U.S. patent application number 10/282413 was filed with the patent office on 2003-07-17 for polyester diol and derived polyurethane and acrylic copolymer.
Invention is credited to Endo, Toshio, Miho, Takuya.
Application Number | 20030135010 10/282413 |
Document ID | / |
Family ID | 27527598 |
Filed Date | 2003-07-17 |
United States Patent
Application |
20030135010 |
Kind Code |
A1 |
Endo, Toshio ; et
al. |
July 17, 2003 |
Polyester diol and derived polyurethane and acrylic copolymer
Abstract
The present invention Nos. 1-3 provide a spandex filament which
is excellent in view of a recovering ability of elasticity, high
tensile strength, and hydrolysis resistance, and a polyurethane
which can provide thereof and, further, a polyester polyester diol
obtained from a specified diol. Further, the present invention No.
4 provides a polyester polyol containing a polyol having an
ultraviolet ray-absorbable group, a lactone-modified polyol
therefrom, and a polyester polyol containing other polyol
components and adipic acid as constructing component units, and
provides a polyurethane having washing resistance obtained
therefrom and, further provides a spandex filament comprising the
polyurethane. The present invention No. 5 provides a dialkyl amino
group-contained additive having a high solubility to a DMAc solvent
which protects a spandex polymer from deterioration or
discoloration, and which is employed for a spandex polymer having
an improved permanent extension property, and a polyurethane
composition and a spandex composition having an improved permanent
extension property. Still further, the present invention No. 6
provides a polyurethane having a soft feeling, an excellent
hydrolysis resistance, a wrinkle resistance, and an adhesive
property, and which is particularly excellent as an artificial
leather.
Inventors: |
Endo, Toshio; (Ohtake-shi,
JP) ; Miho, Takuya; (Yamaguchi-ken, JP) |
Correspondence
Address: |
MORGAN & FINNEGAN, L.L.P.
345 Park Avenue
New York
NY
10154-0053
US
|
Family ID: |
27527598 |
Appl. No.: |
10/282413 |
Filed: |
October 29, 2002 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
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10282413 |
Oct 29, 2002 |
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09744345 |
Mar 8, 2001 |
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6500911 |
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09744345 |
Mar 8, 2001 |
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PCT/JP00/03265 |
May 22, 2000 |
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Current U.S.
Class: |
528/73 |
Current CPC
Class: |
C08G 18/4661 20130101;
D01F 6/70 20130101; C08G 18/664 20130101; Y10T 428/2913 20150115;
C08G 18/10 20130101; C08G 18/0895 20130101; C08G 18/4238 20130101;
C08G 18/4277 20130101; Y10S 528/906 20130101; C08G 63/60 20130101;
C08G 18/4236 20130101; C08G 18/10 20130101; C08G 18/2865 20130101;
C08G 18/10 20130101; C08G 18/3228 20130101 |
Class at
Publication: |
528/73 |
International
Class: |
C08G 018/28 |
Foreign Application Data
Date |
Code |
Application Number |
May 20, 1999 |
JP |
140 727/1999 |
May 20, 1999 |
JP |
140 739/1999 |
May 20, 1999 |
JP |
140 745/1999 |
May 20, 1999 |
JP |
140 749/1999 |
Aug 18, 1999 |
JP |
231 307/1999 |
Claims
1. A polyester diol containing at least one diol selected from the
group consisting of 2-n-butyl-2-ethyl-1,3-propanediol,
2,2-diethyl-1,3-propaned- iol and 2,4-diethyl-1,5-pentanediol,
.epsilon.-caprolactone, and adipic acid as constructing
components.
2. A polyester diol as claimed in claim 1, wherein a number average
molecular weight ranges in 500-5,000.
3. A polyester diol as claimed in claim 1 or 2, wherein (the
content of a polyester constructing unit)/(the content of
constructing unit of .epsilon.-caprolactone) is 5/95-80/20 (weight
ratio), and said polyester is composed of at least one diol
selected from the group consisting of
2-n-butyl-2-ethyl-1,3-propanediol, 2,2-diethyl-1,3-propanediol and
2,4-diethyl-1,5-pentanediol, and adipic acid.
4. A polyurethane obtained from a polyester diol as claimed in any
one of claims 1-3 and an organic diisocyanate.
5. A spandex filament which comprises the polyurethane as claimed
in claim 4.
6. A polyester diol containing a branched aliphatic diol,
.epsilon.-caprolactone, and an aliphatic dicarboxylic acid having a
carbon number of 10-12 as constructing components.
7. A polyester diol as claimed in claim 6, wherein a number average
molecular weight ranges in 500-5,000.
8. A polyester diol as claimed in claim 6 or 7, wherein (the
content of a polyester constructing unit composed of a branched
diol and an aliphatic dicarboxylic acid having a carbon number of
10-12)/(the content of constructing unit of .epsilon.-caprolactone)
is 5/95-80/20 (weight ratio).
9. A polyurethane obtained from a polyester diol as claimed in any
one of claims 6-8 and an organic diisocyanate.
10. A spandex filament which comprises the polyurethane as claimed
in claim 9.
11. A polyurethane obtained by allowing to react a polyester diol
containing 2,4-diethyl-1,5-pentanediol as a constructing component
with an organic diisocyanate.
12. A polyurethane as claimed in claim 11, wherein a number average
molecular weight in said polyester diol ranges in 500-5,000.
13. A spandex filament which comprises the polyurethane as claimed
in claim 11 or 12.
14. A polyurethane obtained from a polyether polyol (X) containing
a polyol component (A) composed of a polyol (A1) having an
ultraviolet ray-absorbable group or a lactone-modified polyol (A2)
therefrom and other polyol components (A3), adipic acid (B), and an
organic diisocyanate (Y).
15. A polyurethane as claimed in claim 14, wherein the polyol (A1)
having an ultraviolet ray-absorbable group is a compound
represented by formula (1). 6
16. A polyurethane as claimed in claim 14 or 15, wherein said
lactone is .epsilon.-caprolactone.
17. A polyurethane as claimed in any one of claims 14-16, wherein a
number average molecular weight of said polyester polyol ranges in
500-5,000.
18. A polyurethane as claimed in any one of claims 14-17, wherein
said (constructing unit content of the polyester composed of the
polyol compound (A) and adipic acid)/(the content of constructing
unit of a lactone) is 5/95-80/20 (weight ratio).
19. A polyurethane as claimed in any one of claims 14-18, wherein a
molar ratio of constructing unit content in said polyol
{(A1)+(A2)}/{(A1)+(A2)+- (A3)} is 0.01-10.
20. A spandex filament which comprises a polyurethane as claimed in
any one of claims 14-19.
21. A dialkylamino group-contained acrylic-based copolymer formed
by an essential copolymer component which includes a
dialkylaminoethyl(meth)acr- ylate represented by a general formula
(1) described below and a reactive monomer represented by a general
formula (2) described below.
CH.sub.2.dbd.CRCOOCH.sub.2CH.sub.2NR.sup.0R.sup.0 (1) (in the
formula, R is a hydrogen or a methyl group, R.sup.0 is an alkyl
group having a carbon number of 1-4)
CH.sub.2.dbd.CRCOOCH.sub.2CH.sub.2O[--C(.dbd.O) (CR.sup.1R.sup.2)
.sup.2x--O--].sub.n--H (2) (in the formula, R is a hydrogen or a
methyl group, x pieces of R.sup.1 and R.sup.2 are independently a
hydrogen or an alkyl group having a carbon number of 1-12,
respectively, and n pieces of ring-opened lactone chains may be
identical or different from each other. "x" is an integer of 4-7,
and an average value of "n" is 1-5)
22. A polyurethane composition characterized by containing a
dialkylamino group-contained acrylic-based copolymer as claimed in
claim 21.
23. A spandex composition as claimed in claim 22, wherein the
content of said dialkylamino group-contained acrylic-based
copolymer is 0.5-10% by weight.
24. A spandex composition containing a dialkylamino group-contained
acrylic-based copolymer as claimed in claim 21.
25. A spandex composition as claimed in claim 24, wherein the
content of said dialkylamino group-contained copolymer is 0.5-10%
by weight.
26. A polyester diol containing at least an aliphatic dicarboxylic
acid having a carbon number of 9-12, an aliphatic diol, and
.epsilon.-caprolactone as constructing component units.
27. A polyester diol as claimed in claim 26, wherein a number
average molecular weight in said polyester polyol ranges in
500-5,000.
28. A polyester diol as claimed in claim 26 or 27, wherein said
(constructing unit content of the polyester composed of an
aliphatic diol and an aliphatic dicarboxylic acid having a carbon
number of 9-12)/(the content of constructing unit of
.epsilon.-caprolactone) is 5/95-80/20 (weight ratio).
29. A polyurethane obtained from a polyester diol as claimed in
claims 26-28 and an organic diisocyanate.
30. A polyurethane as claimed in claim 29 which is a polyurethane
for an artificial leather.
Description
TECHNICAL FIELD
[0001] The present inventions No. 1 and No. 2 relate to a spandex
filament (a polyurethane elastic fiber) which is excellent in view
of a recovering ability of elasticity, high tensile strength and,
further, hydrolysis resistance, and relate to a polyurethane which
can provide thereof and, further, relate to a polyester diol.
[0002] The present invention No. 3 relates to a spandex filament
which is excellent in view of hydrolysis resistance and a novel
polyurethane which can provide thereof.
[0003] The present invention No. 4 relates to a polyurethane which
is excellent in weatherability. In more detail, it relates to a
polyurethane having a (washing resistance) property in which the
weatherability does not almost lower even though being repeatedly
washed, and relates to a spandex filament comprising the
polyurethane.
[0004] The present invention No. 5 relates to a dialkyl amino
group-contained acrylic-based copolymer which is useful as a high
molecular-state amine stabilizer for a polyurethane. In more
detail, the present invention relates to an improvement of the
amine stabilizer for, particularly, a polyurethane/spandex filament
and a film. It is to be noted that the terminology "spandex"
employed in the No. 5 means a synthesized elastomeric composition
having a long chain which contains at least 85% by weight of a
segment-state polyurethane.
[0005] The present invention No. 6 relates to a polyurethane having
properties which are excellent in a soft feeling, hydrolysis
resistance, wrinkle resistance, and an adhesive property and,
particularly, it is excellent as an artificial leather.
TECHNICAL BACKGROUND
[0006] In the present inventions No. 1 and No. 2, a polyurethane
having a linear-state structure is obtained by allowing to react a
long chain diol having hydroxyl groups at both terminals with an
organic diisocyanate and a diol or a diamine, etc. which is named a
relatively low molecular weight chain extender having two active
hydrogens. Concerning a recovering ability of elasticity and
hydrolysis resistance in thus-obtained polyurethane, various
attempts for an improvement have been proposed. As described in
JP-A-58059212 Official Gazette, although a polyurethane using a
polyethylene glycol adipate polyester is excellent in a recovering
ability of elasticity, it is poor in hydrolysis resistance.
[0007] Further, although a 1, 4-butylene glycol adipate polyester
has a certain extent of hydrolysis resistance, a recovering ability
of elasticity is poor in a polyurethane therefrom. Still further,
although a polyurethane prepared from a polycaprolactone polyol is
excellent in hydrolysis resistance, weatherability, and heat
resistance, it is poor in a recovering ability of elasticity. In
the JP-A-58059212 Official Gazette, there is described a technology
using a specified polycaprolactone polyester polyol obtained by an
esterification reaction of a polyester polyol synthesized by a
dehydration esterification of neopentylglycol with adipic acid with
.epsilon.-caprolactone as a method for solving a drawback of a
polycaprolactone-based polyurethane. Further, in the JP-A-11001822
Official Gazette, there are disclosed polyurethane elastic fibers
which are excellent in alkali-hydrolysis resistance in which there
are employed 2-n-butyl-2-ethyl-1,3-propane diol and 2,2-diethyl
-1,3-propane diol as a diol component which constructs a polyester
polyol.
[0008] In relation to the present invention No. 2, in JP-A-63097617
Official Gazette, there is described a spandex filament, etc. which
is improved in bacteria resistance, and which is prepared from a
poly(2,2-dimethyl-1,3-propane dodecanedioate).
[0009] However, since the recovering ability of elasticity and
hydrolysis resistance are not always sufficient in the polyurethane
described in the JP-A-58059212 Official Gazette, there is desired a
polyurethane in which those are improved. Further, although the
polyurethane elastic fibers in the JP-A-11001822 Official Gazette
are excellent in hydrolysis resistance, it is desired to further
improve a recovering ability of elasticity and strength. Still
further, in the spandex filaments described in the JP-A-630978617
Official Gazette, there is desired a further improved strength.
[0010] In relation to the present invention No. 3, a polyurethane
having a linear structure is obtained by allowing to react a long
chain diol having hydroxyl groups at both terminals with an organic
diisocyanate and a relatively low molecular weight diol or diamine
which is named a chain extender having two active hydrogens.
[0011] For improvement of characteristics of thus-obtained
polyurethane, various proposes have been made. For example, in the
JP-A-11001822 Official Gazette, there are disclosed polyurethane
elastic fibers which are excellent in alkali hydrolysis resistance
in which there are employed 2-n-butyl-2-ethyl-1,3-propane diol and
2,2-diethyl-1,3-propane diol as a diol component which constructs a
polyester polyol.
[0012] Further, in JP-A-63097617 Official Gazette, there is
described a spandex filament, etc. which is improved in bacteria
resistance, and which is prepared from a
poly(2,2-dimethyl-1,3-propane dodecanedioate).
[0013] However, although the polyurethane described in the
JP-A-11001822 Official Gazette is excellent in a certain extent of
hydrolysis resistance, there is further desired an improvement.
