U.S. patent application number 17/623165 was filed with the patent office on 2022-08-18 for dyed fabric, fiber product in which same is used, and method for dyeing fabric.
This patent application is currently assigned to TEIJIN LIMITED. The applicant listed for this patent is TEIJIN LIMITED. Invention is credited to Kenji IWASHITA, Hiroki SHIMADA.
Application Number | 20220259800 17/623165 |
Document ID | / |
Family ID | 1000006349664 |
Filed Date | 2022-08-18 |
United States Patent
Application |
20220259800 |
Kind Code |
A1 |
SHIMADA; Hiroki ; et
al. |
August 18, 2022 |
DYED FABRIC, FIBER PRODUCT IN WHICH SAME IS USED, AND METHOD FOR
DYEING FABRIC
Abstract
An object of the present invention is to provide a dyed fabric
and a textile product made thereof, as well as a dyeing method,
which achieve color uniformity of a meta-type wholly aromatic
polyamide fiber, a para-type wholly aromatic polyamide fiber and a
polyester fiber, even in the case of a fabric containing a
meta-type- and para-type-wholly aromatic polyamide fibers and a
polyester fiber which are difficult to dye. The present invention
relates to a dyed fabric dyed after being shaped into a fabric,
characterized in that the fabric includes a meta-type wholly
aromatic polyamide fiber, a para-type wholly aromatic polyamide
fiber and a polyester fiber and the fabric is a fabric dyed with a
cationic dyestuff and a disperse dyestuff, and in that the
afterflame time and afterglow time defined in JISL1091A-1 are 1
second or less.
Inventors: |
SHIMADA; Hiroki; (Osaka-shi,
JP) ; IWASHITA; Kenji; (Osaka-shi, JP) |
|
Applicant: |
Name |
City |
State |
Country |
Type |
TEIJIN LIMITED |
Osaka-shi, Osaka |
|
JP |
|
|
Assignee: |
TEIJIN LIMITED
Osaka-shi, Osaka
JP
|
Family ID: |
1000006349664 |
Appl. No.: |
17/623165 |
Filed: |
June 26, 2020 |
PCT Filed: |
June 26, 2020 |
PCT NO: |
PCT/JP2020/025385 |
371 Date: |
December 27, 2021 |
Current U.S.
Class: |
1/1 |
Current CPC
Class: |
D06P 1/41 20130101; D06P
3/54 20130101 |
International
Class: |
D06P 3/54 20060101
D06P003/54; D06P 1/41 20060101 D06P001/41 |
Foreign Application Data
Date |
Code |
Application Number |
Jun 28, 2019 |
JP |
2019-120749 |
Jul 18, 2019 |
JP |
2019-132671 |
Claims
1. A dyed fabric dyed after being shaped into a fabric,
characterized in that the fabric comprises a meta-type wholly
aromatic polyamide fiber, a para-type wholly aromatic polyamide
fiber and a polyester fiber, and the fabric is dyed with a cationic
dyestuff and a disperse dyestuff, and in that the afterflame time
and afterglow time defined in JISL1091A-1 are 1 second or less.
2. The dyed fabric according to claim 1, wherein both of the dry
rubbing fastness and the wet rubbing fastness defined in JIS L 0849
II method are grade 3 or more.
3. The dyed fabric according to claim 1, wherein the polyester
fiber is dyed with the disperse dyestuff by ring-dyeing.
4. The dyed fabric according to claim 1, wherein the residual
disperse dyestuff is from 0.01% o.w.f. to 0.5% o.w.f.
5. The dyed fabric according to claim 1, wherein the residual
cationic dyestuff is from 0.01% o.w.f. to 16.0% o.w.f
6. The dyed fabric according to claim 1, wherein the weights of the
meta-type wholly aromatic polyamide fiber, the para-type wholly
aromatic polyamide fiber and the polyester fiber are in the ratio
of 60 to 80:1 to 10:5 to 20.
7. The dyed fabric according to claim 1, wherein the fabric
comprises an electrically-conductive fiber, and the weights of the
meta-type wholly aromatic polyamide fiber, the para-type wholly
aromatic polyamide fiber, the polyester fiber and the
electrically-conductive fiber are in the ratio of 60 to 80:1 to
10:5 to 20:1 to 4.
8. The dyed fabric according to claim 1, which is made of a blended
spun yarn comprising the meta-type wholly aromatic polyamide fiber,
the para-type wholly aromatic polyamide fiber and the polyester
fiber.
9. The dyed fabric according to claim 7, which is made of a blended
spun yarn comprising the meta-type wholly aromatic polyamide fiber,
the para-type wholly aromatic polyamide fiber, the polyester fiber
and the electrically-conductive fiber.
10. The dyed fabric according to claim 1, wherein the water
absorption performance defined in AATCC79 prior to washing is 2
seconds or less, and the water absorption performance defined in
AATCC79 after 10 washing cycles defined in ISO6330:2012 (6N-F) is
10 seconds or less.
