U.S. patent application number 10/561155 was filed with the patent office on 2006-08-10 for polyether ester elastic fiber and fabric, clothes made by using the same.
Invention is credited to Shoji Makino, Seiji Mizohata, Shigeru Morioka, Bunsow Nagasaka, Masao Uchida.
Application Number | 20060177655 10/561155 |
Document ID | / |
Family ID | 33543484 |
Filed Date | 2006-08-10 |
United States Patent
Application |
20060177655 |
Kind Code |
A1 |
Mizohata; Seiji ; et
al. |
August 10, 2006 |
Polyether ester elastic fiber and fabric, clothes made by using the
same
Abstract
A polyether ester elastic fiber comprising a polyether ester
elastomer containing polybutylene terephthalate as a hard segment
and polyoxyethylene glycol as a soft segment and copolymerized with
a specific metal organic sulfonate, having a coefficient of
moisture absorption of not less than 5% at 35.degree. C. and at a
RH of 95% and a coefficient of water absorption extension of not
less than 10%. The above-mentioned polyether ester elastic fiber
has a good moisture-absorbing property, and is reversibly largely
expanded or contracted by the absorption or release of water.
Therefore, a fabric giving excellent comfortableness can be
obtained from said elastic fibers, and can be recycled.
Inventors: |
Mizohata; Seiji; (Ehime,
JP) ; Makino; Shoji; (Ehime, JP) ; Morioka;
Shigeru; (Ehime, JP) ; Uchida; Masao; (Ehime,
JP) ; Nagasaka; Bunsow; (Tokyo, JP) |
Correspondence
Address: |
SUGHRUE MION, PLLC
2100 PENNSYLVANIA AVENUE, N.W.
SUITE 800
WASHINGTON
DC
20037
US
|
Family ID: |
33543484 |
Appl. No.: |
10/561155 |
Filed: |
June 18, 2004 |
PCT Filed: |
June 18, 2004 |
PCT NO: |
PCT/JP04/08940 |
371 Date: |
December 16, 2005 |
Current U.S.
Class: |
428/364 |
Current CPC
Class: |
D01F 6/86 20130101; Y10T
428/2913 20150115 |
Class at
Publication: |
428/364 |
International
Class: |
D02G 3/00 20060101
D02G003/00 |
Foreign Application Data
Date |
Code |
Application Number |
Jun 20, 2003 |
JP |
2003-175788 |
Sep 22, 2003 |
JP |
2003-329584 |
Claims
1. A polyether ester elastic fiber comprising a polyether ester
elastomer containing polybutylene terephthalate as a hard segment
and polyoxyethylene glycol as a soft segment, characterized by
having a coefficient of moisture absorption of not less than 5% at
35.degree. C. and at a RH of 95% and a coefficient of water
absorption extension of not less than 10%.
2. The polyether ester elastic fiber according to claim 1, wherein
the polyether ester elastomer is copolymerized with a metal organic
sulfonate represented by the following general formula (1), and the
intrinsic viscosity of the elastic fiber is not less than 0.9.
##STR8## (wherein, R1 represents an aromatic hydrocarbon group or
an aliphatic hydrocarbon group, X1 represents an ester-forming
functional group, X2 represents an ester-forming functional group
identical to or different from X1 or a hydrogen atom, M1 represents
an alkali metal or an alkaline earth metal, j represents 1 or
2).
3. The polyether ester elastic fiber according to claim 2, wherein
the shrinkage percentage of the elastic fiber in boiling water is
not less than 10%.
4. The polyether ester elastic fiber according to claim 2, wherein
the metal organic sulfonate is a compound represented by the
following general formula (2). ##STR9## (wherein, R2 represents an
aromatic hydrocarbon group or an aliphatic hydrocarbon group, M2
represents an alkali metal or an alkaline earth metal).
5. The polyether ester elastic fiber according to claim 2, wherein
the copolymerization quantity of the metal organic sulfonate is in
a range of 0.1 to 20 percent by mole based on the acid component
constituting the polyether ester elastomer.
6. The polyether ester elastic fiber according to claim 1, wherein
the elastic fiber has two crystal-melting peaks in a DSC curved
line obtained with a differential scanning calorimeter, has a
Hm1/Hm2 ratio of the height Hm1 of the crystal-melting peak on the
lower temperature side/the height Hm2 of the crystal-melting peak
on the higher temperature side in a range of 0.6 to 1.2, and has a
breaking elongation of not less than 400%.
7. The polyether ester elastic fiber according to claim 6, wherein
the temperature Tm1 of the crystal-melting peak on the lower
temperature side and the temperature Tm2 of the crystal-melting
peak on the higher temperature side among the two crystal-melting
peaks satisfy the following expression. 200.degree.
C..ltoreq.Tm1<Tm2.ltoreq.225.degree. C.
8. The polyether ester elastic fiber according to claim 1, wherein
the ratio of the hard segment: the soft segment is in a range of
30:70 to 70:30 based on weight.
9. The polyether ester elastic fiber according to claim 1, wherein
a finishing oil in which at least one lubricant selected from the
group consisting of mineral oils, silicones and aliphatic esters
and an ether-based or ester-based nonionic surfactant occupy 70 to
100 percent by weight and 0 to 30 percent by weight, respectively,
of said finishing oil is adhered to the surface of the elastic
fiber in an amount of 0.5 to 5.0 percent by weight based on the
weight of said fiber.
10. The polyether ester elastic fiber according to claim 9, wherein
the viscosity of the finishing oil at 30.degree. C. is
5.times.10.sup.-6 to 4.times.10.sup.-5 m.sup.2/s.
11. A fabric in whose at least one portion the polyether ester
elastic fibers according to claim 1 are used.
12. Clothing in whose at least one portion the polyether ester
elastic fibers according to claim 1 are used.
13. Underwear, sportswear, lining, pantyhose, or socks in whose at
least one portion the polyether ester elastic fibers according to
claim 1 are used.
14. The polyether ester elastic fiber according to claim 2, wherein
the ratio of the hard segment: the soft segment is in a range of
30:70 to 70:30 based on weight.
15. The polyether ester elastic fiber according to claim 6, wherein
the ratio of the hard segment: the soft segment is in a range of
30:70 to 70:30 based on weight.
16. The polyether ester elastic fiber according to claim 2, wherein
a finishing oil in which at least one lubricant selected from the
group consisting of mineral oils, silicones and aliphatic esters
and an ether-based or ester-based nonionic surfactant occupy 70 to
100 percent by weight and 0 to 30 percent by weight, respectively,
of said finishing oil is adhered to the surface of the elastic
fiber in an amount of 0.5 to 5.0 percent by weight based on the
weight of said fiber.
17. The polyether ester elastic fiber according to claim 6, wherein
a finishing oil in which at least one lubricant selected from the
group consisting of mineral oils, silicones and aliphatic esters
and an ether-based or ester-based nonionic surfactant occupy 70 to
100 percent by weight and 0 to 30 percent by weight, respectively,
of said finishing oil is adhered to the surface of the elastic
fiber in an amount of 0.5 to 5.0 percent by weight based on the
weight of said fiber.
18. A fabric in whose at least one portion the polyether ester
elastic fibers according to claim 2 are used.
19. A fabric in whose at least one portion the polyether ester
elastic fibers according to claim 6 are used.