[0014] Also in the spandex filament described in the JP-A-63097617
Official Gazette, it is in the same situation.
[0015] The polyurethane having a linear structure in relation to
the present invention No. 4 is prepared by allowing to react a long
chain diol having hydroxyl groups at both terminals with an organic
diisocyanate and a relatively low molecular weight diol or diamine
which is named a chain extender having two active hydrogens.
[0016] Thus-obtained polyurethanes are employed for a variety of
uses, for example, a thermoplastic elastomer, a hard or soft
urethane foam, an adhesive, an artificial leather, a synthetic
leather, a coating, and an elastic fiber (a spandex filament),
etc.
[0017] The polyurethanes are naturally excellent in weatherability
(including a light resistance) and durability and, in order to
further give weatherability, there are employed publicly-known
ultraviolet ray absorbents, for example, benzotriazoles such as
2-(2'-hydroxy-5'-methylph- enyl)benzotriazole and
5-chloro-2-(2'-hydroxy-3' 5'-di-t-butylphenyl)benzo- triazole, and
benzophenones such as 2,4-dihydroxybenzophenone and
2-hydroxy-4-octyloxybenzophenone.
[0018] However, since the conventional ultraviolet ray absorbents
are a low molecular weight compound having a low boiling point, the
addition thereof to a polyurethane causes various
inconveniences.
[0019] For example, the addition of a large amount of the
ultraviolet ray absorbents causes a phase separation, resulting in
that whiteness and mechanical strength are lowered in the
polyurethane.
[0020] Therefore, although the ultraviolet ray absorbent is added
as a small amount as possible and, in the case, light resistance is
not elevated until a satisfying extent in the polyurethane.
Further, since the ultraviolet ray absorbent is lost by evaporation
or decomposed during processing or molding, or it oozes out on the
surface of a molded article, it becomes impossible to give a stable
light resistance over a long time of period. Still further, when a
spandex filament product is repeatedly washed, the ultraviolet ray
absorbent is removed from the product, and an effect is gradually
reduced.
[0021] By the way, an object is not limited to the polyurethane, in
order to solve the above-described drawbacks, there is tried an
attempt (JP-A-60038411 Official Gazette, JP-A-62181360 Official
Gazette, and JP-A-03281685 Official Gazette, etc.) for giving a
polymerizable double bond such as vinyl group to the
above-described ultraviolet ray absorbent, for highly-polymerizing
the absorbent to improve a compatibility with a variety of resins,
and for preventing evaporation, thermal decomposition, and
bleeding, etc. of the ultraviolet ray absorbent.
[0022] However, these ultraviolet ray absorbable polymers also have
drawbacks as described below, and a space for an improvement is
remained. That is, although thermoplastic resins such as
thermoplastic polyurethane resins have an exceedingly high
mechanical strength and those are widely employed as a various
molding materials, since the thermoplastic polyurethane resins have
a drawback of decline in the mechanical strength by decomposition
due to alkali components, and there has been desired an improvement
of chemical resistance such as an alkali resistance and solvent
resistance.
[0023] It is to be noted that JP-A-10265557 Official Gazette
describes a lactone-modified polyol made from a polyol having an
ultraviolet ray absorbable group. However, it does not describe the
use thereof as a constructing component for a polyester diol which
is a raw material for a polyurethane.
[0024] In relation to the present invention No. 5, a segment-state
polyurethane is well known, which is prepared by forming an
isocyanate-terminated polymer through allowing to react a high
molecular weight diol (most of those are a polyether glycol or a
polyester glycol) with an organic diisocyanate, and by
chain-extending through allowing to react thereof with a diamine or
a diol.
[0025] The terminology "fiber" includes staple fibers and
continuous filaments.
[0026] U.S. Pat. No. 3,428,711 by Hunt discloses the use of a high
molecular weight tertiary aminoalkyl acrylate and methacrylate for
stabilizing a segment-state polyurethane, and a large commercial
use is found out as fibers for spandex. Hunt discloses a large
amount of such additives. A preferred stabilizer disclosed by Hunt
is a copolymer of diisopropyl amino ethylmethacrylate (hereinafter,
named "DIPAM") which has a steric hindrance with
n-decylmethacrylate (hereinafter, named "DM"). The copolymer
(hereinafter, named "poly(DIPAM/DM)") provides a polymer for a
spandex which has a large resistance to deterioration by exposure
to chlorine than a similar amine which does not have a steric
hindrance.
[0027] Additives containing a tertiary amino group having a high
molecular weight and a steric hindrance are useful for preventing
deterioration and discoloration of for a spandex polymer. However,
the additives are occasionally cause a problem in the preparation
and/or a change to worse of properties in a fiber prepared from the
spandex polymer. For example, the use of the poly(DIPAM/DM)
additives causes a certain kind of a problem in the case of
dry-spinning a filament from a spandex polymer solution. Dimethyl
acetoamide (hereinafter, named "DMAc") is a solvent to be most
preferably employed for the preparation of the spandex polymer
solution. The poly(DIPAM/DM), an antioxidant, and other additives
such as pigments are usually changed to a slurry together with the
DMAc, followed by being mixed with the spandex polymer solution
prior to spinning. However, such the slurry usually prepared at
room temperatures occasionally causes a phase-separation in the
case that a high molecular weight amine lacks a solubility to the
DMAc solvent. The phase-separation has a possibility of causing
aggregation of the additives, a problem during spinning and/or an
uniform distribution of the additives into a solution for spinning
and filaments spun therefrom. That is, the polymer for spandex
containing the poly(DIPAM/DM) or the (DPAM) additives adversely
affects to a preparation step because of inferiority of solubility
to solvent when being spun, and it causes a certain kind of
drawback to elasticity in filaments prepared from the spandex
polymer, that is, an undesired decline (that is, permanent
extension (set)) of elasticity in the spandex filaments made by
dry-spinning.
[0028] A great parts of high molecular weight tertiary
aminoalkyl(meth)acrylate additives have any one of or both
drawbacks.
[0029] On the other hand, JP-A-02086655 by Roden et al suggests the
DIPAM and a hydroxybutyl acrylate- or methacrylate-based copolymer
in order to provide an additive containing a high molecular weight
tertiary amine having a steric hindrance which is employed for a
spandex polymer.
[0030] However, in the copolymer described in the JP-A-02086655,
although it suppresses a manifestation of the decline (that is,
permanent extension (set)) in elasticity related to the use of
already known additives containing a high molecular weight tertiary
amino group having a steric hindrance to a certain extent, it is
not always sufficient in solubility to the DMAc solvent, and it
still has a possibility of a manifestation of the decline in
elasticity.
[0031] In relation to the present invention No. 6, it is usually
and widely known that an artificial leather is obtained by
processing of adding a variety of polymer compounds to a nonwoven
sheet-like material primarily composed of an ultra-fine fiber. As
the polymer compounds in the case, there are employed many elastic
polymer compounds such as a polyurethane, etc. in order to obtain
physical properties such as a soft and elastic feeling as an
artificial leather, durability, and dimensional stability. And, the
elastic polymer compounds are coated on a nonwoven sheet-like
material as a solution dissolved in an organic solvent, and then,
very often moisture-solidified.
[0032] On the other hand, since the organic solvent employed in the
case is often a substance which is very inflammable and highly
toxic, many attention must be paid when recollecting the solvent
for preventing a fire and a danger by toxicity. Further, there is a
drawback that the solvent is expensive and many costs are required
for recollecting it from a diluted aqueous solution.
[0033] Because of the various drawbacks, a variety of
investigations are made for shifting from an organic solvent type
to a water-based emulsion in the elastic polymer compound for
coating on the nonwoven sheet-like material. However, it is the
existing state that there is not still obtained an artificial
leather having a satisfying a feeling and physical properties using
a water-based emulsion.
[0034] In general, a polyurethane having a linear structure is
obtained by allowing to react a long chain diol having hydroxyl
groups at both terminals with an organic diisocyanate and a
relatively low molecular weight diol or diamine which is named a
chain extender having two active hydrogens, and a technical
background relating to the polyurethane is as described in
technical background relating to the present inventions No. 1 and
No. 2.
DISCLOSURE OF THE INVENTION
[0035] Accordingly, purpose of the present inventions No. 1 and No.
2 is to provide a spandex filament which is excellent in recovering
ability of elasticity, strength, and hydrolysis resistance, a
polyurethane which provides it, and a polyester diol which provides
thereof.
[0036] The present inventors found out that the above-described
problems can be solved by the use of a polyester diol obtained from
a specified branched aliphatic diol, .epsilon.-caprolactone, and
adipic acid, which is a raw material for a polyurethane, and the
present invention No. 1 has been completed.
[0037] Further, the present inventors found out that the
above-described problems can be solved by the use of a polyester
diol obtained from a specified branched aliphatic diol,
.epsilon.-caprolactone, and an aliphatic dicarboxylic acid having a
carbon number of 10-12, and the present invention No. 2 has been
completed.
[0038] That is, according to the present invention No. 1, as (1),
there is provided a polyester diol containing at least one diol
selected from the group consisting of
2-n-butyl-2-ethyl-1,3-propanediol, 2,2-diethyl-1,3-propanediol and
2,4-diethyl-1,5-pentanediol, .epsilon.-caprolactone, and adipic
acid as constructing components.
[0039] Further, as (2), there is provided a polyester diol as
described in the (1), in which a number average molecular weight
ranges in 500-5,000.
[0040] Still further, as (3), there is provided a polyester diol as
described in the (1) or (2), in which (the content of a
constructing unit polyester)/(the content of constructing unit of
.epsilon.-caprolactone) ranges in 5/95-80/20 (weight ratio), and
the polyester is composed of at least one diol selected from the
group consisting of 2-n-butyl-2-ethyl-1,3-propanediol,
2,2-diethyl-1,3-propanediol and 2,4-diethyl-1,5-pentanediol, and
adipic acid.
[0041] Also, as (4), there is provided a polyurethane obtained from
a polyester diols as described in any one of the (1)-(3) and an
organic diisocyanate.
[0042] And also, as a (5), there is provided a spandex filament
which comprises the polyurethane in the (4).
[0043] Further, according to the present invention No. 2, as (1),
there is provided a polyester diol containing a branched aliphatic
diol, .epsilon.-caprolactone, and an aliphatic dicarboxylic acid
having a carbon number of 10-12 as constructing components.
[0044] Further, as a (2), there is provided a polyester diol as
described in the (1), in which a number average molecular weight
ranges in 500-5,000.
[0045] Still further, as a (3), there is provided a polyester diol
as described in the (1) or (2), in which (the content of a
constructing unit polyester)/(the content of constructing unit of
.epsilon.-caprolactone) ranges in 5/95-80/20 (weight ratio), and
the polyester is composed of a branched diol and an aliphatic
dicarboxylic acid having a carbon number of 10-12.
[0046] Also, as (4), there is provided a polyurethane obtained from
a polyester diols as described in any one of the (1)-(3) and an
organic diisocyanate.
[0047] And also, as a (5), there is provided a spandex filament
which comprises the polyurethane described in the (4).
[0048] Purpose of the present invention No. 3 is to provide a
spandex filament which is particularly excellent in view of
hydrolysis resistance, and a polyurethane which provides
thereof.
[0049] The present inventors found out that the above-described
problems in the present invention No. 3 can be solved by the use of
a polyester diol containing a specified diol as a raw material for
the polyurethane, and the present invention has been completed.
[0050] That is, according to the present invention No. 3, as (1),
there is provided a polyurethane obtained by allowing to react a
polyester diol containing 2,4-diethyl-1,5-pentanediol as a
constructing component with an organic diisocyanate.
[0051] Further, as (2), there is provided a polyurethane described
in the (1), in which a number average molecular weight ranges in
500-5,000.
[0052] Still further, as (3), there is provided a spandex filament
which comprises the polyurethane described in the (1) and (2).
[0053] Purpose of the present invention No. 4 is to provide a
spandex filament in which there is improved washing resistance as a
weatherability, and to provide a polyurethane which provides
thereof.
[0054] The present inventors found out that the above-described
problems can be solved by the use of a polyester diol in which a
polyol component (A) is composed of a polyol (A1) having an
ultraviolet ray-absorbable group or a lactone-modified polyol (A2)
therefrom and other polyol (A3) as a raw material for the
polyurethane, and the present invention has been completed.
[0055] That is, according to the present invention No. 4, as (1),
there is provided a polyurethane obtained from a polyetherpolyol
(X) containing a polyol component (A) composed of a polyol (A1)
having an ultraviolet ray-absorbable group or a lactone-modified
polyol (A2) therefrom and other polyol components (A3), adipic acid
(B), and an organic diisocyanate (Y).
[0056] Further, as (2), there is provided a polyurethane described
in the (1), in which the polyol (A1) having an ultraviolet
ray-absorbable group is a compound represented by formula (1) 1
[0057] Still further, as (3), there is provided a polyurethane
described in the (1) or (2), in which the lactone is
.epsilon.-caprolactone.
[0058] Also, as (4), there is provided a polyurethane described in
any one of the (1)-(3), in which a number average molecular weight
of the polyester polyol ranges in 500-5,000.
[0059] And also, as (5), there is provided a polyurethane described
in any one of the (1)-(4), in which (a constructing unit content of
the polyester)/(the content of constructing unit of a lactone) is
5/95-80/20 (weight ratio), and the polyester is composed of the
polyol compound (A) and adipic acid.
[0060] And also, as the present invention (6), there is provided a
polyurethane described in any one of the (1)-(5), in which a molar
ratio of constructing unit content in the polyol
{(A1)+(A2)}/{(A1)+(A2)+(A3)} ranges in 0.01-10.
[0061] And also, as the present invention (7), there is provided a
spandex filament which comprises the polyurethane described in any
one of the (1)-(6).