11. The dyed fabric according to claim 1, which is dyed with 2%
o.w.f. or less of the disperse dyestuff after dyed with 20% o.w.f.
or less of the cationic dyestuff.
12. A textile product made of the dyed fabric according to claim 1,
which is selected from the group consisting of protective suits,
fire resistant suits for fire-fighting, firefighter suits, rescue
suits, workwear, a police uniform, a camouflage uniform, and a
military uniform.
13. A method for dyeing a fabric, characterized in that dyeing a
fabric comprising a meta-type wholly aromatic polyamide fiber, a
para-type wholly aromatic polyamide fiber and a polyester fiber
with a dye solution for wholly aromatic polyamide fiber comprising
20% o.w.f. or less of a cationic dyestuff, and then dyeing the
fabric with a dye solution for polyester fiber comprising 2% o.w.f.
or less of a disperse dyestuff.
14. The dyeing method according to claim 13, wherein the dyeing is
performed by thermosol dyeing.
Description
FIELD
[0001] The present invention relates to a dyed fabric for use in a
flame resistant clothing or the like suitable for wearing by a
person who is engaged in a work which is likely to be exposed to a
flame, such as a firefighter, a pilot, a race driver, an operator
of a power company or a chemical company, and the like; the present
invention also relates to a dyeing method for obtaining the dyed
fabric.
BACKGROUND
[0002] Wholly aromatic polyamide fibers have high mechanical
strength and heat resistance, as well as flame retardancy. They are
in particular widely used in the design of suits for a firefighter,
an astronaut, and a pilot, as a textile fiber intended to come into
contact with fire or high temperatures. In recent years, there has
been an increasing need for designability of clothes, and therefore
a fabric having high dyeability is required.
[0003] On the other hand, the meta-type- and para-type-wholly
aromatic polyamide fibers have a molecular structure having high
crystallinity and strong intermolecular bonding force, and
therefore they are difficult to dye, and, even if they can be dyed,
a dyestuff will be washed off easily by washing or the like.
Therefore, there has been a problem that it is difficult to dye
these fibers by a conventional dyeing technique.
[0004] Patent Document 1 discloses a method in which a fiber
swelling agent (carrier) is used to dye a para-type wholly aromatic
polyamide fiber with a cationic dyestuff.
[0005] Patent Document 2 discloses a method in which a fabric is
dyed with a cationic dyestuff and then dyed with a Vat
dyestuff.
CITATION LIST
Patent Literature
[0006] [Patent document 1] U.S. Pat. No. 3,674,420
[0007] [Patent document 2] JP-A-2013-209776
SUMMARY
Technical Problem
[0008] According to the conventional dyeing method, in the case of
a blended product of a meta-type wholly aromatic polyamide fiber
and a para-type wholly aromatic polyamide fiber, a cationic
dyestuff is selectively adsorbed to the meta-type wholly aromatic
polyamide fiber; therefore it was difficult to dye the para-type
wholly aromatic polyamide fiber.
[0009] In addition, according to the conventional dyeing method, in
the case of a blended product of a meta-type wholly aromatic
polyamide fiber, a para-type wholly aromatic polyamide fiber and a
polyester fiber, the color shade of the polyester fiber becomes
mediocre; therefore, in the market, there is a need for a dyed
fabric having further improved quality.
[0010] In view of the above problems, it is an object of the
present invention to provide a dyed fabric and a textile product
made thereof which achieve color uniformity of a meta-type wholly
aromatic polyamide fiber, a pare-type wholly aromatic polyamide
fiber and a polyester fiber, and which are excellent in heat
resistance and flame resistance, even in the case of a fabric
containing a meta-type- and para-type-wholly aromatic polyamide
fibers and a polyester fiber which are difficult to dye. The
present invention also provides a dyeing method.
Solution to Problem
[0011] The present disclosure includes the following
embodiments:
Embodiment 1
[0012] A dyed fabric dyed after being shaped into a fabric,
[0013] characterized in that the fabric comprises a meta-type
wholly aromatic polyamide fiber, a para-type wholly aromatic
polyamide fiber and a polyester fiber, and the fabric is dyed with
a cationic dyestuff and a disperse dyestuff,
[0014] and in that the afterflame time and afterglow time defined
in JISL1091A-1 are 1 second or less.
Embodiment 2
[0015] The dyed fabric according to the embodiment 1, wherein both
of the dry rubbing fastness and the wet rubbing fastness defined in
JIS L 0849 II method are grade 3 or more.
Embodiment 3
[0016] The dyed fabric according to the embodiment 1 or 2, wherein
the polyester fiber is dyed with the disperse dyestuff by
ring-dyeing.
Embodiment 4
[0017] The dyed fabric according to any one of the embodiments 1 to
3, wherein the residual disperse dyestuff is from 0.01% o.w.f. to
0.5% o.w.f.