20. Clothing in whose at least one portion the polyether ester
elastic fibers according to claim 2 are used.
Description
TECHNICAL FIELD
[0001] The present invention relates to a polyether ester elastic
fiber giving a fabric which has a good moisture-absorbing or
releasing property, is reversibly expanded or contracted by the
absorption or release of water, and especially gives
non-conventional comfortableness for sports uses, inner wear uses
and the like.
BACKGROUND ART
[0002] Hitherto, polyurethane elastic fibers have mainly been used
as elastic fibers for clothes and industrial materials, but have
defects that heat resistance, chemical resistance and weather
(light) resistance are inferior. The polyurethane elastic fibers
need a dry spinning process on their production, and the recovery
of a solvent is therefore needed. The polyurethane elastic fibers
have problems of low productivity and large energy consumption.
Furthermore, the polyurethane elastic fibers have many problems
directed to the coming of a future recycling-oriented society, such
as the difficulty of recycling and the production of harmful gases
on combustion.
[0003] Under such the background, polyether ester elastic fibers
containing a highly crystalline polyester such as a polyalkylene
terephthalate as a hard segment and a polyalkylene glycol as a soft
segment and capable of being melt-spun have been put to practical
uses, while utilizing advantages such as high productivity,
excellent heat resistance and excellent heat set resistance.
Furthermore, the future development of the polyether ester elastic
fibers has been expected as elastic fibers suitable for the
recycling-oriented society, because the polyether ester elastic
fibers can be recycled and do not produce a harmful gas (for
example, JP-B 47-14054 (hereinafter, JP-B means "Japanese Examined
Patent Publication"), JP-A 48-10346 (hereinafter, JP-A means
"Japanese Unexamined Patent Publication"), JP-A 57-77317).
[0004] As such the polyether ester elastic fibers, polyether ester
elastic fibers using polybutylene terephthalate as a hard segment
and polyoxybutylene glycol as a soft segment, or the like, have
been used as elastic fibers having elastic performances comparable
to those of polyurethane elastic fibers. However, both these hard
segment and soft segment are generally hydrophobic, and polyether
ester elastic fibers having hydrophilic properties such as a
moisture-absorbing property or a water-absorbing property have
little been put to a practical use.
[0005] On the other hand, in the pamphlet of WO 00/47802, elastic
fibers having a moisture-absorbing performance given thereto have
been proposed, but only the concrete examples of a polyurethane
elastomer containing a water-absorbing resin having a coefficient
of water absorption of 500 to 4,000 percent by weight have been
described.
[0006] Additionally, only by imparting a moisture-absorbing
property to fibers themselves as having been proposed, there is a
limit for improving their comfortableness as a fabric or further
clothing. Therefore, elastic fibers having new functions have been
demanded.
DISCLOSURE OF INVENTION
[0007] The present invention has been completed on the basis of the
above-mentioned conventional techniques as the background, and the
object of the present invention is to provide the recyclable
polyether ester elastic fibers giving fabrics which have a good
moisture-absorbing property and is reversibly largely expanded or
contracted by the absorption or release of water to give excellent
comfortableness, and to provide a fabric, clothing using the
elastic fibers.
[0008] The inventors of the present invention have repeatedly
examined in view of such the background techniques. Consequently,
it has been found that the object of the present invention can be
achieved with the following polyether ester elastic fibers.
[0009] 1. A polyether ester elastic fiber comprising a polyether
ester elastomer containing polybutylene terephthalate as a hard
segment and polyoxyethylene glycol as a soft segment, characterized
by having a coefficient of moisture absorption of not less than 5%
at 35.degree. C. and at a RH of 95% and a coefficient of water
absorption extension of not less than 10%.
[0010] 2. The polyether ester elastic fiber according to Claim 1,
wherein the polyether ester elastomer is copolymerized with a metal
organic sulfonate represented by the following general formula (1),
and the intrinsic viscosity of the elastic fiber is not less than
0.9. ##STR1##
[0011] (wherein, R1 represents an aromatic hydrocarbon group or an
aliphatic hydrocarbon group, X1 represents an ester-forming
functional group, X2 represents an ester-forming functional group
identical to or different from X1 or a hydrogen atom, M1 represents
an alkali metal or an alkaline earth metal, j represents 1 or
2).
[0012] 3. The polyether ester elastic fiber according to Claim 2,
wherein the shrinkage percentage of the elastic fiber in boiling
water is not less than 10%.
[0013] 4. The polyether ester elastic fiber according to Claim 2,
wherein the metal organic sulfonate is a compound represented by
the following general formula (2). ##STR2##
[0014] (wherein, R2 represents an aromatic hydrocarbon group or an
aliphatic hydrocarbon group, M2 represents an alkali metal or an
alkaline earth metal).
[0015] 5. The polyether ester elastic fiber according to Claim 2,
wherein the copolymerization quantity of the metal organic
sulfonate is in a range of 0.1 to 20 percent by mole based on the
acid component constituting the polyether ester elastomer.
[0016] 6. The polyether ester elastic fiber according to Claim 1,
wherein the elastic fiber has two crystal-melting peaks in a DSC
curve obtained with a differential scanning calorimeter, has a
Hm1/Hm2 ratio of the height Hm1 of the crystal-melting peak on the
lower temperature side/the height Hm2 of the crystal-melting peak
on the higher temperature side in a range of 0.6 to 1.2, and has a
breaking elongation of not less than 400%.
[0017] 7. The polyether ester elastic fiber according to Claim 6,
wherein temperature Tm1 at the crystal-melting peak on the lower
temperature side and temperature Tm2 at the crystal-melting peak on
the higher temperature side between the two crystal-melting peaks
satisfy the following expression. 200.degree.
C..ltoreq.Tm1<Tm2.ltoreq.225.degree. C.
[0018] 8. The polyether ester elastic fiber according to one of
Claims 1, 2 and 6, wherein the ratio of the hard segment: the soft
segment is in a range of 30:70 to 70:30 based on weight.
[0019] 9. The polyether ester elastic fiber according to one of
Claims 1, 2 and 6, wherein a finishing oil in which at least one
lubricant selected from the group consisting of mineral oils,
silicones and aliphatic esters and an ether-based or ester-based
nonionic surfactant occupy 70 to 100 percent by weight and 0 to 30
percent by weight, respectively, of said finishing oil is adhered
to the surface of the elastic fiber in an amount of 0.5 to 5.0
percent by weight based on the weight of said fiber.
[0020] 10. The polyether ester elastic fiber according to Claim 9,
wherein the viscosity of the finishing oil at 30.degree. C. is
5.times.10.sup.-6 to 4.times.10.sup.-5 m.sup.2/s.
[0021] 11. A fabric in whose at least one portion the polyether
ester elastic fibers according to one of Claims 1, 2 and 6 are
used.
[0022] 12. Clothing in whose at least one portion the polyether
ester elastic fibers according to one of Claims 1, 2 and 6 are
used.
[0023] 13. Underwear, sportswear, lining, pantyhose, or socks in
whose at least one portion the polyether ester elastic fibers
according to one of Claims 1, 2 and 6 are used.
BEST MODE FOR CARRYING OUT THE INVENTION
[0024] The polyether ester elastomer is an elastic fiber comprising
a polyether ester elastomer containing polybutylene terephthalate
as a hard segment and polyoxyethylene glycol as a soft segment.