[0062] Purpose of the present invention No. 5 is to provide a
tertiary amino group-contained additive which is employed for a
spandex polymer, in which solubility into DMAc which is a solvent
is higher, by which the spandex polymer is protected from
deterioration and discoloration, and in which a decrease of
elasticity (permanent extension (set)) is further improved in
relation to the use of an already-known tertiary amino
group-contained additive having a high molecular weight and steric
hindrance, to provide a polyurethane composition and a spandex
composition containing the additives.
[0063] The present inventors, as an intensive investigation for
solving the above-described problems, found out that an
acrylic-based copolymer has a high solubility into DMAc which is a
solvent and has an exact effect, and the above-described problems
can be solved, which contains a novel tertiary amino group formed
by a dialkylaminomethyl(meth)acrylate and a reactive monomer having
a specified structure which are an essential copolymerizable
component, and the present invention No. 5 has been completed.
[0064] That is, according to the present invention No. 5, as (1),
there is provided a dialkylamino group-contained acrylic-based
copolymer formed by an essential copolymer component which includes
a dialkylaminoethyl(meth)- acrylate represented by a general
formula (1) described below and a reactive monomer represented by a
general formula (2) described below.
CH.sub.2.dbd.CRCOOCH.sub.2CH.sub.2NR.sup.0R.sup.0 (1)
[0065] (in the formula, R is a hydrogen atom or a methyl group,
R.sup.0 is an alkyl group having a carbon atom number of 1-4)
CH.sub.2.dbd.CRCOOCH.sub.2CH.sub.2O[--C(.dbd.O)
(CR.sup.1R.sup.2).sup.2x--- O--].sub.n--H (2)
[0066] (in the formula, R is a hydrogen atom or a methyl group, x
pieces of R.sup.1 and R.sup.2 are independently a hydrogen atom or
an alkyl group having a carbon atom number of 1-12, respectively,
and n pieces of ring-opened lactone chains may be identical or
different from each other. x is an integer of 4-7, and an average
value of n is 1-5)
[0067] Further, as (2), there is provided a polyurethane
composition characterized by containing a dialkylamino
group-contained acrylic-based copolymer described in the present
invention (1).
[0068] Still further, as (3), there is provided a polyurethane
composition as described in the invention (3), in which the content
of the dialkylamino group-contained acrylic-based copolymer is
0.5-10% by weight.
[0069] Also, as (4), there is provided a spandex composition
containing a dialkylamino group-contained acrylic-based copolymer
as described in the invention (1)
[0070] Also, as (5), there is provided a spandex composition as
described in the invention (4), in which the content of the
dialkylamino group-contained copolymer is 0.5-10% by weight.
[0071] Purpose of the present invention No. 6 is to provide a
polyurethane which provides an artificial leather which is
excellent in a recovering ability of elasticity, strength, and
hydrolysis resistance, that is, which satisfies hydrolysis
resistance, wrinkle resistance, an adhesive property, and a
feeling.
[0072] The present inventors, as a result of an intensive
investigation for solving the purpose in the present invention No.
6, have attained to the present invention.
[0073] That is, according to the present invention No. 6, as (1),
there is provided a polyester diol containing at least an aliphatic
dicarboxylic acid, an aliphatic diol, and .epsilon.-caprolactone as
constructing component units.
[0074] Further, as (2), there is provided a polyester diol as
described in the (1), in which a number average molecular weight of
the polyester polyol ranges in 500-5,000.
[0075] Still further, as (3), there is provided a polyester diol as
described in the (1) or (2), in which (the content of a polyester
constructing unit composed of an aliphatic diol and an aliphatic
dicarboxylic acid having a carbon number of 9-12)/(the content of
.epsilon.-caprolactone constructing unit) ranges in 5/95-80/20
(weight ratio).
[0076] Also, as (4), there is provided a polyurethane obtained from
a polyester diol as described in any one of the (1)-(3) and an
organic diisocyanate.
[0077] And also, as (5), there is provided a polyurethane described
in the (4) for an artificial leather.
BEST MODE FOR CARRYING OUT THE INVENTION
[0078] Hereinafter, embodiments for carrying out the present
invention No. 1 and the present invention No. 2 will be illustrated
one after another.
[0079] The present invention No. 1 will be illustrated
[0080] The diol to be employed in the present invention is a
specified diol, that is, at least one diol selected from the group
of 2-n-butyl-2-ethyl-1,3-propanediol, 2,2-diethyl-1,3-propanediol
and 2,4-diethyl-1,5-pentanediol. These may be employed solely,
respectively, or in mixing of two kinds. Further, within a range in
which an effect by the present invention is not deteriorated, other
diol components can be employed. As such the diol compounds, there
are enumerated ethylene glycol, propylene glycol, 1,4-butanediol,
1, 6-hexanediol, neopentyl glycol, 2-methyl-1,3-propanediol,
3-methyl-1,5-pentanediol, 1,8-nonanediol, diethylene glycol,
dipropylene glycol, and 1,4-cyclohexane dimethanol, etc.
[0081] Although adipic acid is employed as an acid component for
the polyester diol in the present invention, within a range in
which an effect by the present invention is not deteriorated, there
can be employed other acid components, for example, aliphatic or
aromatic dicarboxylic acids such as glutaric acid, pimelic acid,
sberic acid, azelaic acid, sebasic acid, dodecanoic acid,
1,11-undecane dicarboxylic acid, terephthalic acid, isophthalic
acid, and 5-sulphosodium isophthalic acid. The other acid
components may be employed solely or even as a mixture of two or
more kinds together with adipic acid. It is to be noted that the
acid components which are a raw material may be employed in the
form of an ester derivative or an acid anhydride. In the diol
relating to the present invention, other constructing components
are .epsilon.-caprolactone and, within a range in which an effect
by the present invention is not deteriorated, there may be even
employed a methylated .epsilon.-caprolactone such as
monomethyl-.epsilon.-caprolacto- ne, and
trimethyl-.epsilon.-caprolactone, .gamma.-butyrolactone, and
.delta.-varelolactone as auxiliary components for
.epsilon.-caprolactone.
[0082] A method for the preparation of the polyester diol in the
present invention is not particularly limited and, publicly-known
methods can be applied. For example, it can be prepared according
to a method described in the JP-A-58059212 Official Gazette. That
is, it can be prepared through (a one-pot method) a dehydration
esterification and a ring-opening reaction, and a
transesterification by heating after mixing the above-described
diols, .epsilon.-caprolactone, and adipic acid. Otherwise, it can
be also prepared by mixing and heating a polyester diol obtained by
a dehydration esterification of a diol with adipic acid with a
polycaprolactone polyol which is synthesized by allowing to conduct
a ring-opening polymerization of .epsilon.-caprolactone with a
polyvalent alcohol, followed by a transesterification thereof.
Further, it can be also prepared by ring-opening polymerization of
.epsilon.-caprolactone with a polyester polyol having a low
molecular weight. Of those, the one-pot method is preferred owing
to be convenient.
[0083] The reactions can be conducted at 130-240.degree. C.,
preferably 140-230.degree. C. from a viewpoint of preventing
discoloration and from a viewpoint of preventing a decomposition
reaction of .epsilon.-caprolactone.
[0084] In the reactions, catalysts are usually employed in
0.05-1000 ppm by weight, preferably 0.1-100 ppm by weight based on
total monomers. As the catalysts, there can be employed organic
titanium compounds such as tetrabutyl titanate and tetrapropyl
titanate, tin compounds such as dibutyltin laurate, tin octylate,
dibutyltin oxide, stannous chloride, stannous bromide, and stannous
iodide.
[0085] The reactions can be preferably conducted while streaming an
inert gas such as nitrogen gas from a viewpoint of preventing
discoloration of a desired product obtained.
[0086] As content of constructing unit of the polyester diol in the
present invention, respective raw materials are employed in a range
of a proportion so that (content of constructing unit of the
polyester)/(content of constructing unit of .epsilon.-caprolactone)
becomes a range of 5/95-80/20 (weight ratio), which is composed of
at least one kind selected from the group consisting of
2-n-butyl-2-ethyl-1,3-propanediol, 2,2-diethyl-1,3-propanediol and
2,4-diethyl-1,5-pentanediol and adipic acid. Also in the case that
a poly-.epsilon.-caprolactone is employed, it is the same. In
thus-obtained polyester diol, a number average molecular weight
ranges in 500-5,000, preferably 1,500-4,000. In the case of not
less than 5,000, crystallinity increases in a soft segment,
resulting in that there is not apt to be obtained a spandex
filament having sufficient physical properties. The number average
molecular weight can be measured by a hydroxyl value (JIS
K1557).
[0087] A polyurethane is prepared from the polyester diol obtained
as described hereinabove and an organic diisocyanate. As a method
for the preparation of the polyurethane, there are enumerated
publicly-known methods, for example, the methods described in the
JP-A-58059212 Official Gazette and JP-A-11001822 Official Gazette
and, it may be conducted according to these. That is, there are a
one-shot method in which a polyester diol, a low molecular weight
diol or diamine, etc. which are a chain extender, and an organic
diisocyanate are allowed to collectively react under the presence
or absence of solvents and a prepolymer method in which a
prepolymer is prepared by allowing to previously react a polyester
diol with an organic diisocyanate, and then, a low molecular weight
diol is allowed to react under the presence or absence of
solvents.
[0088] A melting polymerization method which is conducted under the
absence of solvents is preferred from a viewpoint of costs. In the
case, a formulation ratio of raw materials is 0.5-1.5, preferably
0.8-1.2 as (NCO group in the organic diisocyanate)/(total OH group
in the polyester diol and a low molecular weight diol). As the
solvents, there are enumerated toluene, xylene, ethyl acetate,
butyl acetate, methylethyl ketone, dimethyl formamide, and
tetrahydrofran, etc.
[0089] As the organic diisocyanate to be employed in the present
invention, there are enumerated 2,4-tolylene diisocyanate,
2,6-tolylene diisocyanate, p-phenylene diisocyanate,
4,4'-diphenylmethane diisocyanate, m-phenylene diisocyanate,
hexamethylene diisocyanate, tetramethylene diisocyanate,
2,4-naphthalene diisocyanate, 4,4'-diphenylene diisocyanate,
p-xylene diisocyanate, m-xylene diisocyanate, 4,4'-diisocyanate
dicyclohexane, and isophorone diisocyanate, etc. These may be even
employed solely or in combination of two or more kinds.
[0090] As the above-described low molecular weight diol which is a
chain extender, there can be employed the diols to be employed in
the present invention or the diol compounds which can be employed
together as described hereinabove.
[0091] As the diamine which is a chain extender, there can be
employed ethylenediamine, hydrazine, isophoronediamine,
metaphenylene diamine, 4,4'-diaminodiphenylmethane,
4,4'-diaminodiphenylsulphone, and
3,3'-dichloro-4,4'-diaminodiphenylmethane, etc.
[0092] The polyurethane obtained by the above-described methods is
employed in a variety of uses in which a usual polyurethane is
employed, for example, a thermoplastic elastomer, a hard or soft
urethane foam, an adhesive, an artificial leather, and coating,
etc., and particularly, it is preferred to employ for a spandex
filament.
[0093] As a spinning method for obtaining a spandex filament from
the polyurethane in the present invention, there can be employed
publicly-known methods, for example, a dry-spinning method, a
wet-spinning method, and a melt-spinning method, etc. Of the
methods, the melt-spinning method is preferred from a viewpoint of
costs.
[0094] Further, there is obtained a filament having a further high
physical properties by heat treatment of an elastic filament after
spinning.
[0095] In the spandex filament of the present invention, there can
be also optionally added an antioxidant such as a
phenol-derivative, an ultraviolet ray absorbent such as a
substituted benzotriazole, and an anti-blocking agent such as a
higher fatty acid metal salt and a silicone compound, etc.
[0096] The spandex filament provided by the present invention is
excellent in a recovering property of elasticity, strength, and
hydrolysis resistance, and it is employed in a general use form for
a spandex filament, that is, a mix-knitting and mix-weaving with a
nylon and cotton, etc. Particularly, in the case that the cotton is
employed as a material for mixing, it shows an excellent hydrolysis
resistance even through post treatment steps after mix-knitting and
mix-weaving, that is, a boiling-off step, a bleaching step, and a
mercerization step, etc. in which it is treated at a high
temperature under an acid or alkali atmosphere.
[0097] Hereinafter, there are illustrated embodiments for carrying
out the present invention No. 2.
[0098] As the branched diols to be employed in the present
invention, for example, there are enumerated 1,2-propylene glycol,
1,3-butylene glycol, 2-methyl-1,3-propane diol, neopentyl glycol,
3-methyl-1,5-pentane diol, 2-n-butyl-2-ethyl-1,3-propane diol,
2,2-dimethyl-1,3-propane diol, 2,2-diethyl-1,3-propane diol,
2,4-diethyl-1,5-pentane diol, 1,2-hexane glycol, and 1,2-octyl
glycol, etc. These may be employed solely or even in mixing of two
or more kinds. Further, within a range in which an effect by the
present invention is not deteriorated, other diol components can be
also employed as auxiliary components. As such the diol compounds,
there are enumerated aliphatic diols not having branches, for
example, ethylene glycol, 1,3-propylene glycol, 1,4-butanediol,
1,6-hexanediol, 1,8-nonanediol, and diethylene glycol, etc.
[0099] As an acid component for the polyester diol relating to the
present invention, there are enumerated aliphatic dicarboxylic
acids having a carbon number of 10-12, for example, sebasic acid,
dodecanoic diacid, and 1,11-undecane dicarboxylic acid, etc. Of
those, sebasic acid and dodecanoic diacid are preferred.
