduced pressure
for about 30 seconds, it was heated and cured at 80.degree. C. for
two hours. Then, it was allowed to stand and cooled for 8 hours,
and removed from the mold to obtain a molded product.
COMPARATIVE EXAMPLE 13
[0247] 74 parts of a compound containing an active
hydrogen-containing group (A2-7), 24 parts of hollow microsphere
(C24-1), and 2 parts of dehydrating agent (C25-1) were put into a
planetary mixer and stirred at 130 rpm for 10 minutes to obtain an
active hydrogen component. 74 parts of organic polyisocyanate
(B-1), 24 parts of hollow microsphere (C24-1), and 2 parts of
dehydrating agent (C25-1) were put into a planetary mixer and
stirred at 130 rpm for 10 minutes to obtain a NCO component. Then,
160 parts of the active hydrogen component, 160 parts of the NCO
component, 80 parts of staple fiber (C26-1), and 0.14 part of
urethanation catalyst (C22-1) were put into a vessel of 1 L and
mixed by a propeller blade. However, the mixing could not be
performed uniformly, so that a molded product could not be
obtained.
COMPARATIVE EXAMPLE 14
[0248] 80 parts of a compound containing an active
hydrogen-containing group (A2-7), 20 parts of staple fiber (C26-2),
18 parts of hollow microsphere (C24-1), 2 parts of dehydrating
agent (C25-1), 1 part of foam stabilizer (C21-1), and 0.16 part of
urethanation catalyst (C22-1) were put into a planetary mixer and
stirred at 130 rpm for 10 minutes to obtain an active hydrogen
component. 80 parts of organic polyisocyanate (B-1), 20 parts of
staple fiber (C26-2), 18 parts of hollow microsphere (C24-1), and 2
parts of dehydrating agent (C25-1) were put into a planetary mixer
and stirred at 130 rpm for 10 minutes to obtain a NCO component.
Then, while rotating the rotor of a mechanical froth machine
(MF-350 type mechanical froth foaming apparatus manufactured by
TOHO MACHINERY CO., Ltd.) at 300 rpm, continuously supplied to the
inlet of the mixing head were the active hydrogen component and the
NCO component with a mass ratio of 1:1 at 18.9 L/min in total and
dry air at 1.1 L/min. Then, the mixture liquid in which fine
bubbles were uniformly dispersed, which was continuously discharged
from the outlet, was poured into an aluminum mold having dimensions
of 500 mm.times.500 mm.times.200 mm to a thickness of 100 mm, and
heated and cured at 80.degree. C. for two hours. Then, it was
allowed to stand and cooled for 8 hours, and removed from the mold
to obtain a molded product.
TEST EXAMPLE
[0249] Tables 8 and 9 show the respective measurement results of
the amount of glass fiber, hardness, bending strength, bending
modulus, moldability, and compactness of the obtained molded
products of rigid polyurethane foam. In Tables 8 and 9, the amount
of glass fiber refers to the value calculated from the mass of
glass fiber mixed in the composition. Hardness, bending strength,
and bending modulus were respectively measured according to the
conditions under ASTM D2240 and JIS K7055.
[0250] Moldability was determined as .smallcircle. when a molded
product in which glass fiber is uniformly dispersed and which has
no defect was obtained, and as .times. when it was not.
Furthermore, compactness was determined as .smallcircle. when the
ratio of the microcells having a size of not more than 150 .mu.m to
all microcells that appeared on a photograph of a cut surface of a
molded product taken by a scanning electron microscope with a
magnification of 100 was at least 90%, and as .times. when it was
not.
8 TABLE 8 Comparative Example Example 18 19 20 21 12 13 Amount of
Glass 10.0 20.0 10.0 10.0 10.0 20.0 Fiber (mass %) Density
(g/cm.sup.3) 0.67 0.67 0.68 0.67 0.66 -- Hardness (Shore D) 81 85
79 80 77 -- Bending Strength 6.0 9.5 5.8 6.0 4.5 -- (kgf/mm.sup.2)
Bending Modulus 220 310 190 210 140 -- (kgf/mm.sup.2) Moldability
.largecircle. .largecircle. .largecircle. .largecircle.
.largecircle. X Compactness .largecircle. .largecircle.