[0025] It is preferable that the polybutylene terephthalate as the
hard segment contains butylene terephthalate units in an amount of
at least 70 percent by mole. The content of the butylene
terephthalate is more preferably not less than 80 percent by mole,
furthermore preferably not less than 90 percent by mole.
[0026] The above-mentioned polybutylene terephthalate may be
copolymerized with one or more other components within a range
substantially not affecting the achievement of the object of the
present invention. The dicarboxylic acid component used as the one
or more other copolymerization components includes aromatic,
aliphatic and alicyclic dicarboxylic acid components such as
naphthalene dicarboxylic acid, isophthalic acid, diphenyl
dicarboxylic acid, diphenoxyethane dicarboxylic acid,
.beta.-hydroxyethoxybenzoic acid, p-hydroxybenzoic acid, adipic
acid, sebacic acid and 1,4-cyclohexane dicarboxylic acid.
Furthermore, a trifunctional or more functional polycarboxylic acid
such, as trimellitic acid or pyromellitic acid may be used as a
copolymerization component. Also, the diol component includes
aliphatic, alicyclic and aromatic diol components such as
trimethylene glycol, ethylene glycol, cyclohexane-1,4-dimethanol,
and neopentyl glycol. Furthermore, a trifunctional or more
functional polyol such as glycerol, trimethylolpropane or
pentaerythritol may be used as a copolymerization component.
[0027] On the other hand, it is preferable that the polyoxyethylene
glycol as the soft segment contains oxyethylene glycol units in an
amount of not less than at least 70 percent by mole. The content of
the oxyethylene glycol is more preferably not less than 80 percent
by mole, furthermore preferably not less than 90 percent by mole.
The above-mentioned polyoxyethylene glycol may be copolymerized
with, for example, propylene glycol, tetramethylene glycol,
glycerol or the like within a range substantially not affecting the
achievement of the object of the present invention.
[0028] The number-average molecular weight of the above-mentioned
polyoxyethylene glycol is preferably 400 to 8,000, especially
preferably 1,000 to 6,000.
[0029] In the present invention, the weight ratio of the hard
segment: the soft segment is preferably in a range of 70:30 to
30:70, more preferably in a range of 60:40 to 40:60. When the
weight ratio of the hard segment exceeds 70%, the elongation of the
elastic fiber is lowered, and it becomes difficult to use the
elastic fiber for high stretch uses. The moisture-absorbing
property is liable to be lowered. When the weight ratio of the hard
segment is less than 30%, the strength is liable to be lowered,
because the rate of the crystal portion of the polybutylene
terephthalate is lowered, and it is difficult to copolymerize all
of the added polyoxyethylene glycol. Washing fastness is therefore
liable to be deteriorated in post-processing processes such as
scouring and dyeing processes or when the elastic fiber is used as
a product.
[0030] In the present invention, it is important that the elastic
fiber has a coefficient of moisture absorption of not less than 5%
at 35.degree. C. and at a RH of 95% and a coefficient of water
absorption extension of not less than 10%. Thereby, a woven or
knitted fabric comprising such the elastic fibers is a fabric
giving excellent comfortableness and having the so-called
self-adjusting function wherein, when the woven or knitted fabric
absorbs sweat or the like, the fibers are extended to open the
stitches of the woven or knitted fabric to release moisture in the
clothing, and when the woven or knitted fabric is dried, the fibers
are contracted into the original lengths, thereby clogging the
stitches of the woven or knitted fabric to prevent the release of
temperature in the clothing.
[0031] When the coefficient of moisture absorption is less than 5%,
the woven or knitted fabric gives a sticky sense or stuffy sense,
and when the coefficient of water absorption extension is less than
10%, the reversibly extending or contracting characteristic due to
the absorption or release of water is insufficient. Thereby, the
stitches of the woven or knitted fabric are sufficiently not opened
or closed, and the fabric giving excellent comfortableness is not
obtained. Whereas, when the coefficient of moisture absorption or
the coefficient of water absorption extension in the elastic fibers
of the present invention comprising the above-mentioned polyether
ester is excessively large, elastic performance, heat resistance,
weather (light) resistance, chemical resistance, and the like are
liable to be deteriorated. Hence, the coefficient of moisture
absorption is preferably in a range of 5 to 45%, more preferably in
a range of 10 to 40%. The coefficient of water absorption extension
is preferably in a range of 10 to 100%, more preferably in a range
of 10 to 80%, furthermore preferably in a range of 15 to 60%.
[0032] In the present invention, the finishing oil is adhered to
the surface of the elastic fiber in an amount of 0.5 to 5.0 percent
by weight based on the weight of said fiber, and it is preferable
in said finishing oil that at least one lubricant selected from the
group consisting of mineral oils, silicones, and aliphatic esters
occupies 70 to 100 percent by weight of said finishing oil.
[0033] The above-mentioned lubricant selected from the mineral
oils, the silicones, and the aliphatic esters little swells the
elastic fiber, does not cause the increase of friction and the
deterioration of dynamical characteristics due to the swelling, and
improves process stability in a fiber-producing process and in
post-processing processes. The content (the total content of the
lubricants, when the lubricants are used) of the lubricant is
controlled to 70 to 100 percent by weight. Thereby, the traveling
stability of the fiber on the production of the fiber can be
improved, and the abnormal elongation of the fiber and the
production of scum can be prevented.
[0034] As the above-mentioned mineral oils, the mineral oils having
viscosities in the range of 5.times.10.sup.-6 to 4.times.10.sup.-5
m.sup.2/s at 30.degree. C. are preferable. The mineral oils having
the viscosities in such the viscosity range little evaporate during
storage. Thereby, the composition ratio of the finishing oil on the
elastic fiber is little changed, and the high smoothness can be
maintained. It is preferable that the silicone is
polydimethylsiloxane, and has a viscosity of 5.times.10.sup.-6 to
4.times.10.sup.-5 m.sup.2/s at 30.degree. C. for the same reason as
in the case of the mineral oils. In addition, the above-mentioned
aliphatic esters are compounds such as aliphatic acid monoalkyl
esters, dialkyl aliphatic dicarboxylates, and the mono- or
multi-fatty acid esters of aliphatic polyhydric alcohols, and
preferably have the molecular weights in a range of 250 to 550.
High smoothness can be maintained by controlling the molecular
weights to such the range of the molecular weight. For example, the
fatty acid monoalkyl esters in the aliphatic esters preferably used
include octyl octanoate, octyl stearate, isotridecyl laurate,
isotridecyl oleate, and lauryl oleate. The dialkyl aliphatic
dicarboxylates include diisooctyl adipate. The mono- or multi-fatty
acid esters of the aliphatic polyhydric alcohols include
trimethylol propane trioctanoate. Especially, the aliphatic acid
monoalkyl esters are preferable.