[0100] It is to be noted that within a range in which an effect by
the present invention is not deteriorated, there can be employed
other acid components, for example, aliphatic or aromatic
dicarboxylic acids such as glutaric acid, adipic acid, pimelic
acid, sberic acid, azelaic acid, terephthalic acid, isophthalic
acid, 5-sulphosodium isophthalic acid, etc. These other acid
components may be even employed solely or even in mixing of two or
more kinds together with the aliphatic dicarboxylic acids having a
carbon number of 10-12. It is to be noted that the acid components
for raw materials may be even employed in the form of an ester
derivative or an acid anhydride.
[0101] Other components for constructing the polyester diol
relating to the present invention is .epsilon.-caprolactone as well
as in the present invention No. 1, and other lactones may be even
employed as auxiliary components as well as in the present
invention No. 1.
[0102] As a method for the preparation of the polyester diol
relating to the present invention, there can be applied the same
methods as described in the present invention No. 1.
[0103] As content of constructing unit of the polyester diol of the
present invention, respective raw materials are employed in a range
of a proportion so that (content of constructing unit of the
polyester which is composed of a branched diol and the aliphatic
dicarboxylic acids having a carbon number of 10-12)/(content of
constructing unit of .epsilon.-caprolactone) becomes a range of
5/95-80/20 (weight ratio). Also in the case that a
poly-.epsilon.-caprolactone is employed, it is the same. In
thus-obtained polyester diol, a number average molecular weight
ranges in 500-5,000, preferably 1,500-4,000. In the case of not
less than 5,000, crystallinity increases in a soft segment,
resulting in that there is not apt to be obtained a spandex
filament having sufficient physical properties. The number average
molecular weight can be measured by a hydroxyl value (JIS
K1557).
[0104] A polyurethane is prepared from the polyester diol obtained
as described hereinabove and an organic diisocyanate, and a method
for the preparation of the polyurethane is the same as described in
the present invention No. 1.
[0105] As a low molecular weight diol which is a chain extender,
there can be employed a branched aliphatic diol to be employed in
the present invention or the above-described diol compounds not
having branches which can be employed together therewith. As an
diamine which is a chain extender, there can be employed the same
ones as exemplified in the present invention No. 1.
[0106] The uses of the polyurethane and descriptions relating to
the spandex filament in the present invention No. 1 can be applied
to the present invention No. 2 as it is.
[0107] Hereinafter, there are illustrated embodiments for carrying
out the present invention No. 3.
[0108] As the diols to be employed in the present invention, there
is employed 2,4-diethyl-1,5-pentane diol. However, there may be
employed at least one of other diols together with the diol, for
example, ethylene glycol, propylene glycol,
2-n-butyl-2-ethyl-1,3-propane diol, 2,2-diethyl-1,3-propane diol,
1,4-butanediol, 1,6-hexanediol, neopentyl glycol,
2-methyl-1,3-propane diol, 3-methyl-1,5-pentane diol,
1,8-nonanediol, diethylene glycol, dipropylene glycol, and
1,4-cyclohexane dimethanol, etc. In the case,
2,4-diethyl-1,5-pentane diol is employed in not less than 5% by
mol, and preferably not less than 10% by mol from a viewpoint of an
effect by the present invention, and it is preferably employed in
not more than 80% by mol, more preferably not more than 70% by mol
from an economical viewpoint.
[0109] An acid component for the polyester diol relating to the
present invention is not particularly limited, there are enumerated
aliphatic or aromatic dicarboxylic acids such as glutaric acid,
adipic acid, pimelic acid, sberic acid, azelaic acid, sebasic acid,
dodecanoic diacid, and 1,11-undecane dicarboxylic acid,
terephthalic acid, isophthalic acid, and 5-sulphosodium isophthalic
acid, etc. These acid components may be even employed solely or
even in mixing of two or more kinds. It is to be noted that the
acid components for raw materials may be even employed in the form
of an ester derivative or an acid anhydride. Of those, adipic acid
is particularly preferred.
[0110] A method for the preparation of the polyester diol relating
to the present invention is not particularly limited and,
publicly-known methods can be applied. In the reactions, catalysts
are usually employed in 0.05-1000 ppm by weight, preferably 0.1-100
ppm by weight based on total monomers. As the catalysts, there can
be employed organic titanium compounds such as tetrabutyl titanate
and tetrapropyl titanate, tin compounds such as dibutyltin laurate,
tin octylate, dibutyltin oxide, stannous chloride, stannous
bromide, and stannous iodide. The reactions can be preferably
conducted while streaming an inert gas such as nitrogen gas from a
viewpoint of preventing discoloration of an desired product
obtained.
[0111] In the polyester diol, a number average molecular weight
ranges in 500-5,000, preferably 1,500-4,000. In the case of not
less than 5,000, crystallinity increases in a soft segment,
resulting in that there is not apt to be obtained a spandex
filament having sufficient physical properties. The number average
molecular weight can be measured by a hydroxyl value (JIS
K1557).
[0112] A polyurethane is prepared from the polyester diol obtained
as described hereinabove and an organic diisocyanate, and a method
for the preparation of the polyurethane is the same as described in
the present invention No. 1.
[0113] As a low molecular weight diol which is a chain extender,
there can be employed a diol to be employed as an essential raw
material in the present invention or the above-described diol
compounds which can be employed together therewith. As an diamine
which is a chain extender, there can be employed the same ones as
exemplified in the present invention No. 1.
[0114] The uses of the polyurethane and descriptions relating to
the spandex filament in the present invention No. 1 can be applied
to the present invention No. 3 as it is.
[0115] Hereinafter, there are illustrated embodiments for carrying
out the present invention No. 4.
[0116] The polyol (A1) having ultraviolet ray absorbable groups to
be employed in the present invention is not particularly limited
and, for example, there is enumerated a diol having two alcoholic
hydroxyl groups represented by formula (1) described below.
[0117] This is bis[3-(2H-benzotriazole-2-yl)-4-hydroxy-benzene
ethanol]. As this diol, there can be employed a synthetic product
and a commercially supplied product. 2
[0118] Further, a lactone-modified polyol is not particularly
limited, and there is enumerated a diol compound represented by the
formula (2). It is to be noted that the lactone-modified polyol
(A2) can be employed solely or together with the polyol (A1) in the
preparation of a polyester polyol described hereinafter. 3
[0119] (R.sup.1-R.sup.2; H, an alkyl group having a carbon number
of 1-10, n and n' are an integer of 4-8, and m and m' are an
integer of 1-20)
[0120] In a method for the preparation of the ultraviolet ray
absorbable compound represented by the formula (2), lactones
represented by formula (3) described below are introduced into the
diol represented by formula (1) described hereinabove by a
ring-opening addition polymerization. 4
[0121] (R.sup.1-R.sup.2; H, an alkyl group having a carbon number
of 1-10, n and n' are an integer of 4-8) As the lactones
represented by the formula (3) described above,
.epsilon.-caprolactone, trimethyl-.epsilon.-caprolactone,
monomethyl-.epsilon.-caprolactone, .gamma.-butyrolactone, and
8-varelolactone. Of those, .epsilon.-caprolactone is preferred.
[0122] As the catalysts to be employed in the ring-opening addition
polymerization of the lactones represented by the formula (3)
described above to the diol represented by the formula (1)
described above, there can be employed organic titanium compounds
such as tetraethyl titanate, tetrabutyl titanate, and tetrapropyl
titanate, tin compounds such as tin octylate, dibutyltin oxide,
dibutyltin laurate, a mono-n-butyltin fatty acid salt, and a
halogenated tin compound such as stannous chloride, stannous
bromide, and stannous iodide, etc.
[0123] Use amount of the catalysts is 0.1-10000 ppm, and preferably
1-5000 ppm based on raw materials to be supplied. In the case that
the use amount of the catalysts is less than 0.1 ppm, a
ring-opening reaction is remarkably slow and it is not economical.
Contrarily, in the case that it is not less than 10000 ppm,
although the ring-opening reaction becomes quick, there become
unpreferably worse physical properties such as durability and water
resistance in a synthetic resin in which a compound obtained is
employed.
[0124] Reaction temperature is 90-240.degree. C., and preferably
100-220.degree. C.
[0125] In the case that the reaction temperature is less than
90.degree. C., the ring-opening reaction of the lactones is
remarkably slow, it is not economical. Contrarily, in the case of
not less than 240.degree. C., there is caused a decomposition
reaction of a polylactone which is addition-polymerized by
ring-opening. Accordingly, the both cases are not preferred.
Further, a product having a good color hue is obtained by
synthesizing in an atmosphere of an inert gas such as nitrogen
during the reaction. As described hereinabove, an ultraviolet
ray-absorbent of the present invention is synthesized.
[0126] These details are as described in the above-described
JP-A-10265557 Official Gazette.
[0127] As other polyols (A3), for example, there are enumerated
ethylene glycol, 1,2-propylene glycol, 1,3-butylene glycol,
2-methyl-1,3-propanediol, neopentyl glycol, 1,4-butanediol,
1,6-hexanediol, neopentyl glycol, 2-methyl-1,3-propanediol,
3-methyl-1,5-pentanediol, 1,8-nonanediol, diethylene glycol,
dipropylene glycol, 1,4-cyclohexane dimethanol,
2-n-butyl-2-ethyl-1,3-propanediol, 2,2-diethyl-1,3-propanediol,
2,4-diethyl-1,5-pentanediol, 1,2-hexane glycol, and 1,2-octyl
glycol, etc. These may be solely or even in mixing of two or more
kinds.
[0128] As the acid components in the polyester diol relating to the
present invention, adipic acid is employed and, as other acid
components, there may be also even employed the same ones as
described in the present invention No. 1 by the same
embodiments.
[0129] A method for the preparation of the polyester polyol
relating to the present invention is not particularly limited and,
publicly-known methods can be applied. In the reactions, catalysts
are usually employed in 0.05-1000 ppm (weight), preferably 0.1-100
ppm based on total monomers. As the catalysts, there can be
employed organic titanium compounds such as tetrabutyl titanate and
tetrapropyl titanate, tin compounds such as dibutyltin laurate, tin
octylate, dibutyltin oxide, stannous chloride, stannous bromide,
and stannous iodide. The reactions can be preferably conducted
while streaming an inert gas such as nitrogen gas from a viewpoint
of preventing discoloration of a desired product obtained.
[0130] In the polyester polyol, a number average molecular weight
ranges in 500-5,000, preferably 1,500-4,000. In the case of not
less than 5,000, crystallinity increases in a soft segment,
resulting in that there is not apt to be obtained a spandex
filament having sufficient physical properties. The number average
molecular weight can be measured by a hydroxyl value (JIS
K1557).
[0131] As content of constructing unit of the polyester polyol of
the present invention, respective raw materials are employed in a
range of a proportion so that (the content of constructing unit
composed of the polyester and adipic acid)/(content of constructing
unit of the lactone) becomes a range of 5/95-80/20 (weight
ratio).
[0132] A polyurethane is prepared from the polyester diol obtained
as described hereinabove and an organic diisocyanate, and a method
for the preparation of the polyurethane is the same as described in
the present invention No. 1.
[0133] As a low molecular weight diol which is a chain extender,
there can be employed a diol to be employed as an essential raw
material in the present invention or the above-described diol
compounds not having branches which can be employed together
therewith. A diamine which is a chain extender is the same ones as
exemplified in the present invention No. 1.
[0134] The uses of the polyurethane obtained by the above-described
method can be applied to the uses described in the present
invention No. 1 and, further, it is preferred to be employed as a
spandex filament in which washing resistance is particularly
required.
[0135] In the present invention No. 4, as a method for giving a
spandex filament from the polyurethane, there can be applied the
descriptions in the present invention No. 1.
[0136] The spandex filament provided by the present invention is
excellent in the washing resistance as weatherability, and it is
employed in a general use form for a spandex filament, that is, a
mix-knitting and mix-weaving with a nylon and cotton, etc.
[0137] Particularly, in the case that the cotton is employed as a
material for mixing, it shows an excellent weatherability even
through post treatment steps after mix-knitting and mix-weaving,
that is, a boiling-off step, a bleaching step, and a mercerization
step, etc. in which it is treated at a high temperature under an
acid or alkali atmosphere. Further, even though it is repeatedly
washed after use as a final product, decline of the weatherability
is not almost observed.
[0138] Hereinafter, there are illustrated embodiments for carrying
out the present invention No. 5.
[0139] A high molecular-state tertiary amine compound which is
appropriate for employing in the present invention is a copolymer
of a dialkylaminoethyl(meth)acrylate. In more detail, a
dialkylaminoethyl(meth)acrylate represented by a general formula
(1) described below is employed as a comonomer.
CH.sub.2.dbd.CRCOOCH.sub.2CH.sub.2NR.sup.0R.sup.0 (1)
[0140] (in the formula, R is a hydrogen or a methyl group, R.sup.0
is an alkyl group having a carbon number of 1-4)
[0141] As a kind of specific monomers, there are employed
diisopropyl amino ethylmethacrylate (DIPAM), dimethylaminoethyl
methacrylate (DMAM), diethylaminoethyl methacrylate (DEAM),
diisopropyl amino ethylacrylate (DIPAA), dimethylaminoethyl
acrylate (DMAA), and diethylaminoethyl acrylate (DEAA), etc. Of the
monomers, the DIPAM is a most preferably employed monomer.
[0142] Use amount of the monomer ranges in usually 60% to 90% by
weight, and preferably 70% to 80% by weight in a copolymer.
[0143] On the other hand, a comonomer to be copolymerized with the
above-described dialkylaminoethyl(meth)acrylate is a reactive
monomer represented by a general formula (2) described below.