.largecircle. .largecircle. .largecircle. X
[0251]
9 TABLE 9 Comparative Example Example 22 14 Amount of Glass 16.6
16.6 Fiber (mass %) Density (g/cm.sup.3) 0.66 0.66 Hardness (Shore
D) 83 80 Bending Strength 9.0 6.0 (kgf/mm.sup.2) Bending Modulus
300 220 (kgf/mm.sup.2) Moldability .largecircle. .largecircle.
Compactness .largecircle. X
[0252] Evaluation of Polyurethane Foam [2]
EXAMPLE 23
[0253] 5 parts of glycerol monoacrylate (A1-1), 100 parts of a
polyol (A2-3) obtained by adding PO (73 mole) and further EO (16
mole) to glycerol (1 mole), 1 part of diethanolamine (A2-8), 1 part
of "SILICONE SRX-253" (silicone-based foam stabilizer produced by
TORAY DOW CORNING SILICONE CO., Ltd.), 3.5 parts of water, 0.4 part
of "TEDA L33" (amine catalyst produced by TOSOH CO., Ltd.), and
further 0.07 part of "TOYOCAT ET" (amine catalyst produced by TOSOH
CO., Ltd.) were mixed, and controlled at a temperature of
25.degree. C. To this mixture liquid, 51.3 parts of a mixture of
TDI/crude MDI (=80/20 mass %) (NCO index of 100) controlled at
25.degree. C. was added, and stirred by "Homodisper" (an agitator
manufactured by TOKUSHU KIKA INDUSTRIES Ltd.) at 4000 rpm for 10
seconds. Then, the mixture liquid was poured into an aluminum mold
of 300 mm (length).times.300 mm (width).times.100 mm (height)
controlled at 60.degree. C. After 10 minutes, it was removed from
the mold to obtain a flexible polyurethane foam.
EXAMPLE 24
[0254] 5 parts of glycerol diacrylate (A1-2), 100 parts of the
polyol (A2-3), 1 part of diethanolamine (A2-8), 1 part of "SILICONE
SRX-253" (silicone-based foam stabilizer produced by TORAY DOW
CORNING SILICONE CO., Ltd.), 3.5 parts of water, 0.4 part of "TEDA
L33" (amine catalyst produced by TOSOH CO., Ltd.), and further 0.07
part of "TOYOCAT ET" (amine catalyst produced by TOSOH CO., Ltd.)
were mixed, and controlled at a temperature of 25.degree. C. To
this mixture liquid, 47.1 parts of a mixture of TDI/crude MDI
(=80/20 mass %) (NCO index of 100) controlled at 25.degree. C. was
added and stirred by "Homodisper" (an agitator manufactured by
TOKUSHU KIKA INDUSTRIES Ltd.) at 4000 rpm for 10 seconds. Then, the
mixture liquid was poured into an aluminum mold of 300 mm
(length).times.300 mm (width).times.100 mm (height) controlled at
60.degree. C. After 10 minutes, it was removed from the mold to
obtain a flexible polyurethane foam.
EXAMPLE 25
[0255] 5 parts of pentaerythritol PO 4-molar adduct triacrylate
(A1-3), 100 parts of the polyol (A2-3), 1 part of diethanolamine
(A2-8), 1 part of "SILICONE SRX-253" (silicone-based foam
stabilizer produced by TORAY DOW CORNING SILICONE CO., Ltd.), 3.5
parts of water, 0.4 part of "TEDA L33" (amine catalyst produced by
TOSOH CO., Ltd.), and further 0.07 part of "TOYOCAT ET" (amine
catalyst produced by TOSOH CO., Ltd.) were mixed, and controlled at
a temperature of 25.degree. C. To this mixture liquid, 46.1 parts
of a mixture of TDI/crude MDI (=80/20 mass %) (NCO index of 100)
controlled at 25.degree. C. was added and stirred by "Homodisper"
(an agitator manufactured by TOKUSHU KIKA INDUSTRIES Ltd.) at 4000
rpm for 10 seconds. Then, the mixture liquid was poured into an
aluminum mold of 300 mm (length).times.300 mm (width).times.100 mm
(height) controlled at 60.degree. C. After 10 minutes, it was
removed from the mold to obtain a flexible polyurethane foam.