[0035] Whereas, it is preferable that the ether-based or
ester-based nonionic surfactant is the nonionic surfactant having a
viscosity of 8.times.10.sup.-6 to 5.times.10.sup.-5 m.sup.2/s at
30.degree. C. The ether-based nonionic surfactant preferably used
includes polyalkylene glycol alkyl ethers and polyalkylene glycol
aryl ethers. The ester-based nonionic surfactant includes the
alkylene oxide adducts of polyhydric alcohol partial esters, and
polyalkylene glycol alkyl ethers are especially preferable. When
the alkyl group has the carbon atoms within a range of 8 to 20
carbon atoms, the elastic fiber is hardly swollen, and high
smoothness can also simultaneously be achieved. It is preferable
that the alkylene group of the polyalkylene glycol chain has two or
three carbon atoms, especially two carbon atoms, and it is suitable
that the number of the chains (the molar number of ethylene oxide
added to the alcohol) is within a range of 3 to 20. When the number
of the chains is within the range, compatibility with the
lubricants comprising the above-mentioned mineral oils, the
silicones or the aliphatic esters is not deteriorated.
[0036] Therein, when the above-mentioned mineral oils, the
silicones, and the like have viscosities of 5.times.10.sup.-6 to
2.times.10.sup.-5 m.sup.2/s at 30.degree. C., the above-mentioned
ether-based or ester-based nonionic surfactant is not necessarily
contained in the finishing oil, but it is preferable at the point
of handleability that said nonionic surfactant is contained in an
amount of not more than 30 percent by weight, when the
above-mentioned viscosity exceeds 2.times.10.sup.-5 m.sup.2/s.
[0037] The finishing oil used in the present invention is comprised
of the above-mentioned components, but one or more other components
may, if necessary, be added in small amounts within a range not
affecting the object of the present invention. Lubricating
auxiliaries, for example, another nonionic surfactant, an anionic
or cationic surfactant, stability-improving agents such as an
antioxidant and an ultraviolet absorber, may be added in small
amounts.
[0038] Additionally, it is preferable that the above-mentioned
finishing oil used in the present invention has a viscosity in a
range of 5.times.10.sup.-6 to 4.times.10.sup.-5 m.sup.2/s at
30.degree. C. When the viscosity is controlled to such the range,
the components in the finishing oil are hardly evaporated during
the storage of the elastic fiber, and the high smoothness can be
maintained. When the finishing oil has a high viscosity in a range
of 2.times.10.sup.-5 to 4.times.10.sup.-5 m.sup.2/s at 30.degree.
C., and is imparted as a neat finishing oil in a spinning process,
it is preferable that the finishing oil is, for example, heated to
lower the viscosity to not more than 2.times.10.sup.-5 m.sup.2/s.
But, when the finishing oil is heated at too high temperature, the
physical properties of the obtained fiber are affected. Therefore,
it is preferable that the temperature is controlled to at most
60.degree. C.
[0039] Next, the amount of the above-mentioned finishing oil
adhered to the elastic fiber is preferably 0.5 to 5.0 percent by
weight, more preferably 1.0 to 4.0 percent by weight, based on the
weight of said fiber. Thereby, a trouble such as the breakage of
the fiber or the production of scum is hardly caused in a process
for producing the fiber to improve the stability of the
process.
[0040] The above-mentioned high coefficient of moisture absorption
and the above-mentioned high coefficient of water absorption
extension can easily be achieved by copolymerizing the
above-mentioned polyether ester elastomer with a metal organic
sulfonate represented by the following general formula (1) and
controlling the intrinsic viscosity of the elastic fiber to not
less than 0.9. ##STR3##
[0041] Therein, R1 represents an aromatic hydrocarbon group or an
aliphatic hydrocarbon group, preferably an aromatic hydrocarbon
group having 6 to 15 carbon atoms or an aliphatic hydrocarbon group
having not more than 10 carbon atoms. Particularly preferable R1
represents an aromatic hydrocarbon group having 6 to 12 carbon
atoms, especially a benzene ring. M1 represents an alkali metal or
an alkaline earth metal, and j represents 1 or 2. Especially, M1
represents preferably an alkali metal (for example, lithium, sodium
or potassium), and j represents preferably 1. X1 represents an
ester-forming functional group, and X2 represents an ester-forming
functional group identical to or different from X1 or a hydrogen
atom, but represents preferably the ester-forming functional group.
The ester-forming functional group may be a group for reacting and
binding to the main chain or terminal of the polyether ester, and
include concretely by the following groups. ##STR4##
[0042] (wherein, R' represents a lower alkyl group or a phenyl
group; a and d represent each an integer of 1 to 10; b represents
an integer of 2 to 6).
[0043] The preferably concrete examples of the metal organic
sulfonate represented by the above-mentioned general formula (1)
include sodium 3,5-dicarbomethoxybenzenesulfonate, potassium
3,5-dicarbomethoxybenzenesulfonate, lithium
3,5-dicarbomethoxybenzenesulfonate, sodium
3,5-dicarboxybenzenesulfonate, potassium
3,5-dicarboxybenzenesulfonate, lithium
3,5-dicarboxybenzenesulfonate, sodium
3,5-di(.beta.-hydroxyethoxycarbonyl)benzenesulfonate, potassium
3,5-di(.beta.-hydroxyethoxycarbonyl)benzenesulfonate, lithium
3,5-di(.beta.-hydroxyethoxycarbonyl)benzenesulfonate, sodium
2,6-dicarbomethoxynaphthalene-4-sulfonate, potassium
2,6-dicarbomethoxynaphthalene-4-sulfonate, lithium
2,6-dicarbomethoxynaphthalene-4-sulfonate, sodium
2,6-dicarboxynaphthalene-4-sulfonate, sodium
2,6-dicarbomethoxynaphthalene-1-sulfonate, sodium
2,6-dicarbomethoxynaphthalene-3-sulfonate, sodium
2,6-dicarbomethoxynaphthalene-4,8-disulfonate, sodium
2,6-dicarboxynaphthalene-4,8-disulfonate, sodium
2,5-bis(hydroethoxy)benzenesulfonate, and .alpha.-sodium
sulfosuccinate. Only one of the above-mentioned metal organic
sulfonates may singly be used, or two or more of the
above-mentioned metal organic sulfonates may together be used.
[0044] In the present invention, the copolymerization of the metal
organic sulfonate represented by the following general formula (2)
is preferable at a point capable of easily increasing the intrinsic
viscosity of the polyether ester elastomer to not less than 0.9 and
further at a point capable of remarkably enhancing the coefficient
of moisture absorption and the coefficient of water absorption
extension of the obtained elastic fiber. According to our
researches, it has been found by the copolymerization of such the
metal organic sulfonate that an extremely high level coefficient of
water absorption extension of not less than 20% can be achieved to
easily give a fabric giving excellent comfortableness. ##STR5##
[0045] Wherein, R2 represents an aromatic hydrocarbon group or an
aliphatic hydrocarbon group which is the same as the definition of
R1 in the above-mentioned general formula (1), M2 represents an
alkali metal or an alkaline earth metal which is the same as the
definition of M1 in the above-mentioned general formula (1). The
preferable concrete examples of such the metal organic sulfonate
includes sodium
3,5-di(.beta.-hydroxyethoxycarbonyl)benzenesulfonate, potassium
3,5-di(.beta.-hydroxyethoxycarbonyl)benzenesulfonate, and lithium
3,5-di(.beta.-hydroxyethoxycarbonyl)benzenesulfonate.
[0046] When the copolymerization quantity of the above-mentioned
metal organic sulfonate is too much, the melting point of the
elastic fiber tends to be lowered to deteriorate heat resistance,
weather (light) resistance, chemical resistance, and the like.