CH.sub.2.dbd.CRCOOCH.sub.2CH.sub.2O[--C(.dbd.O)
(CR.sup.1R.sup.2).sup.2x--- O--].sub.n--H (2)
[0144] (in the formula, R is a hydrogen or a methyl group, x pieces
of R.sup.1 and R.sup.2 are independently a hydrogen atom or an
alkyl group having a carbon number of 1-12, respectively, and n
pieces of ring-opened lactone chains may be identical or different
from each other. x is an integer of 4-7, and an average value of n
is 1-5)
[0145] In the case that an average value of n exceeds 5, there is
caused a problem in view of solubility to a solvent in a copolymer
obtained and compatibility with a polyurethane resin and spandex
composition.
[0146] A method for the preparation of the reactive monomer
comprises allowing to react a lactone represented by a general
formula (3) described below with a monoacrylate or methacrylate of
ethylene glycol. 5
[0147] (in the formula, x pieces of R.sup.1 and R.sup.2 are
independently a hydrogen or an alkyl group having a carbon number
of 1-12, respectively, and x is an integer of 4-7)
[0148] As the lactones represented by the formula (3), there are
enumerated .epsilon.-caprolactone,
trimethyl-.epsilon.-caprolactone,
monomethyl-.epsilon.-caprolactone, .gamma.-butyrolactone, and
.delta.-varelolactone, etc.
[0149] Preferred lactones are .epsilon.-caprolactone,
4-methyl-.epsilon.-caprolactone, 3-methyl-.epsilon.-caprolactone,
and a mixture thereof.
[0150] A more specific method for the preparation is conducted by
allowing to react the lactone with a monoacrylate or methacrylate
of ethylene glycol under the presence of approximately not more
than 200 ppm, and preferably not more than 100 ppm of
catalysts.
[0151] As the catalysts to be employed in the present invention,
there are enumerated one or two or more kinds of organic metal
compounds and other metal compounds, for example, tin compounds
such as stannous chloride, stannous bromide, stannous iodide, and
dibutyltin oxide, or ferric chloride, and other Levis acids and
protonic acids. As preferred catalysts, there are enumerated
stannous chloride, tin octylate, dibutyltin laurate, and other tin
compounds; titanates such as tetraisopropyl titanate, etc.
[0152] The reaction is conducted at temperatures of approximately
100-140.degree. C., and preferably approximately 110-130.degree. C.
The reaction is conducted at ordinary pressure, and may be even
conducted at a higher pressure or a lower pressure. The reaction is
conducted at an atmosphere in which oxygen concentration is
adjusted to 4% to 8%, whereby, there is preferably suppressed a
polymerization of a monoacrylate or a methacrylate of
ethyleneglycol. Reaction time of period is approximately 2-30
hours, and preferably approximately 3-20 hours.
[0153] The reaction is conducted under the presence of an
appropriate inhibitor in order to prevent a polymerization of a
double bond in a monoacrylate or a methacrylate of ethyleneglycol.
As the inhibitor, there are enumerated monomethylether of
hydroquinone, benzoquinone, phenothiazine, methyhydroquinone,
2,5-di-t-butylquinone, hydroquinone, and other free radical (a free
group) inhibitors which are publicly-known in a related field. Use
amount of the inhibitors is not more than 1000 ppm, preferably not
more than 800 ppm, and most preferably not more than 600 ppm.
[0154] In a preferred specific example, the method in the present
invention is conducted by adding a lactone to a reaction vessel
while sparging (dispersing) the lactone by an inert gas such as
nitrogen, followed by heating at reaction temperatures
(approximately 100.degree. C.-140.degree. C.). The lactone to be
employed may be dried using a common desiccating agent such as, for
example, Molecular Sieves, prior to adding to the reaction vessel.
In the case of attaining to the reaction temperature or immediately
after thereof, sparging of the inert gas is changed to an
atmospheric mixture in which oxygen concentration is adjusted to 4%
to 8%.
[0155] Various other methods may be applied. For example, a gas
mixture may be even employed only for the purpose of flushing a gas
space in the reaction vessel during through the reaction after a
reaction system is sparged by the atmospheric gas mixture in which
oxygen concentration is adjusted to 4% to 8% for a short time of
period, that is, approximately 5-10 minutes, and then, sparging is
interrupted. Otherwise, sparging of the inert gas is stopped, and
the reaction system is flushed using the mixture through the total
reaction system. And, otherwise, the gas mixture is sparged through
the system and, separately, the gas space may be even flushed
further using an inert gas. Optionally, combination of other
methods may be even conducted.
[0156] The monoacrylate or methacrylate of ethyleneglycol is mixed
with the catalysts and inhibitors, followed by adding mixture
thereof to the lactone heated. In other methods, the inhibitors may
be even added to the lactone prior to heating. Further, the lactone
is added to the heated monoacrylate or methacrylate of
ethyleneglycol, or, all reaction materials are added to the
reaction vessel in an initial stage, and the reaction may be even
conducted. In a style for adding the lactone, the monoacrylate or
methacrylate, catalysts, and inhibitors, various variations can be
employed. Final reaction mixture is maintained at the reaction
temperatures for approximately 2-30 hours.
[0157] Further, for example, the present method may be even
conducted under the presence of an appropriate solvent not
containing an active hydrogen or a polymerizable ethylenic
unsaturated group. As such the solvent, there are enumerated a
ketone, an ester, an aromatic and aliphatic hydrocarbon etc., and a
mixture thereof. As a preferred solvent, there are esters, such as
cellosolve acetate, etc.
[0158] Preferably, .epsilon.-caprolactone,
4-methyl-.epsilon.-caprolactone- , 3-methyl-.epsilon.-caprolactone,
and a mixture thereof are allowed to react with the monoacrylate or
methacrylate of ethyleneglycol in a proportion of 1 mol of the
acrylate or methacrylate with respect to 1-12 mol of the lactone.
Composition thereof may be a solid or a liquid, and most preferred
composition is a liquid.
[0159] The most preferred composition can be prepared by allowing
to react .epsilon.-caprolactone, 4-methyl-.epsilon.-caprolactone,
3-methyl-.epsilon.-caprolactone, and a mixture thereof with the
monoacrylate or methacrylate of ethyleneglycol in a proportion of 1
mol of the monoacrylate or methacrylate of ethyleneglycol with
respect to 1-5 mol of .epsilon.-caprolactone,
4-methyl-.epsilon.-caprolactone, 3-methyl-.epsilon.-caprolactone,
and a mixture thereof.
[0160] Reaction mixture is taken out, and it can be employed
without refining. Optionally, the reaction mixture can be refined
by common methods such as vacuum stripping.
[0161] As a method of the preparation of the copolymer of the
present invention, there can be applied a preparation method by a
usual radical solution polymerization as described in JP-A-02086655
by Roden et al.
[0162] Specific detailed preparation method of the copolymer is
illustrated in Examples of the present invention.
[0163] In the copolymer of the present invention, a number average
molecular weight ranges in preferably 2000-2000000, and more
preferably 5000-500000, and a weight average molecular weight
ranges in preferably 4000-4000000, and more preferably
10000-1000000 from a viewpoint of solubility to solvents and
compatibility with a polyurethane and a spandex.
[0164] The copolymer relating to the present invention is
particularly useful in a polyurethane/spandex filament. The present
invention provides an improved polyurethane composition and spandex
composition containing a dialkylamino group-contained acrylic based
copolymer. The polyurethane composition and the spandex composition
containing additives relating to the present invention have an
excellent resistance to deterioration and discoloration, and those
show an excellent processability and permanent extension property
compared to a similar polymer containing a publicly-known high
molecular weight tertiary amine additive.
[0165] The improved spandex composition of the present invention is
prepared from a segmented polyurethane, for example, polyether, a
polyester, and a polyesterether. Such the spandex polymers are well
known and, above all, those can be prepared by the methods
disclosed in U.S. Pat. Nos. 2,929,804, 3,097,192, 3,428,711,
3,533,290, and 3,555,115. The composition of the present invention
is most useful in a spandex prepared by the polyether.
[0166] The polyurethane composition and the spandex composition
relating to the present invention are prepared by allowing to react
a polyol and/or a polyester polyol which have hydroxyl groups at
both terminals with an organic diisocyanate, and a relatively-low
molecular weight diol or diamine, etc. having two active hydrogens
which is named a chain extender and, optionally, under the presence
of catalysts.
[0167] As the polyols, for example, there are enumerated
ethyleneglycol, 1,2-propylene glycol, 1,3-butylene glycol,
2-methyl-1,3-propanediol, neopentyl glycol, 1,4-butanediol,
1,6-hexanediol, neopentyl glycol, 2-methyl-1,3-propanediol,
3-methyl-1,5-pentanediol, 1,8-nonanediol, diethylene glycol,
dipropylene glycol, 1,4-cyclohexane dimethanol,
2-n-butyl-2-ethyl-1,3-propanediol, 2,2-diethyl-1,3-propanediol,
2,4-diethyl-1,5-pentanediol, 1, 2-hexaneglycol, 1, 2-octylglycol, a
polyol in which there are added ethyleneoxide, propyleneoxide, and
butyleneoxide, etc. to those, and a modified product thereof, etc.
These may be solely or even in mixing of two or more kinds.
[0168] Adipic acid is employed as an acid component for the
polyester diol and, as other acid components, there may be even
employed other acid components such as aliphatic or aromatic
dicarboxylic acids such as glutaric acid, pimelic acid, sberic
acid, azelaic acid, sebasic acid, dodecanoic acid, 1,11-undecane
dicarboxylic acid, terephthalic acid, isophthalic acid, and
5-sulphosodium isophthalic acid. The other acid components may be
employed solely or even as a mixture of two or more kinds. It is to
be noted that the acid components which are a raw material may be
even employed in the form of an ester derivative or an acid
anhydride.
[0169] An organic diisocyanate is the same as described in the
present invention No. 1.
[0170] As a low molecular weight diol which is a chain extender,
there can be employed the above-described diol compounds. A diamine
which is a chain extender is the same ones as exemplified in the
present invention No. 1.
[0171] Amount of the additives which are useful for protecting the
spandex polymer of the present invention usually ranges in a wide
scope from a small amount of 0.5% by weight or so to a large amount
of 10% by weight or so. Preferably, concentration of the additives
ranges in 2-6% by weight. In less than 0.5% by weight, an effect is
poor and, in largely exceeding 10% by weight, characteristics in
spandex filament unpreferably are lost.
[0172] For adding the dialkylamino(meth)acrylic-based polymer
additive in relation to the present invention to a spandex polymer,
usual methods can be applied. For example, a solution of the
additive may be prepared in the same solvent as for preparing a
spandex spinning solution. The solution can be added to the polymer
solution before molding of the polymer into a final product, for
example, a filament or a film.
[0173] Addition of the polymer in relation to the present invention
is a general style as an addition method disclosed in U.S. Pat. No.
3,428,711 by Hunt et al, and the disclosure can be referred.
[0174] In the spandex polymer composition of the present invention,
other various additives can be added for other purposes. In the
other various additives, there may be even exist a pigment or a
delustering agent, for example, titanium dioxide, an anti-blocking
agent, or a lubricant, for example, magnesium stearate and calcium
stearate, a whiteness accelerator, for example, Ultramarine Blue,
and fillers, for example, talc, etc.
[0175] Further, other than the useful uses in fibers and a film,
the polyurethane polymer containing the dialkylamino(meth)acrylate
of the present invention can be applied in, for example, uses such
as an artificial leather, etc.
[0176] Hereinafter, there are illustrated embodiments for carrying
out the present invention No. 6.
[0177] As aliphatic diols to be employed in the present invention,
in addition to the branched aliphatic diols exemplified in the No.
2 of the present invention, there are enumerated the aliphatic
diols not having branches exemplified as auxiliary components in
the No. 2 of the present invention. There are employed solely,
respectively, and there may be employed in mixing of two or more
kinds.
[0178] As an acid component for the polyester diol relating to the
present invention, there are enumerated aliphatic dicarboxylic
acids having a carbon number of 9-12, for example, azelaic acid,
sebasic acid, dodecanoic diacid, and 1,11-undecane dicarboxylic
acid, etc. Of those, azelaic acid, sebasic acid, and dodecanoic
diacid are preferred.
[0179] It is to be noted that within a range in which an effect by
the present invention is not deteriorated, there can be employed
other acid components, for example, aliphatic or aromatic
dicarboxylic acids such as glutaric acid, adipic acid, pimelic
acid, sberic acid, terephthalic acid, isophthalic acid, and
5-sulphosodium isophthalic acid, etc. These other acid components
may be even employed solely or even in mixing of two or more kinds
together with the aliphatic dicarboxylic acids having a carbon
number of 9-12. It is to be noted that the acid components for raw
materials may be even employed in the form of an ester derivative
or an acid anhydride.
[0180] Other component which constructs the polyester diol in
relation to the present invention is .epsilon.-caprolactone, and
other lactones may be employed as auxiliary components as well as
in the No. 1 of the present invention.
[0181] As a method for the preparation of the polyester diol in the
present invention, the same method can be applied as described in
the No. 1 of the present invention.
[0182] As content of constructing unit of the polyester diol of the
present invention, respective raw materials are employed in a range
of a proportion so that (content of constructing unit of the
polyester composed of an aliphatic diol and adipic acid)/(content
of constructing unit of .epsilon.-caprolactone) becomes a range of
5/95-80/20 (weight ratio). Also in the case that a
poly-.epsilon.-caprolactone is employed, it is the same. In
thus-obtained polyester diol, a number average molecular weight
ranges in 500-5,000, preferably 1,500-4,000. In the case of not
less than 5,000, crystallinity increases in a soft segment,
resulting in that there is not apt to be obtained a spandex
filament having sufficient physical properties. The number average
molecular weight can be measured by a hydroxyl value (JIS
K1557).
[0183] A polyurethane is prepared from the polyester diol obtained
as described hereinabove and an organic diisocyanate, as described
in the present invention No. 1.