COMPARATIVE EXAMPLE 15
[0256] 75 parts of the polyol (A2-3), 25 parts of a polymer polyol
(20 mass % polyacrylonitrile) (A2-4) obtained by polymerizing
acrylonitrile in the polyol (A2-3), 1 part of diethanolamine
(A2-8), 1 part of "SILICONE SRX-253" (silicone-based foam
stabilizer produced by TORAY DOW CORNING SILICONE CO., Ltd.), 3.5
parts of water, 0.4 part of "TEDA L33" (amine catalyst produced by
TOSOH CO., Ltd.), and further 0.07 part of "TOYOCAT ET" (amine
catalyst produced by TOSOH CO., Ltd.) were mixed, and controlled at
a temperature of 25.degree. C. To this mixture liquid, 44.7 parts
of a mixture of TDI/crude MDI (=80/20 mass %) (NCO index of 100)
controlled at 25.degree. C. was added, and the same procedures as
in Example 23 were carried out to obtain a flexible polyurethane
foam.
TEST EXAMPLE
[0257] Hardness, elongation, tear strength, and compression set
were measured respectively in accordance with the conditions under
JIS K 6401 and JIS K 6301. Table 10 shows the M' value, K1, K2, and
the measurement results of the hardness, elongation, tear strength,
and compression set of the foams obtained in each of Examples 23 to
25 and Comparative Example 15.
10 TABLE 10 Comparative Example Example 23 24 25 15 M' value 1284
1167 1557 4885 K1 0.3 0.1 0.3 0.3 K2 2000 2000 2000 -- Weight of
Foam (g) 342 338 342 340 Density of Foam 38.0 37.5 38.0 37.8
(kg/m.sup.3) Hardness (kgf) 14.2 15.8 13.2 10.4 Elongation (%) 103
99 101 100 Tear Strength 0.48 0.45 0.49 0.45 (kgf/cm) Compression
Set (%) 19 18 20 24
INDUSTRIAL APPLICABILITY
[0258] The polyurethane foam of the present invention has the
following characteristics and effects:
[0259] 1) The present invention provides a polyurethane foam
excellent in mechanical properties based on the technique
applicable to a wide variety of rigid or flexible foams.
[0260] 2) The present invention provides a foam having mechanical
properties such as excellent hardness and dimensional stability in
the case of forming a rigid foam, and such as small compression set
in the case of forming a flexible foam.
[0261] 3) The present invention provides a rigid foam blown with a
blowing agent such as a hydrogen atom-containing halogenated
hydrocarbon, water, low boiling point hydrocarbon, liquefied carbon
dioxide gas, or the like, which has the same dimensional stability
and the same or higher mechanical strength as in the case of using
conventional CFC-11, and which has good thermal insulation and
flame resistance.
[0262] 4) The present invention provides not only a rigid foam
blown with a blowing agent that is excellent in these mechanical
properties, but also a rigid foam excellent in these mechanical
properties in the form of a mechanical froth foam or a syntactic
foam produced in the absence of a blowing agent.
[0263] 5) The present invention provides a rigid polyurethane foam
which is of light weight and has an even density distribution, has
a fine surface when cut, and the reduction in the mechanical
properties is small when its density is decreased.
[0264] 6) The present invention provides a staple fiber-reinforced
rigid polyurethane foam having high bending strength and high
bending modulus.
[0265] 7) The present invention provides a mechanical froth foam
that is applicable for repeated uses such as for materials of molds
or for uses subject to a bending stress. In producing this
mechanical froth foam, even when the amount of the staple fiber
used in the composition is increased, viscosity of the composition
does not become as high as in a conventional case. Thus, mechanical
stirring can be sufficiently performed, so that inert gas is
uniformly dispersed. Thus, the obtained foam has high mechanical
strength.
[0266] 8) The present invention provides a flexible foam in which
its hardness and ball rebound are not reduced when its density is
decreased.
[0267] 9) The present invention provides a process for producing a
polyurethane foam using an active hydrogen component having low
viscosity.
[0268] 10) The present invention provides a process for producing a
polyurethane foam excellent in mechanical properties.
[0269] 11) The present invention provides a composition for forming
a polyurethane foam excellent in mechanical properties.
[0270] 12) The present invention provides an addition-polymerizable
active hydrogen component for forming a polyurethane foam excellent
in mechanical properties.
[0271] Because of the above-mentioned effects, the polyurethane
foam of the present invention is useful as a rigid polyurethane
foam that can be used as a thermal insulator, shock absorbing
material, synthetic wood (including for the use of structural
materials or materials for models, etc.), etc., or as a flexible
polyurethane foam that can be used as a cushioning material,
shock-absorbing material, sound insulating/absorbing material,
etc.
* * * * *