Therefore, it is preferable that the copolymerization quantity is
in the range of 0.1 to 20 percent by mole based on all the acid
components constituting the polyether ester elastomer. To the
contrary, when the above-mentioned copolymerization quantity is too
little, the coefficient of moisture absorption and the coefficient
of water absorption extension trends to be lowered. Therefore, it
is more preferable that the copolymerization quantity is in the
range of 0.5 to 15 percent by mole.
[0047] The polyether ester elastomer used in the present invention
can be obtained, for example, by subjecting raw materials
comprising dimethyl terephthalate, tetramethylene glycol and
polyoxyethylene glycol to an ester interchange reaction in the
presence of an ester interchange catalyst to form the
bis(.omega.-hydroxybutyl) terephthalate and/or the oligomer and
then melt-polycondensing the bis(.omega.-hydroxybutyl)
terephthalate and/or the oligomer in the presence of a
polycondensation catalyst and a stabilizer at high temperature
under reduced pressures.
[0048] It is preferable to use the salt of an alkali metal such as
sodium, the salt of an alkaline earth metal such as magnesium or
calcium, or the compound of a metal such as titanium, zinc or
manganese as the above-mentioned ester interchange catalyst.
[0049] It is preferable to use a germanium compound, an antimony
compound, a titanium compound, a cobalt compound, a tin compound as
the polycondensation catalyst. When being an amount necessary for
advancing the ester interchange reaction or the polycondensation
reaction, the amount of the used catalyst is especially not
limited. A plurality of the catalysts can also together be
used.
[0050] Additionally, it is more preferable that a hindered
phenol-based compound or a hindered amine-based compound described
later is added to the above-mentioned polyether ester, because of
having effects for not only preventing the lowering in the
intrinsic viscosity of the polymer, when melt-molded, but also
controlling the thermal deterioration, oxidation deterioration,
photo-deterioration and the like of said obtained elastic
fiber.
[0051] Especially, the employment of a hindered phenol-based
compound having a double bond in the molecule and represented by
the general formula (3) described below is more preferable at a
point that the elastic fiber having a high intrinsic viscosity is
easily obtained and at a point that the polyether ester elastic
fiber having the high coefficient of moisture absorption and the
high coefficient of water absorption extension can easily be
produced, because the hindered phenol-based compound represented by
the general formula (3) has an effect for promoting the
polycondensation reaction of the polyether ester elastomer of the
present invention.
[0052] In the formula (3), the substituents R3 and R4 represent
each independently a monovalent organic group having one to six
carbon atoms, wherein when there are a plurality of the
substitutents R3 and/or a plurality of the substitutents R4, the
substituents may be identical or different each other; m and n
represent each independently an integer of 0 to 4; and R5
represents a hydrogen atom or an organic group having one to five
carbon atoms.
[0053] The concrete examples of such the hindered phenol-based
compound having the double bond in the molecule include the
compounds represented by the following formulas (4) to (7).
Especially, the hindered phenol-based compound represented by the
following formula (4) is especially preferable, because of giving
the above-mentioned elastic fiber having the high coefficient of
moisture absorption and the high coefficient of water absorption
extension. ##STR6##
[0054] The ester interchange catalyst can be supplied at the early
stage of the ester interchange reaction in addition to the time for
the preparation of raw materials. Also, the stabilizer can be
supplied until the early time of the polycondensation reaction, but
it is preferable to add the stabilizer at the finish of the ester
interchange reaction. Further, the polycondensation catalyst can be
supplied until the early time of the polycondensation reaction
process.
[0055] Additionally, as a method for enhancing the intrinsic
viscosity of the elastic fiber to not less than 0.9, adopted can be
a method for polymerizing the polyether ester elastomer in a solid
phase, a method for using a chain extender at a stage for
synthesizing the polyester ether elastomer and at a stage for
melt-spinning the polyester ether elastomer, and the like, in
addition to the above-mentioned method. The preferable concrete
examples of the chain extender used herein include oxazoline
compounds such as 2,2'-bis(2-oxazoline), and
N,N'-terephthaloylbiscaprolactam.
[0056] As mentioned above, it is preferable that the elastic fiber
comprises the above-mentioned polyether ester elastomer, and has an
intrinsic viscosity of not less than 0.9. When the above-mentioned
intrinsic viscosity is not less than 0.9, the extremely high
coefficient of moisture absorption and the extremely high
coefficient of water absorption extension can be realized, and a
fabric giving excellent comfortableness can easily be obtained. On
the other hand, when the intrinsic viscosity is too large, the
fiber productivity of the polymer is not only deteriorated, but the
cost for producing the fiber is also enhanced. Therefore, it is
more preferable that the intrinsic viscosity is in a range of 0.9
to 1.2.
[0057] In the above-mentioned elastic fiber, a breaking elongation
of not less than 400% is preferable at a point that the coefficient
of moisture absorption and the coefficient of water absorption
extension can be enhanced to not less than 5% and not less than
10%, respectively, and as a point that the breakage of the elastic
fiber caused by the slight changes of conditions in a process on
weaving or knitting can be reduced. The above-mentioned breaking
elongation is more preferably in a range of 400 to 900%,
furthermore preferably in a range of 400 to 800%.
[0058] Further, it is more preferable on the enhancement of the
coefficient of moisture absorption and the coefficient of water
absorption extension to not less than 5% and not less than 10%,
respectively, that the shrinkage percentage of the elastic fiber in
boiling water is not less than 10%.
[0059] The elastic fiber of the present invention can be produced,
for example, by melt-extruding the polyether ester in a pellet-like
state from a spinneret, thermally insulating a space ranging from a
place just under the spinneret to a place apart from the spinneret
at a distance of at least 10 cm, preferably at least 15 cm,
imparting a finishing oil to the spun fiber at a place within 5 m,
preferably 4 m, from the place just under the spinneret, taking off
the fiber at a take-off speed of 300 to 1,200 m/minute, preferably
400 to 980 m/minute, and then winding up the fiber at a wind-up
draft ratio of 1.3 to 1.6, preferably 1.4 to 1.5, based on said
take-off speed. However, the wind-up draft rate of less than 1.3 is
not preferable, because tensions added to the fiber between Godet
rollers and between the Godet roller and a winder are insufficient
to cause the winding of the fiber on the Godet roller and the
subsequent breakage of the fiber. As mentioned above, it is
preferable for controlling the coefficient of moisture absorption
and the coefficient of water absorption extension to not less than
5% and not less than 10%, respectively, to thermally insulate the
space under the spinneret, control the spinning speed to a low
value as much as possible, shorten a distance to an oiling device
to stop an advance in the orientation of the fiber, and further
wind up the taken elastic fiber at a small wind-up draft ratio as
much as possible within a range in which the elastic fiber can be
wound up without being drawn as much as possible. From such the
viewpoint, it is not preferable to wind up or take off the elastic
fiber and then continuously draw or further thermally treat the
elastic fiber.
[0060] Meanwhile, an elastic fiber comprising the polyether ester
substantially not copolymerized with the metal organic sulfonate
can also give the elastic fiber having the coefficient of moisture
absorption of not less than 5% % at 35.degree. C. and at a RH of
95% and the coefficient of water absorption extension of not less
than 10.