[0184] As the above-described low molecular weight diol which is a
chain extender, there can be employed the branched aliphatic diols
to be employed in the present invention or the diol compounds which
can be employed together therewith. As an diamine which is a chain
extender, there can be employed the same ones as exemplified in the
present invention No. 1.
[0185] The polyurethane obtained by the above-described methods is
employed in a variety of uses in which a usual polyurethane is
employed, for example, a thermoplastic elastomer, a hard or soft
urethane foam, an adhesive, an artificial leather, and coating,
etc., and particularly, it is preferred to employ for a spandex
filament.
[0186] It is to be noted that the polyurethane to be employed for
the artificial leather in the present invention can be employed in
a mode of any one of a solvent-based urethane or water-based
urethane and, hereinafter, both will be illustrated.
[0187] In the solvent-based urethane to be employed in the present
invention, modulus in 100% extension preferably ranges in 15-150
kg/cm.sup.2, and preferably 15-70 kg/cm.sup.2. In the case that the
modulus in 100% extension is less than 15 kg/cm.sup.2, durability
occasionally becomes worse in a sheet obtained and, it becomes
difficult to industrially produce because of a large longitudinal
extension in a step for extracting-removing components of a matrix
region.
[0188] Further, in the case that the modulus in 100% extension is
more than 150 kg/cm.sup.2, there cannot be obtained an artificial
leather having a high density, a low repellent property, and
excellent feeling at which the present invention aims.
[0189] Since the polyurethane to be employed in the present
invention is impregnated into a cloth, it is employed as a
solution. As a preferred solvent in the case, there are enumerated
dimethyl formamide, dimethyl acetoamide, dioxane, and
tetrahydrofran, etc.
[0190] In the present invention, an impregnated polyurethane is
coagulated by a nonsolvent, and it requires to apply a so-called
wet coagulation method. There is not preferred a method in which a
solvent is removed by impregnation and drying without coagulating
by a nonsolvent, that is, since feeling becomes very hard in a
dry-coagulation method and a low repellent feeling is not obtained,
it is not preferred. As a liquid in a bath for wet-coagulating a
polyurethane, there are typically enumerated water and a mixed
solution of water with the above-described solvents. Further, as a
solvent to be employed for extracting matrix components of a fine
fibers-producible type fiber, there are enumerated aromatic
hydrocarbons such as benzene, toluene, and xylene, halogenated
hydrocarbons such as trichloroethylene, tetrachloroethylene, and
carbon tetrachloride, etc.
[0191] In the polyurethane to be employed in the present invention,
there can be added a variety of additives such as, for example, a
phosphorous-based compound and a halogen-contained compound which
are a flame retardant, an antioxidant, an ultraviolet ray
absorbent, pigments, dyes, and plasticizers, etc. However, an
effect is not shown even though there are added substances
simultaneously extracted in a step for extracting a matrix resin
component.
[0192] Cloth to be employed in the present invention is not
particularly limited, and nonwoven cloth and woven cloth can be
employed. Of those, there is preferred a nonwoven cloth
three-dimensionally entangled. Fibers or filaments constructing the
clothes are a fine fibers or filament-producible type fiber or
filament having a matrix-domain structure in which a thermoplastic
resin which can be extracted and removed by a solvent is a matrix
resin components and a fiber-formable thermoplastic resin is a
domain component. As the thermoplastic resin which is employed as
the domain component, there are enumerated, for example, a
polyamide resin and a polyester resin, and as the thermoplastic
resin which is employed as the matrix component which can be
extracted by a solvent, there are enumerated, for example, a
polyolefine, a polystyrene, a modified polyvinyl alcohol-based
resin, and a water-soluble polyester resin, etc.
[0193] In more detail, as a specific example of the domain
component resin for employing in the present invention, there are
enumerated 6-nylon, 6,6-nylon, 6,10-nylon, 12-nylon, a spinnable
polyamide having an aromatic group, polyethylene terephthalate,
polybutylene terephthalate, sulphoisophthalic acid-based
polyethylene terephthalate, and sulphoisohpthalic-based
polybutylene terephthalate, etc. On the other hand, as a polymer
constructing the matrix component resin, there is enumerated a
resin which has a different solubility to a solvent from the domain
component resin, and which has only a small affinity to the domain
component resin and, moreover, which has a smaller melt viscosity
than that in the domain component resin under spinning conditions.
For example, there are enumerated a polyethylene, a polypropylene,
an ethylene-propylene copolymer, an ethylene-vinyl acetate
copolymer, an ethylene-acrylate copolymer, an ethylene-a-olefine
copolymer, a polystyrene, a hydrogenated product of a
styrene-isoprene copolymer, a styrene-butadiene copolymer, a
hydrogenated product of a styrene-butadiene copolymer, a modified
polyvinyl alcohol, and a modified polyester, etc.
[0194] As a method for the preparation of fibers composed of the
matrix component resin and the domain component resin, there are
enumerated a method in which a spinning is conducted by forming a
mixed system while dissolving in an identical dissolving system
after mixing the matrix component resin and the domain component
resin in a fixed proportion, a method in which a spinning is
conducted by dissolving in an independent system, respectively, and
by forming a mixed system through repeating a combining-separating
of both polymer streams at a head portion of a spinning machine in
plural times, and a method in which a spinning is conducted by
dissolving in an independent dissolving system, respectively, and
by combining both polymer streams each other through regulating a
fiber shape at a head portion of a spinning machine. Proportion
occupied by the the domain component resin in the fibers is
preferably 40-80% by weight, and pieces of very fine fibers in the
cross-section of fibers are not less than 5, particularly, those
preferably range in 5-10000 pieces. Thus-spun very fine
fiber-producible type fibers are optionally through a usual
treatment step for fibers such as an extension step and
heat-setting step to prepare fibers having size of 2-15 deniers, an
average size of not more than 0.2 denier in the very fine fibers,
and preferably not more than 0.1 denier and not less than 0.001
denier.
[0195] Thus-spun very fine fiber-producible type fibers are bloomed
through a blooming machine, followed by forming random web or cross
wrap through a weaver and by piling a fiber web obtained in order
to give a desired weight and thickness. Subsequently, the fiber web
is treated for entangling through conventionally publicly-known
methods such as needle punching, water jetting, and air jetting to
prepare a nonwoven cloth in which fibers are entangled. Of course,
a textile may be even formed after preparing spun fibers or
multi-filaments from the very fine fiber-producible type fibers by
conventional methods. Further, the nonwoven cloth may be even piled
with the textiles.
[0196] In fibrous base materials, a density of 0.2-0.5 g/cm.sup.3
is preferred before impregnating a polyurethane in order to obtain
an excellent filled up-touch and a good feeling and, more
preferably, it ranges in 0.25-0.40 g/cm.sup.3. In the fibrous base
materials, when the density is less than 0.2 g/cm.sup.3, surface
flatness becomes worse in a sheet obtained. Further, in the case of
being more than 0.5 g/cm.sup.3, there are not occasionally obtained
an excellent filled up-touch and a good feeling which are a purpose
in the present invention by high-densification in a sheet
obtained.
[0197] The sheet which is an artificial leather in relation to the
present invention is comprised a cloth which is a textile of very
fine fibers and a polyurethane existing in inside clearance of
fibers, and the polyurethane exists between a very fine fiber
bundle and a very fine fiber bundle and, it is preferred that it
does not exist in inside of the very fine fiber bundle. In the case
that the polyurethane does not substantially exist in inside of the
very fine fiber bundle, very fine fibers are not fixed by the
polyurethane, whereby, a sheet obtained is rich in the filled
up-touch and, moreover, the fibers in the sheet obtained are
sufficiently released from the polyurethane, whereby, there is
obtained a rubber-like soft feeling not having a repellent
feeling.
[0198] In the sheet of the present invention, ratio of the
polyurethane in the sheet preferably ranges in 15-60% by weight,
and preferably 25-50% by weight. In the case that the ratio of the
polyurethane is less than 15% by weight, physical properties such
as surface strength occasionally become large with a lapse of time,
or feeling by hands occasionally becomes bulky and paper-like. In
the case that the ratio of the polyurethane is higher than 60% by
weight, surface flatness occasionally becomes worse in the sheet
obtained, or feeling occasionally becomes hard.
[0199] By forming a surface layer through coating a resin with
spraying or gravure, etc. onto a polyurethane-impregnated cloth
obtained by the above methods, or, by a method in which a cloth is
unified with a resin layer formed on a releasing paper, there can
be obtained an artificial leather-like sheet having a
silver-colored surface. Further, a suede-like sheet can be also
obtained by conducting buffing the surface of the
polyurethane-impregnated cloth using a sandpaper, etc.
[0200] On the other hand, in the case that the polyurethane
emulsion prepared by using a specified polyester diol in the
present invention is applied to the artificial leather, hydrolysis
resistance is improved compared to an artificial leather obtained
by impregnating a polyurethane emulsion prepared using a polyester
polyol obtained by condensation reaction of a dibasic acid with
glycols, and it is excellent in hydrolysis resistance and heat
resistance even though being compared to an artificial leather
obtained by impregnating a polyurethane emulsion prepared using a
polyether polyol such as polyalkylene glycols or alkylene
oxide-adducts. Further, in the case of an artificial leather in
which a polyurethane emulsion is impregnated which is prepared by
using a specified polyester diol in the present invention, a soft
feeling is obtained. As described hereinabove, in a word, there is
obtained a very excellent artificial leather having many satisfied
physical properties by using a specified polyester diol in the
present invention.
EXAMPLES
[0201] Hereinafter, although the present inventions No. 1 to No. 5
are specifically illustrated by Examples, the present invention is
not limited thereto. It is to be noted that "part" in the Examples
and Comparative Examples is "part by weight", so far as not being
particularly noticed.
[0202] Hereinafter, the present invention No. 1 is specifically
illustrated by Examples.
[0203] In the Examples and Comparative Examples, compounds employed
are named by abbreviations. Table 1-1 shows relationship between
the abbreviations and the compounds. Further, there were measured
retention ratio of strength, 200%-modulus, and retention ratio of
200%-modulus by the following methods.
[0204] (1) Retention ratio of strength: {stress in fracture after
an alkali treatment (in the Table, "strength after
treatment")/stress in fracture (in the Table,
"strength")}.times.100%
[0205] (2) 200%-modulus: Stress in 200% extension
[0206] (3) Retention ratio of 200%-modulus; (200%-modulus after an
alkali treatment/200%-modulus).times.100
1 TABLE 1-1 Abbreviated word Compound BEPD
2-n-butyl-2-ethyl-1,3-propanediol DEPD 2,2-diethyl-1,3-propanediol
DEND 2,4-diethyl-1,5-propanediol AA adipic acid CL
.epsilon.-caprolactone NPG neopentylglycol BD 1,4-butanediol HD
1,6-hexanediol MPD 3-methyl-1,5-pentanediol
[0207] It is to be noted that evaluation of hydrolysis resistance
in alkali in relation to a polyurethane elastic fiber obtained was
conducted under an alkali atmosphere as shown below. (Hydrolysis
resistance in alkali in relation to a polyurethane elastic
fiber)
[0208] Polyurethane elastic fiber was immersed in 60 g/liter
aqueous solution of sodium hydroxide at 98.degree. C. while
maintaining a constant length, and the polyurethane elastic fiber
was evaluated by retention ratio of strength and retention ratio of
200%-modulus.
Examples 1-1 to 1-10
[0209] There were fed 101 parts a polyester polyol thermally-melted
at 80.degree. C. having an average molecular weight of 2000 which
has a composition shown in Table 1-2, 39 parts of MDI
(4,4'-diphenylmethane diisocyanate) thermally-melted at 45.degree.
C., and 9.5 parts of BD into a twin-screw extruder using a volume
displacement pump to conduct a continuous melt-polymerization at
240.degree. C. A polyurethane prepared was extruded into water in a
strand state to pelletize by cutting. Pellets were dried at
80.degree. C. for 24 hours under a nitrogen stream.
[0210] The pellets were spun at a spinning temperature of
217.degree. C. and spinning speed of 600 m/minute by a spinning
machine which is a single-screw extruder to obtain an elastic
monofilament of the polyurethane having 40 deniers.
[0211] Using the elastic monofilament of the polyurethane, various
physical properties and hydrolysis resistance in alkali were
evaluated. Results are shown in Table 1-3. In all cases, it is
excellent in physical properties as fibers and hydrolysis
resistance in alkali.
Comparative Examples 1-1 to 1-7
[0212] Using polyester polyols as shown in Table 1-3, a
polyurethane elastic fiber was obtained by the same procedures as
in the Examples. The polyester polyols have (a constructing unit
content of a polyester composed of at least one kind selected from
the group of 2-n-butyl-2-ethyl-1,3-propanediol,
2,2-diethyl-1,3-propanediol, and 2,4-diethyl-1,5-pentanediol)/(a
constructing unit content of .epsilon.-caprolactone) of an outside
range of 5/95-80/20 (weight ratio). Physical properties and
hydrolysis resistance in alkali were evaluated. Results are shown
in Table 1-3.
2 TABLE 1-2 Component ratio of Diol (%) PE (wt %) CL (wt %) BEPD
DEPD DEND NPG ED BD HD Diol/AA CL Example 1-1 100 40 60 Example 1-2
100 40 60 Example 1-3 100 40 60 Example 1-4 100 20 80 Example 1-5
100 60 40 Example 1-6 100 80 20 Example 1-7 50 50 40 60 Example 1-8
50 50 40 60 Example 1-9 50 50 40 60 Example 1-10 50 50 40 60
C.Exam. 1-1 30 70 100 0 C.Exam. 1-2 50 50 100 0 C.Exam. 1-3 100 40
60 C.Exam. 1-4 100 100 0 C.Exam. 1-5 100 100 0 C.Exam. 1-6 0 100
C.Exam. 1-7 100 95 5 In the Table 1-2, C.Exam. means Comparative
Example.
[0213] In the Table, PE (wt %) means the weight proportion of the
constructing unit content of a polyester composed obtained from a
various diols and dicarboxylic acids, and CL means the constructing
unit content of .epsilon.-caprolactone.
3 TABLE 1-3 Alkali Strength Extension 200% modulus Strength A.T
Rete. Ratio 200% modulus Ret. Ratio (g/d) (%) (g/d) (g/d) (%) (g/d)
(%) Example 1-1 1.56 510 0.36 1.45 93 0.33 92 Example 1-2 1.54 514
0.36 1.46 95 0.34 94 Example 1-3 1.58 518 0.36 1.50 95 0.34 94
Example 1-4 1.65 504 0.39 1.35 82 0.32 82 Example 1-5 1.50 528 0.34
1.38 92 0.31 90 Example 1-6 1.40 547 0.32 1.37 98 0.31 96 Example
1-7 1.41 513 0.33 1.27 90 0.29 89 Example 1-8 1.48 521 0.32 1.30 88
0.28 86 Example 1-9 1.52 524 0.34 1.35 89 0.29 86 Example 1-10 1.58
512 0.36 1.45 92 0.32 88 C.Exam. 1-1 1.28 460 0.32 1.10 86 0.26 82
C.Exam. 1-2 1.19 512 0.28 0.98 82 0.23 82 C.Exam. 1-3 1.52 518 0.35
0.99 65 0.22 63 C.Exam. 1-4 0.75 320 0.12 0.56 75 0.09 72 C.Exam.
1-5 1.76 405 0.44 0.97 55 0.23 53 C.Exam. 1-6 1.79 402 0.47 0.98 55
0.25 53 C.Exam. 1-7 1.29 458 0.33 1.10 85 0.27 81 In the Table 1-3,
abbreviations are as follows. C. Exam.: Comparative Example
Strength A.T: Strength after treatment Rete. Ratio: Retention
Ratio
[0214] As clearly shown in the Table 1-3, it is confirmed that the
polyurethane elastic fibers in the Examples 1-1 to 1-10 do not show
a remarkable decline of strength and modulus in 200%-extension
after hydrolysis in alkali compared to those of the Comparative
Examples, and have a satisfied physical properties as fibers. The
polyurethane elastic fibers in the Examples 1-1 to 1-10 have (a
constructing unit content of a polyester composed of at least one
kind selected from the group of 2-n-butyl-2-ethyl-1,3-propanediol,
2,2-diethyl-1,3-propanediol, and 2,4-diethyl-1,5-pentanediol)/(a
constructing unit content of .epsilon.-caprolactone) of 5/95-80/20
(weight ratio).
[0215] Hereinafter, the present invention No. 2 is specifically
illustrated by Examples.
[0216] In the Examples and Comparative Examples, compounds employed
are named by abbreviations. Table 2-1 shows a relationship between
the abbreviations and the compounds. Measurement methods for
retention ratio of strength, 200%-modulus, and retention ratio of
200%-modulus are the same as in the present inventions No. 1.
4 TABLE 2-1 Abbreviated word Compound BEPD
2-n-butyl-2-ethyl-1,3-propanediol MPD 3-methyl-1,5-pentanediol DEND
2,4-diethyl-1,5-propanediol AA adipic acid DA sebasic acid DDA
dodecanoic diacid CL .epsilon.-caprolactone BD 1,4-butanediol HD
1,6-hexanediol
[0217] It is to be noted that evaluations for hydrolysis resistance
in alkali of a polyurethane elastic fiber obtained were likewise
conducted as in the present inventions No. 1.
Examples 2-1 to 2-10
[0218] There were fed 101 parts a polyester polyol thermally-melted
at 80.degree. C. having an average molecular weight of 2000 which
has a composition shown in Table 2-2, 39 parts of MDI
(4,4'-diphenylmethane diisocyanate) thermally-melted at 45.degree.
C., and 9.5 parts of BD into a twin-screw extruder using a volume
displacement pump to conduct a continuous melt-polymerization at
240.degree. C. A polyurethane prepared was extruded into water in a
strand state to pelletize by cutting. Pellets were dried at
80.degree. C. for 24 hours under a nitrogen stream.
[0219] The pellets were spun at a spinning temperature of
217.degree. C. and spinning speed of 600 m/minute by a spinning
machine which is a single-screw extruder to obtain an elastic
monofilament of the polyurethane having 40 denier.
[0220] Using the elastic monofilament of the polyurethane, various
physical properties and hydrolysis resistance in alkali were
evaluated. Results are shown in Table 2-3. In all cases, it is
excellent in physical properties as fibers and hydrolysis
resistance in alkali.
Comparative Examples 2-1 to 2-7
[0221] Using polyester polyols as shown in Table 2-2, a
polyurethane elastic fiber was obtained by the same procedures as
in the Examples. The polyester polyols have (a constructing unit
content of a polyester composed of a branched diol and an aliphatic
dicarboxylic acid having a carbon number of 10-12)/(a constructing
unit content of .epsilon.-caprolactone) of an outside range of
5/95-80/20 (weight ratio). Physical properties and hydrolysis
resistance in alkali were evaluated. Results are shown in Table
2-3.
5 TABLE 2-2 Component ratio of Diol (%) PE (wt %) CL (wt %) BEPD
MPD DEND BD HD Acid Diol/Acid CL Example 2-1 100 DA 40 60 Example
2-2 100 DA 40 60 Example 2-3 100 DA 40 60 Example 2-4 100 DA 20 80
Example 2-5 100 DA 60 40 Example 2-6 100 DA 80 20 Example 2-7 100
DDA 40 60 Example 2-8 50 50 DA 40 60 Example 2-9 50 50 DA 40 60
Example 2-10 50 50 DDA 40 60 C.Exam. 2-1 30 70 AA 100 0 C.Exam. 2-2
50 50 AA 100 0 C.Exam. 2-3 100 100 AA 40 60 C.Exam. 2-4 100 AA 100
0 C.Exam. 2-5 100 AA 100 0 C.Exam. 2-6 AA 0 100 C.Exam. 2-7 100 AA
95 5 In the Table 2-2, C.Exam. means Comparative Example.
[0222] In the Table, PE (weight %) means the weight proportion of
the constructing unit content of a polyester composed obtained from
a various diols and dicarboxylic acids, and CL means the
constructing unit content of .epsilon.-caprolactone.
6 TABLE 2-3 Alkali Strength Extension 200% modulus Strength A.T
Ret. Ratio 200% modulus Ret. Ratio (g/d) (%) (g/d) (g/d) (%) (g/d)
(%) Example 2-1 1.55 508 0.36 1.43 92 0.33 91 Example 2-2 1.52 513
0.36 1.41 93 0.33 92 Example 2-3 1.51 516 0.36 1.40 93 0.33 92
Example 2-4 1.61 502 0.39 1.43 89 0.34 87 Example 2-5 1.48 519 0.34
1.35 91 0.30 89 Example 2-6 1.42 526 0.32 1.32 93 0.30 93 Example
2-7 1.48 527 0.33 1.36 92 0.30 91 Example 2-8 1.42 530 0.32 1.26 89
0.28 88 Example 2-9 1.52 516 0.34 1.32 87 0.30 88 Example 2-10 1.48
508 0.36 1.35 91 0.31 85 C.Exam. 2-1 1.28 460 0.32 1.10 86 0.26 82
C.Exam. 2-2 1.19 512 0.28 0.98 82 0.23 82 C.Exam. 2-3 1.52 518 0.35
0.99 65 0.22 63 C.Exam. 2-4 0.75 320 0.12 0.56 75 0.09 72 C.Exam.
2-5 1.76 405 0.44 0.97 55 0.23 53 C.Exam. 2-6 1.79 402 0.47 0.98 55
0.25 53 C.Exam. 2-7 1.29 458 0.33 1.10 85 0.27 81 In the Table 2-3,
abbreviations are as follows. C.Exam.: Comparative Example Strength
A.T: Strength after treatment Rete. Ratio: Retention Ratio
[0223] As clearly shown in the Table 2-3, it is confirmed that the
polyurethane elastic fibers in the Examples 2-1 to 2-10 do not show
a remarkable decline of strength and modulus in 200%-extension
after hydrolysis in alkali compared to those of the Comparative
Examples, and have a satisfied physical properties as fibers. The
polyurethane elastic fibers in the Examples 2-1 to 2-10 have (a
constructing unit content of a polyester composed of the branched
diols and dicarboxylic acids having a carbon number of 10-12)/(a
constructing unit content of .epsilon.-caprolactone) of 5/95-80/20
(weight ratio).
[0224] Hereinafter, the present invention No. 3 is specifically
illustrated by Examples.
[0225] In the Examples and Comparative Examples, compounds employed
are named by abbreviations. Table 3-1 shows a relationship between
the abbreviations and the compounds. Measurement methods for
retention ratio of strength, 200%-modulus, and retention ratio of
200%-modulus are the same as in the present inventions No. 1.
7 TABLE 3-1 Abbreviated word Compound BEPD
2-n-butyl-2-ethyl-1,3-propanediol DEPD 2,2-diethyl-1,3-propanediol
DEND 2,4-diethyl-1,5-pentanediol AA adipic acid CL
.epsilon.-caprolactone NPG neopentylglycol BD 1,4-butanediol HD
1,6-hexanediol MPD 3-methyl-1,5-pentanediol
[0226] It is to be noted that evaluations for hydrolysis resistance
in alkali of a polyurethane elastic fiber obtained were likewise
conducted as in the present inventions No. 1.
Examples 3-1 to 3-7
[0227] There were fed 101 parts of a polyester polyol
thermally-melted at 80.degree. C. having an average molecular
weight of 2000 which has a composition shown in Table 3-2, 39 parts
of MDI (4,4'-diphenylmethane diisocyanate) thermally-melted at
45.degree. C., and 9.5 parts of BD into a twin-screw extruder using
a volume displacement pump to conduct a continuous
melt-polymerization at 240.degree. C. A polyurethane prepared was
extruded into water in a strand state to pelletize by cutting.
Pellets were dried at 80.degree. C. for 24 hours under a nitrogen
stream.
[0228] The pellets were spun at a spinning temperature of
217.degree. C. and spinning speed of 600 m/minute by a spinning
machine which is a single-screw extruder to obtain an elastic
monofilament of the polyurethane having 40 denier.
[0229] Using the elastic monofilament of the polyurethane, various
physical properties and hydrolysis resistance in alkali were
evaluated. Results are shown in Table 3-3. In all cases, it is
excellent in physical properties as fibers and hydrolysis
resistance in alkali.
Comparative Examples 3-1 to 3-7
[0230] Using polyester polyols as shown in Table 3-2, a
polyurethane elastic fiber was obtained by the same procedures as
in the Examples. The polyester polyols do not contain
2,4-diethyl-1,5-pentanediol. Physical properties and hydrolysis
resistance in alkali were evaluated. Results are shown in Table
3-3.
8 TABLE 3-2 Component ratio of Diol (%) BEPD DEPD DEND NPG ED BD HD
Example 3-1 10 90 Example 3-2 30 70 Example 3-3 50 50 Example 3-4
70 30 Example 3-5 30 40 30 Example 3-6 30 40 30 Example 3-7 50 30
40 30 C.Exam. 3-1 30 70 C.Exam. 3-2 50 50 C.Exam. 3-3 100 C.Exam.
3-4 100 C.Exam. 3-5 100 C.Exam. 3-6 100 C.Exam. 3-7 100 In the
Table 3-2, C.Exam. means Comparative Example.
[0231]
9 TABLE 3-3 Alkali Strength Extension 200% modulus Strength A.T
Ret. Ratio 200% modulus Ret. Ratio (g/d) (%) (g/d) (g/d) (%) (g/d)
(%) Example 3-1 1.65 504 0.39 1.35 82 0.32 82 Example 3-2 1.50 528
0.34 1.38 92 0.31 90 Example 3-3 1.40 547 0.32 1.37 98 0.31 96
Example 3-4 1.41 513 0.33 1.27 90 0.29 89 Example 3-5 1.56 510 0.36
1.45 93 0.33 92 Example 3-6 1.54 514 0.36 1.46 95 0.34 94 Example
3-7 1.58 518 0.36 1.50 96 0.34 94 C.Exam. 3-1 1.28 460 0.32 1.10 86
0.26 82 C.Exam. 3-2 1.19 512 0.28 0.98 82 0.23 82 C.Exam. 3-3 1.52
518 0.35 0.99 65 0.22 63 C.Exam. 3-4 0.75 320 0.12 0.56 75 0.09 72
C.Exam. 3-5 1.76 405 0.44 0.97 55 0.23 53 C.Exam. 3-6 1.79 402 0.47
0.98 55 0.25 53 C.Exam. 3-7 1.29 468 0.33 1.10 85 0.27 81 In the
Table 3-3, abbreviations are as follows. C.Exam.: Comparative
Example Strength A.T: Strength after treatment Rete. Ratio:
Retention Ratio
[0232] As clearly shown in the Table 3-3, it is confirmed that the
polyurethane elastic fibers in the Examples 3-1 to 3-7 do not show
a remarkable decline of strength and modulus in 200%-extension
after hydrolysis in alkali compared to those of the Comparative
Examples, and have a satisfied physical properties as fibers. The
polyurethane elastic fibers in the Examples 3-1 to 3-7 have a
polyester diol containing 10-70% of a specified diol by mol based
on diol components constructing the polyester diol.
[0233] Hereinafter, the present invention No. 4 is specifically
illustrated by Examples.