[0061] Namely, the elastic fiber having two crystal-melting peaks
in a DSC curved line obtained with a differential scanning
calorimeter, having a Hm1/Hm2 ratio of the height Hm1 of the
crystal-melting peak on the lower temperature side/the height Hm2
of the crystal-melting peak on the higher temperature side in a
range of 0.6 to 1.2, and having a breaking elongation of not less
than 400% can easily achieve such the high coefficient of moisture
absorption and the high coefficient of water absorption extension
as mentioned above.
[0062] It is above-mentioned that the hard segment: soft segment
ratio of the polyether ester is preferably 30:70 to 70:30 based on
weight, and it is preferable for controlling the Hm1/Hm2 ratio to
not more than 1.2 that the rate of the hard segment is not more
than 70 percent by weight.
[0063] As mentioned above, the reason why the elastic fiber having
the Hm1/Hm2 ratio in the range of 0.6 to 1.2 exhibits the high
coefficient of moisture absorption and the high coefficient of
water absorption extension is estimated as follows. It can be
estimated that the two crystal-melting peaks are due to the
presence of two types of crystals having largely different sizes,
and the peak on the lower temperature side and the peak on the
higher temperature are estimated to be the melting temperature peak
of the crystals having the smaller sizes and the melting
temperature peak of the crystals having the higher sizes,
respectively. This has approximately been confirmed by scanning the
hard and soft portions of the cross section of the fiber with an
interatomic force microscope and then estimating that the hard
portions and the soft portions are assigned to the crystalline hard
segments and the soft segments, respectively. Additionally, it can
be estimated that the polyoxyethylene glycol constituting the soft
segment of the polyether ester adsorbs and holds water molecules,
whereby the polyether ester develops the moisture-absorbing
property. From the above-mentioned estimation, the following
estimation can be carried out, when the Hm1/Hm2 ratio is not more
than 1.2. Namely, the number of the crystals having the small sizes
is small, and the number of crystal-cross linking points for
binding the hard segments is also small. Therefore, the swelling of
the soft segment is not obstructed, and the soft segment can
sufficiently hold water. Thus, the coefficient of moisture
absorption and the coefficient of water absorption extension can
remarkably be improved. On the other hand, when the Hm1/Hm2 ratio
is not less than 0.6, the number of the crystal-cross linking
points is excessively not reduced, and the extensive elasticity of
the fiber can be maintained at a practical high level as a fiber
physical property. The more preferable range of the Hm1/Hm2 ratio
is 0.8 to 1.2.
[0064] Furthermore, it is preferable that the temperatures Tm1 and
Tm2 of the two crystal-melting peaks are not less than 200.degree.
C., and sufficient heat resistance can thereby be maintained. On
the other hand, it is preferable that the temperatures Tm1 and Tm2
of the crystal-melting peaks are not more than 225.degree. C., and
the elasticity of the fiber can thereby be enhanced. This can be
estimated to mean that the fiber having the relation between Tm1
and Tm2 has excessively non-large crystal sizes and the excessively
non-reduced number of crystal-cross linking points.
[0065] In addition, the breaking elongation of the elastic fiber is
preferably not less than 400%, more preferably 500 to 1,000%,
furthermore preferably 600 to 900%, as mentioned above. When the
breaking elongation is not less than 400%, the higher coefficient
of moisture absorption and the higher coefficient of water
absorption extension can be achieved. When the elastic fibers are
knitted or woven, the elastic fibers are hardly broken even by the
slight changes of conditions in the processes, because the breaking
strength is sufficiently large.
[0066] The elastic fiber having the above-mentioned two
crystal-melting peak temperatures can be produced, for example, by
melt-extruding the polyether ester in a pellet-like shape from a
spinneret, thermally insulating a space ranged from a place just
under the spinneret to a place apart from the spinneret at a
distance of at least 10 cm, preferably at least 15 cm, imparting a
finishing oil to the melt-extruded polymer at a place within 5 m,
preferably 4 m, from the place just under the spinneret, taking off
the fiber at a take-off speed of 300 to 1,200 m/minute, preferably
400 to 980 m 1 minute, and then winding up the fiber at a wind-up
draft ratio of 1.0 to 1.2, preferably 1.0 to 1.1, based on said
take-off speed. In other words, it is preferable on controlling the
above-mentioned two crystal-melting peak heights to the range of
0.6 to 1.2 without increasing small size crystals to thermally
insulate the space under the spinneret, lower the spinning speed as
much as possible, shorten a distance to an oiling device to prevent
the advance in the orientation of the fiber, and further wind up
the taken elastic fiber at a small winding draft ratio as much as
possible so that the fiber is not drawn as little as possible. From
such the view point, it is not preferable that the polyether ester
elastic fiber is wound up or taken off and then continuously drawn
or further thermally treated.
EXAMPLES
[0067] Hereinafter, the present invention will concretely be
explained with Examples. Herein, physical properties in Examples
were measured by the following methods.
[0068] (1) Coefficient of Moisture Absorption
[0069] A sample was subjected to the control of humidity in an
air-conditioned room controlled to prescribed conditions for 24
hours, and then the coefficient of moisture absorption was
determined from the weight of the absolutely dried sample and the
weight of the humidity-controlled sample according to the following
expression. Coefficient of moisture absorption (%)=(weight of
humidity-controlled sample-weight of absolutely dried
sample).times.100/weight of absolutely dried sample.
[0070] (2) Coefficient of Water Absorption Extension and
Coefficient of Moisture Absorption Extension
[0071] A fiber was reeled, treated in boiling water under
non-tension for 30 minutes, subjected to an air-drying and
humidity-controlling treatment at 20.degree. C. and at 65% RH, and
then subjected to a dry thermal treatment under an environment of
160.degree. C. under non-tension for two minutes. The treated fiber
was left under an environment of 20.degree. C. and 65% RH for 24
hours, and a load of 0.88.times.10.sup.-3 cN/dtex was hung on the
fiber. The length of the fiber was measured as "length of fiber
when dried". Subsequently, the fiber was immersed in softened water
controlled at 20.degree. C. for one minute, lifted from the water,
nipped with filter paper which have been air-dried at 20.degree. C.
and at 65% RH, placed on a horizontal base, subjected to the
putting of a weight of 1.5 g/cm.sup.2 on the fiber, and then left
for two seconds to wipe off excessive water on the surface of the
fiber. After ten seconds, a load of 0.88.times.10.sup.-3 cN/dtex
was hung on the fiber, and the length of the fiber was measured as
"length of fiber when absorbing water". The coefficient of water
absorption extension was calculated according to the following
expression. All the measurements were carried out under an
environment of 20.degree. C. and 65% RH. Coefficient of water
absorption extension=(length of fiber when absorbing water-length
of fiber when dried)/length of fiber when dried.times.100%.
[0072] Further, similarly as mentioned above, "length of fiber when
dried" was measured. Then, the measured fiber was subjected to a
humidity-controlling treatment in an air-conditioned room
controlled to 35.degree. C. and 95% RH for 24 hours. A load of
0.88.times.10.sup.-3 cN/dtex was hung on the fiber in the
air-conditioned room, and the length of the fiber was measured as
"length of fiber when absorbing moisture". The coefficient of
moisture absorption extension was calculated according to the
following expression. Coefficient of moisture absorption
extension=(length of fiber when absorbing moisture-length of fiber
when dried)/length of fiber when dried.times.100%.