Synthesis Example 4-1
[0234] A glass-made flask equipped with a condenser, a tube for
supplying nitrogen, a thermometer, and an agitator was charged with
129.3 g of bis[3-(2H-benzotriazole-2-yl).sub.4-hydroxy-benzene
ethanol]methane (a trade name of "MBEP" manufactured by Otsuka
Kagaku, Ltd.), 170.3 g of .epsilon.-caprolactone, and 50 ppm of
mono-n-butyltin aliphatic acid salt (a trade name of "SCAT-24"
manufactured by Sankyo Yuki Gosei, Ltd.). After having maintained a
reaction temperature at 150.degree. C. for 6 hours, concentration
of .epsilon.-caprolactone in a reaction liquid was measured by a
gas-chromatograph, and the reaction was terminated at the
concentration of 0.43%. Reaction product was a liquid-state
substance at room temperatures having an acid value (mgKOH/g) of
1.8, a viscosity of 2645 CP/60.degree. C., a number average
molecular weight (MN) by GPC of 1391, a weight average molecular
weight (MW) by GPC of 1688, and MW/MN=1.213.
Synthesis Example 4-2
[0235] The same apparatus as in the Synthesis Example 4-1 was
charged with 93.7 g of
bis[3-(2H-benzotriazole-2-yl).sub.4-hydroxy-benzene ethanol]methane
(a trade name of "MBEP" manufactured by Otsuka Kagaku, Ltd.), 206.3
g of .epsilon.-caprolactone, and 50 ppm of mono-n-butyltin
aliphatic acid salt (a trade name of "SCAT-24" manufactured by
Sankyo Yuki Gosei, Ltd.). After having maintained a reaction
temperature at 150.degree. C. for 6 hours, concentration of
.epsilon.-caprolactone in a reaction liquid was measured by a
gas-chromatograph, and the reaction was terminated at the
concentration of 0.55%. Reaction product was a substance which is a
solid at room temperature having an acid value (mgKOH/g) of 2.5, a
viscosity of 987 CP/60.degree. C., MN of 2017, MW of 2465, and
MW/MN=1.222.
Example 4-1
[0236] Polyester polyols were prepared from an
.epsilon.caprolactone-modif- ied polyol obtained in the Synthesis
Example 4-1 and Synthesis Example 4-2 and adipic acid, or MBEP
employed in the Synthesis Examples and adipic acid, respectively.
The polyester polyols and thermally-melted MDI
(4,4'-diphenylmethane diisocyanate), and BD (1,4-butanediol) were
fed into a twin-screw extruder using a volume displacement pump to
conduct a continuous melt-polymerization at 240.degree. C. A
polyurethane prepared was extruded into water in a strand state to
pelletize by cutting. Pellets were dried at 80.degree. C. for 24
hours under a nitrogen stream. The pellets were spun at a spinning
temperature of 217.degree. C. and spinning speed of 600 m/minute by
a spinning machine which is a single-screw extruder to obtain a 40
denier elastic monofilament of the polyurethane. Since the elastic
monofilament of the polyurethane has an ultraviolet ray absorbable
group in the molecule, it is more excellent in weatherability and
washing resistance compared to a spandex filament in which an
ultraviolet ray absorbent is added.
[0237] Hereinafter, the present invention No. 5 is specifically
illustrated by Examples.
[0238] <Experimental Method>
[0239] Various properties and parameters of copolymers in the
present invention were measured as follows.
[0240] (1) Evaluation of Solubility to Solvents
[0241] As being shown in Examples 5-1 to 5-6 and Comparative
Examples 5-1 to 5-2, a polymer solution was prepared, and outer
appearance when cooled to room temperature (25.degree. C.) was
observed. Evaluation is as follows, when the solution is opaque, it
is worse, and when it is transparent, it is good.
[0242] (2) Preparation of an Experimental Sample
[0243] In order to evaluate an applicability as an additive for a
spandex polymer, a polymer film sample was prepared which contains
an additive.
[0244] In the preparation of the film sample, a polymer solution
was prepared, substantially, according to a method described in the
Example 5-1. Subsequently, the polymer solution was completely
mixed with 20 g of an N,N-dimethylacetamide solvent containing a
desired amount of an experimental additive. Subsequently, the
polymer solution containing the additive was stood for 30
minutes.
[0245] Subsequently, a film was cast on "Mylar (Mylar)" which is a
polyester sheet using a doctor knife device having a broad gap of
0.51 cm.
[0246] N,N-dimethylacetamide solution was cast to obtain an
experimental sample having a dimension of approximately 20.3
cm.times.8.9 cm. The film cast was dried in air for 24 hours, and
the experimental sample was stripped from the "Mylar" sheet.
[0247] After preparation of the experimental sample, the sample was
immersed in a water bath. In order to suppose a water bath for
washing, the sample was immersed in a bath having 2 liters of water
containing 8 g of "Duponol (Duponol)" which is an anion surface
active agent (diethanolamine laurylsulphate manufactured by E. I.
Dupon't, Ltd.), 5 g of sodium tetrapirorate, and 1.5 g of
ethylenediamine tetracetate for 1 hour. After having taken out the
sample, and even a trace amount of the additives in the bath was
repeatedly washed and removed using a pure water until becoming not
detected in water.
Example 5-1
[0248] <Preparation of a Copolymer (Copolymer 1) of a Dialkyl
Aminoethyl(Meth)Acrylate with a Monomethacrylate of
.epsilon.-Caprolactone-Modified Ethyleneglycol>
[0249] Using a 300 cc 4-necked flask equipped with an agitator, a
thermometer, a dropping funnel, and a device for supplying
nitrogen, first of all, the flask was sufficiently purged by
nitrogen, and 25 g of dimethylacetamide (DMAc) was added, followed
by heating to 85.degree. C. so that temperature in the flask
becomes constant. Subsequently, various components having the
weight described below were dropped into the flask at a constant
speed over 4 hours.
[0250] 2,2-azobis-2-methylbutyronitrile (ABN-E): 0.675 g
[0251] Diisopropyl aminoethylmethacrylate (DIPAM): 45 g
[0252] Placcel FM2D (an .epsilon.-caprolactone-adduct of
ethyleneglycol monomethacrylate: manufactured by Daicel Chemical
Industries, Ltd.): 15 g
[0253] Dimethylacetamide (DMAc): 15.4 g
[0254] Dropping reaction was terminated after 4 hours,
subsequently, an aging reaction was conducted at 85.degree. C. for
1 hour, followed by adding 0.675 g of ABN-E into the flask. After
that, a reaction was conducted at temperature of 85.degree. C. for
3 hours. Solid components concentration (N.V.) was 57.1%, and a
molecular weight of a polymer was measured by a gel permeation
chromatographic (GPC) method, and the following results were
obtained.
[0255] It is to be noted that in order to evaluate a solubility to
DMAc, an outer appearance was observed at room temperature
(25.degree. C.).
[0256] A solution obtained was transparent, and it was confirmed
that the solubility is excellent.
[0257] Number average molecular weight Mn: 13700
[0258] Weight average molecular weight Mw: 46100
[0259] Molecular weight distribution Mw/Mn: 3.36
Examples 5-2 to 5-6
[0260] <Preparation of Copolymers (Copolymers 2-6) of a Dialkyl
Aminoethyl(Meth)Acrylate with a Monomethacrylate of
.epsilon.-Caprolactone-Modified Ethyleneglycol>
[0261] The same procedures as in the Example 5-1 were likewise
conducted except that a solution having composition shown in Table
5-1 was added dropwise to obtain copolymers 2-6. Table 5-1
collectively shows results (incapability of measuring means
incapability of detecting because of a close refraction index to a
solvent) of a solid concentration, a GPC analysis, and a solubility
to DMAc.
Comparative Examples 5-1 to 5-2
[0262] <Preparation of Dialkyl Aminoethyl(Meth)Acrylate-Based
Copolymers (Comparative Copolymers 1-2) Not Having a
Monomethacrylate of .epsilon.-Caprolactone-Modified Ethyleneglycol
as a Constructing Component>
[0263] The same procedures as in the Example 5-1 were likewise
conducted except that a solution having composition shown in Table
5-1 was added dropwise to obtain copolymers 1 and 2. Table 5-1
collectively shows results (incapability of measuring means
incapability of detecting because of a close refraction index to a
solvent) of a solid components concentration, a GPC analysis, and a
solubility to DMAc.
Examples 5-7 to 5-12 and Comparative Examples 5-3 to 5-4
[0264] <Evaluation of Heat Set Efficiency in a Spandex Film
Containing an Additive Which is a Copolymer (Copolymers 2 to 6) of
a Dialkyl Aminoethyl(Meth)Acrylate with a Monomethacrylate of
.epsilon.-Caprolactone-Modified Ethyleneglycol>
[0265] An N,N-dimethylacetamide solution of a segmented
polyurethane was prepared according to a general method (for
example, first descriptions in Example 11 and descriptions in
Example I) described in U.S. Pat. No. 3,428,711 A mixture was
prepared by completely mixing p,p'-methylenediphenyl diisocyanate
and polytetramethylene glycol (a molecular weight of approximately
1800) in a molar ratio of 1.63, followed by preparing an
isocyanate-terminated polyether (that is, a terminal-treated glycol
having an NCO content of 2.40%) while maintaining temperature at
approximately 80-90.degree. C. for 90-100 minutes. And then, it was
cooled to 60.degree. C. and mixed with N,N-dimethylacetamide to
obtain a solution having a solid content of approximately 45%.
Subsequently, the terminal-treated glycol was allowed to react with
diethylamine, ethylenediamine and 1,3-cyclohexylene diamine of
molar ratio of 90/10 which are a chain extender at temperature of
approximately 75.degree. C. for 2-3 minutes while vigorously
agitating. Molar ratio of the diamine chain extender with respect
to diethylamine was 6.3, and an unreacted segmented polyurethane in
the glycol terminal-treated by the diamine chain extender contained
approximately 36% of solid and showed a viscosity of approximately
2100 poise at 40.degree. C. A variety of additives were dispersed
in dimethylacetamide which is a solvent, followed by completely
mixing with a polymer solution to prepare a solution containing a
solid content of 2% of the copolymers 1-6 obtained in the Examples
5-1 to 5-6, 3% of zinc oxide, 1.5% of "Syanox" 1790 which is a
sterically-hindered phenol-based anti oxidant
[2,4,6-tris(2,6-dimethyl-4-t-butyl-3-hydroxybenzyl)isocyanurate],
and 0.01% of a silicone oil in a final film. Herein, all the
concentration is based on the weight of spandex polymer. A film of
thus-prepared solution was cast, and washed by the water-based
solvent described hereinabove before a test. Efficiency of heat-set
was measured, and results are collectively shown in Table 5-1.
10 TABLE 5-1 Example Comparative Example 1 2 3 4 5 6 1 2 Initial
Feed DMAc 25 25 25 25 25 25 25 25 Dropping composition DMAc 15.4
15.4 15.4 15.4 15.4 15.4 15.4 15.4 ABN-E 0.675 0.675 0.300 0.675
0.675 0.675 0.675 0.675 DIPAM 45 45 45 45 45 DEAM 45 DMAM 45 DMAA
45 PCL-FM2D 15 7.5 15 15 15 15 n-decyl-MA 15 lauryl-MA 7.5 15
Delayed Feed ABN-E 0.675 0.675 0.675 0.675 0.675 0.675 0.675 0.675
N.V.(%) 57.1 58.3 57.8 56.9 59.7 58.2 57.7 58.8 Mn 13700 12500
14000 THF-base THF-base THF-base 14500 12700 d: incapable d:
incapable d: incapable of of of measuring measuring measuring by
GPC by GPC by GPC Mw 46100 33800 246000 32700 29800 Mw/Mn 3.36 2.70
17.6 2.26 2.34 Example Comparative Example 7 8 9 10 11 12 3 4
Solubility to Excellent Excellent Excellent Excellent Excellent
Excellent Bad Bad DMAc HSE(more than 82 80 85 78 76 75 80 81 70%:
excellent) DIPAM: Diisopropyl aminoethylmethacrylate DMAM: Dimethyl
aminoethylmethacrylate DMAC: Dimethylacetoamide DMAA: Dimethyl
aminoethylacrylate DEAM: Diethyl aminoethylmethacrylate HSE:
Heat-set efficiency
[0266] Even in the all experiments, excellent results were
obtained.
[0267] The above-described results in the Examples show an
advantageous effect which affects to an excellent solubility to a
solvent and heat-set efficiency in the case that the additives
which are a copolymer of a dialkyl aminoethyl(meth)acrylate with a
monomethacrylate of .epsilon.-caprolactone-modified ethyleneglycol
is added to a spandex.
[0268] Possibility of Utilization in Industry
[0269] As being clear from the above-described results in the
Examples, since a polyurethane elastic fiber having an excellent
hydrolysis resistance in alkali and a high tensile strength
property can be obtained according to the present inventions No. 1,
2, and 3, it can largely contribute to an industrial field.
[0270] As being clear from the above descriptions, since a
polyurethane elastic fiber having an excellent weatherability and
an excellent washing resistance can be obtained according to the
present invention No. 4, it can largely contribute to an industrial
field.
[0271] The novel dialkylamino group-contained acrylic-based
copolymer which is the present invention No. 5 shows a higher
solubility to DMAc which is a solvent, and it protects a
polyurethane and a spandex polymer from deterioration and
discoloration. In a polyurethane composition and a spandex
composition which contain the copolymer, a decrease of elasticity
is improved in relation to the use of an already-known high
molecular weight tertiary amino group-contained additive having a
steric hindrance, and it has an excellent permanent extension
property.
[0272] An excellent artificial leather can be obtained by the use
of a polyurethane prepared using a specified polyester diol in the
present invention No. 6.
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