[0073] (3) Breaking Strength and Breaking Elongation
[0074] The breaking strength and the breaking elongation were
measured by carrying out a tension test with a Tensilon RTM-100
tension tester manufactured by Toyo Baldwin Co. in an
air-conditioned room controlled to 20.degree. C..times.65% RH.
[0075] (4) Sticky Sense, Stuffy Sense
[0076] The elastic fibers were knitted into the 132 g/m.sup.2
knitted fabrics with a cylindrical knitting machine. The fabrics
were used to cover the elbows and knees of arbitrarily selected
five persons for one day, and then the sticky senses and the stuffy
senses were evaluated. The results were shown as (little) wherein
the sticky senses and the stuffy senses are little, respectively,
or (large) wherein the sticky senses and the stuffy senses are
large, respectively.
[0077] (5) Crystal-Melting Peak Temperatures Tm1, Tm2
[0078] The crystal-melting peak temperatures were measured by
scanning with a differential scanning calorimeter (type 2920 DSC
manufactured by TA Instruments Corp.) at a temperature-rising rate
of 20.degree. C./minute under the flow of nitrogen. Between two
crystal-melting peaks, the peak temperature on the lower
temperature side is referred to as Tm1, and the peak temperature on
the higher temperature side is referred to as Tm2.
[0079] (6) Ratio Hm1/Hm2 of Crystal-Melting Peak Heights
[0080] Heights from the base line to the crystal-melting peak tops
on the lower temperature side (peak temperature Tm1 side) and the
higher temperature side (peak temperature Tm2 side) among the
above-mentioned two crystal-melting peaks were measured and
referred to as Hm1 and Hm2, respectively, and then their ratio
Hm1/Hm2 was determined.
Example 1
[0081] 100 parts by weight of dimethyl terephthalate, 23 parts by
weight (5.0 percent by mole based on all the acid components) of
the 40 percent by weight ethylene glycol solution of sodium
3,5-di(.beta.-hydroxyethoxycarbonyl)benzenesulfonate, 113.4 parts
by weight of polyoxyethylene glycol (number-average molecular
weight: 4,000), 73.5 parts by weight (1.4 molar times based on all
the acid components) of 1,4-butanediol, and 0.4 part by weight of
tetrabutyl titanate as a catalyst were charged in a reaction vessel
and then subjected to an ester interchange reaction at an inner
temperature of 200.degree. C. When methanol was distilled out in an
amount of about 80% of a theoretical amount, 0.4 part by weight of
the above-mentioned hindered phenol-based compound (4) was added,
and a polycondensation reaction was started by raising the
temperature and reducing the inner pressure. The polycondensation
reaction was carried by reducing the inner pressure to 30 mmHg over
about 30 minutes, further reducing to 3 mmHg over 30 minutes, then
reacting at an inner temperature of 250.degree. C. under a vacuum
of 1 mmHg for 200 minutes, adding 1 part by weight of the following
hindered phenol-based compound (8) and 2 parts by weight of the
following hindered amine-based compound (9) at the time, and then
further reacting at 250.degree. C. under a vacuum of not more than
1 mmHg for 20 minutes. The produced polyether ester elastomer had
an intrinsic viscosity of 1.10, and a polybutylene terephthalate
(hard segment)/polyoxyethylene glycol (soft segment) weight ratio
of 50/50. ##STR7##
[0082] The obtained polyether ester elastomer was melted at
230.degree. C., and extruded from a spinneret at an extrusion rate
of 3.05 g/minute. At this time, a space ranged from a place just
under the spinneret to a place apart from the spinneret at a
distance of 9 cm was thermally insulated. A finishing oil
comprising 100% polydimethyl siloxane having a viscosity of
1.times.10.sup.-5 m.sup.2/s at 30.degree. C. was imparted to the
melted and extruded polymer in an amount of 3.0 percent by weight
based on the weigh of the fibers at a place of 3 m below the
spinneret, and the oiled fibers were taken off on a Godet roller at
a speed of 510 m/minute, and further wound up at a speed of 750 m 1
minute (winding draft ratio: 1.47) to obtain the polyether ester
elastic fibers of 44 dtex/filament. The results are shown in Table
1.
[0083] Subsequently, the above-mentioned elastic fibers were
knitted with a cylindrical knitting machine to form the knitted
fabric of 132 g/m.sup.2. The knitted fabric was left under an
environment of 20.degree. C. and 65% RH for 24 hours, immersed in
20.degree. C. softened water for one minute, taken out from the
water, and then nipped with filter paper to remove the water
adhered to the surface of the knitted fabric. Then, the stitch
openings of the treated knitted fabric were observed. Consequently,
it was confirmed that the stitch openings of the knitted fabric
were enlarged, after the knitted fabric was immersed in the
softened water.
Example 2
[0084] The operations were carried out similarly as in Example 1
except that polyoxyethylene glycol (number-average molecular weight
2,000) was used instead of the polyoxyethylene glycol
(number-average molecular weight: 4,000), and the elastic fibers
having an intrinsic viscosity of 1.16 were consequently obtained.
The results are shown in Table 1.
Example 3
[0085] The operations were carried out similarly as in Example 1
except that the copolymerization ratio of the polyoxyethylene
glycol (number-average molecular weight: 4,000) was changed to a
hard segment/soft segment weight ratio of 60/40 percent by weight,
and the polyether ester elastic filaments having an intrinsic
viscosity of 1.12 were consequently obtained. The results are shown
in Table 1.
Example 4
[0086] The operations were carried out similarly as in Example 1
except that the copolymerization quantity of dihydroxyethyl 5-Na
sulfoisophthalate (the same as sodium
3,5-di(.beta.-hydroxyethoxycarbonyl)benzenesulfonate) was changed
to 2.0 percent by mole based on all the acid components
constituting the polyether ester elastomer, and the polyether ester
elastic filaments having an intrinsic viscosity of 1.18 were
consequently obtained. The results are shown in Table 1.
Comparative Example 1
[0087] The operations were carried out similarly as in Example 1
except that dimethyl 5-Na sulfoisophthalate was used instead of the
dihydroxyethyl 5-Na sulfoisophthalate (the same as sodium
3,5-di(.beta.-hydroxyethoxycarbonyl)benzenesulfonate), and the
polyether ester elastomer having an intrinsic viscosity of 1.10 was
consequently obtained. The polyether ester elastomer was used to
melt-spin the elastomer similarly as in Example 1. The results are
shown in Table 1.
Example 5 and Comparative Example 2
[0088] The operations were carried out similarly as in Example 1
except that the spinning speed and the winding speed were changed
as shown in Table 1. The results are shown in Table 1.
Comparative Example 3
[0089] Elastic fibers obtained by the same method as in Example 1
were drawn between two non-heated rollers at a draw ratio of 2.0
and then wound up to obtain the elastic fibers. The results are
shown in Table 1.
Example 6
[0090] The elastic fibers obtained in Example 1 were knitted into a
circular knitted fabric (smooth) having an end spacing of 52
warps/2.54 cm and a pick spacing of 60 wefts/2.54 cm, and male
underwear (upper half portion) and sportswear (upper half portion)
in whose armpits and chest portions the pieces of the knitted
fabric were used were formed. The underwear and the sportswear were
worn by five persons and then subjected to their physical exercises
for two hours, respectively. Consequently, the sticky senses and
stuffy senses of the used underwear and the sportswear were less
than those of underwear and sportswear not using the
above-mentioned elastic fibers, and the comfortableness was
excellent. TABLE-US-00001 TABLE 1 Example 1 Example 2 Example 3
Example 4 Example 5 #7 1 #7 2 #7 3 #1 50 50 40 50 50 50 50 50 #2
4000 2000 4000 4000 4000 4000 4000 4000 #3 5.0 5.0 5.0 2.0 5.0 5.0
5.0 5.0 Intrinsic viscosity 1.07 1.16 1.12 1.18 1.07 0.81 1.07 1.07
Spinning speed 510 510 510 510 770 510 600 510 (m/minute) Wind-up
speed 750 750 750 750 1000 750 750 750 (m/minute) Wind-up draft
ratio 1.47 1.47 1.47 1.47 1.30 1.47 1.25 1.47 Drawing Nothing
Nothing Nothing Nothing Nothing Nothing -- Drawn Strength (cN/dtex)
0.60 0.65 0.74 0.63 0.64 0.58 #8 1.20 Elongation (%) 568 534 435
604 487 430 250 #4 20.8 15.3 18.8 16.5 25.3 9.7 35.4 #5 31.3 26.5
23.6 26.4 27.6 27.3 23.3 #6 25.2 18.6 16.4 18.1 21.6 7.9 8.7 Stitch
openings on Large Large Large Large Large Small Small absorption of
water Sticky sense Little Little Little Little Little Large Large
Stuffy sense Little Little Little Little Little Large Large #1:
Soft component (polyoxyethylene glycol) ratio #2: Average molecular
weight of polyoxyethylene glycol #3: Copolymerization quantity
(percent by mole) of metal organic sulfonate #4: Shrinkage
percentage (%) in boiling water #5: Coefficient of moisture
absorption at 35.degree. C. and at 95% RH #6: Coefficient of water
absorption extension (%) #7: Comparative example #8: Wound around
the Godet roller and broken
Example 7
[0091] A polyether ester comprising 49.8 parts by weight of
polybutylene terephthalate as a hard segment and 50.2 parts by
weight of polyoxyethylene glycol having a molecular weight of 4,000
as a soft segment was melted at 230.degree. C., and melt-extruded
from a spinneret as an extrusion rate of 3.05 g/minute. Herein, a
space ranged from a place just under the spinneret to a place apart
from the spinneret at a distance of 9 cm. A finishing oil
comprising polydimethylsiloxane having a viscosity of
1.times.10.sup.-5 m.sup.2/s at 30.degree. C. to the melted polymer
in an amount of 3.0 percent by weight based on the weight of the
fibers at a place of 3 m below the spinneret, taken off on a Godet
roller at a speed of 705 m/minute, and further wound up at 750
m/minute (winding draft ratio: 1.06) to obtain the elastic fibers
of 40 denier/filament. The results are shown in Table 2.
[0092] The elastic fibers were knitted into a knitted fabric of 132
g/m.sup.2. After the knitted fabric was left in an environment of
20.degree. C. and 65 RH % for 24 hours, and after the knitted
fabric was furthermore left in an air-conditioned room of
35.degree. C. and 95 RH % for 24 hours, the stitch openings of the
knitted fabric were observed, and it was consequently confirmed
that the spaces were enlarged at 35.degree. C. and 95 RH %.
[0093] In addition, after a knitted fabric of 132 g/m.sup.2
prepared separately from the above-mentioned knitted fabric was
left in an environment of 20.degree. C. and 65 RH % for 24 hours,
and after the knitted fabric was immersed in softened water
controlled to 20.degree. C. for one minute, lifted from the water
and then nipped with filter paper to remove the water left on the
surface of the knitted fabric, the stitch openings of the knitted
fabrics were observed, and it was consequently confirmed that the
spaces were enlarged, after the knitted fabric was immersed in the
softened water.
Examples 8 to 11 and Comparative Example 4
[0094] Elastic fibers were obtained similarly as in Example 7
except that the ratio, spinning speed and winding speed of the
polyoxyethylene glycol were changed as shown in Table 2. The
results are shown in Table 2.
[0095] In addition, the stitch openings of the knitted fabrics were
observed before and after the absorption of moisture and before or
after the absorption of water, respectively, similarly as in
Example 7. It was consequently confirmed that the spaces in
Examples 8 to 11 were enlarged similarly as in Example 7, but the
spaces were scarcely changed in Comparative Example 4.
Example 12
[0096] The elastic fibers obtained in Example 7 were used to make,
wear and evaluate male underwear and sportswear similarly as in
Example 6. Any of the wear gives less sticky sense, less stuffy
sense and more excellent comfortableness than wear not using the
above-mentioned fibers. TABLE-US-00002 TABLE 2 Example Example #7
Example 7 Example 8 Example 9 10 11 4 #1 50.2 59.7 69.5 65.0 50.2
10.0 Spinning temperature 230 230 230 230 230 230 (.degree. C.)
Spinning speed 705 705 705 475 925 705 (m/minute) Take-off speed
750 750 750 500 1000 750 (m/minute) Take-off draft 1.06 1.06 1.06
1.05 1.08 1.06 Drawing Nothing Nothing Nothing Nothing Nothing
Nothing Tm1(.degree. C.) 204 202 200 201 205 220 Tm2(.degree. C.)
217 215 214 215 217 226 Hm1/Hm2 1.01 0.95 0.82 0.61 1.19 3.56
Strength (cN/dtex) 0.67 0.56 0.45 0.43 0.73 1.24 Elongation (%) 816
845 915 928 745 242 #2 2.8 3.5 4.8 3.8 2.6 0.7 #3 22.9 25.4 32.3
29.5 22.3 3.6 #4 20.1 21.9 27.5 25.7 19.7 2.9 #5 17.6 18.9 19.6
19.4 16.4 1.4 #6 12.9 13.5 17.1 14.4 13.2 0.9 Sticky sense Little
Little Little Little Little Large Stuffy sense Little Little Little
Little Little Large #1: Ratio (percent by weight) of
polyoxyethylene glycol #2: Coefficient (%) of moisture absorption
at 20.degree. C. and 65 RH % #3: Coefficient (%) of moisture
absorption at 35.degree. C. and 95 RH % #4: Difference (%) between
coefficients of moisture absorption #5: Coefficient (%) of water
absorption extension #6: Coefficient (%) of moisture absorption
extension #7: Comparative Example
INDUSTRIAL APPLICABILITY
[0097] The elastic fibers of the present invention have excellent
recyclability, because of comprising the polyether ester.
Additionally, the elastic fibers of the present invention exhibit a
self-adjusting function for changing the stitch openings of the
fabric by the absorption or release of water, because of having the
good moisture-absorbing or releasing property and being reversibly
expanded or contracted by the absorption or release of the water,
and can give a fabric having excellent comfortableness. Therefore,
the above-mentioned elastic fibers exhibit excellent performances
in the uses of clothes, especially sportswear, inner wear, linings,
stockings, socks and the like.
* * * * *