Embodiment 5
[0018] The dyed fabric according to any one of the embodiments 1 to
4, wherein the residual cationic dyestuff is from 0.01% o.w.f. to
16.0% o.w.f.
Embodiment 6
[0019] The dyed fabric according to any one of the embodiments 1 to
5, wherein the weights of the meta-type wholly aromatic polyamide
fiber, the pam-type wholly aromatic polyamide fiber and the
polyester fiber are in the ratio of 60 to 80:1 to 10:5 to 20.
Embodiment 7
[0020] The dyed fabric according to any one of the embodiments 1 to
6, wherein the fabric comprises an electrically-conductive fiber,
and the weights of the meta-type wholly aromatic polyamide fiber,
the para-type wholly aromatic polyamide fiber, the polyester fiber
and the electrically-conductive fiber are in the ratio of 60 to
80:1 to 10:5 to 20:1 to 4.
Embodiment 8
[0021] The dyed fabric according to any one of the embodiments 1 to
6, which is made of a blended spun yarn comprising the meta-type
wholly aromatic polyamide fiber, the para-type wholly aromatic
polyamide fiber and the polyester fiber.
Embodiment 9
[0022] The dyed fabric according to the embodiment 7, which is made
of a blended spun yarn comprising the meta-type wholly aromatic
polyamide fiber, the para-type wholly aromatic polyamide fiber, the
polyester fiber and the electrically-conductive fiber.
Embodiment 10
[0023] The dyed fabric according to any one of the embodiments 1 to
9, wherein the water absorption performance defined in AATCC79
prior to washing is 2 seconds or less, and the water absorption
performance defined in AATCC79 after 10 washing cycles defined in
ISO6330:2012 (6N-F) is 10 seconds or less.
Embodiment 11
[0024] The dyed fabric according to any one of the embodiments 1 to
10, which is dyed with 2% o.w.f. or less of the disperse dyestuff
after dyed with 20% o.w.f. or less of the cationic dyestuff.
Embodiment 12
[0025] A textile product made of the dyed fabric according to any
one of the embodiments 1 to 11, which is selected from the group
consisting of protective suits, fire resistant suits for
fire-fighting, firefighter suits, rescue suits, workwear, a police
uniform, a camouflage uniform, and a military uniform.
Embodiment 13
[0026] A method for dyeing a fabric, characterized in that
[0027] dyeing a fabric comprising a meta-type wholly aromatic
polyamide fiber, a para-type wholly aromatic polyamide fiber and a
polyester fiber with a dye solution for wholly aromatic polyamide
fiber comprising 20% o.w.f. or less of a cationic dyestuff, and
then
[0028] dyeing the fabric with a dye solution for polyester fiber
comprising 2% o.w.f. or less of a disperse dyestuff.
Embodiment 14
[0029] The dyeing method according to the embodiment 13, wherein
the dyeing is performed by thermosol dyeing.
Advantageous Effects of Invention
[0030] According to the present invention, even in the case of a
fabric comprising a meta-type- and para-type-wholly aromatic
polyamide fibers and a polyester fiber which are difficult to dye,
it is possible to obtain a dyed fabric which achieves color
uniformity of the meta-type wholly aromatic polyamide fiber, the
para-type wholly aromatic polyamide fiber and the polyester fiber,
and which exhibits excellent heat resistance and flame resistance.
Further, according to the present invention, a textile product made
of this dyed fabric can be obtained.
[0031] Further, according to the present invention, there is
provided a textile product made of the dyed fabric described above,
which is selected from the group consisting of protective suits,
fire resistant suits for firefighting, firefighting suits, rescue
suits, workwear, a police uniform, a camouflage uniform, and a
military uniform.
[0032] Further, according to the present invention, there is
provided a method for dyeing a fabric.
DESCRIPTION OF EMBODIMENTS
[0033] In the following, embodiments of the present invention will
be described in detail.
<<Dyed Fabric>>
[0034] According to the present invention, there is provided a dyed
fabric dyed after being shaped into a fabric, which comprises a
meta-type wholly aromatic polyamide fiber, a para-type wholly
aromatic polyamide fiber and a polyester fiber and is a fabric dyed
with a cationic dyestuff and a disperse dyestuff, and which
exhibits 1 second or less of the afterflame time and afterglow time
defined in JISL1091A-1.
[0035] When a fabric contains a polyester fiber in addition to a
meta-type wholly aromatic polyamide fiber and a para-type wholly
aromatic polyamide fiber, it is possible to provide a relatively
inexpensive fabric which retains high heat resistance and flame
resistance. Conventional fabric having such a configuration may be
inferior in color shade. However, the present inventor has found
that, even in the case of fibers comprising a meta-type wholly
aromatic polyamide fiber and a para-type wholly aromatic polyamide
fiber and a polyester fiber, by dyeing the fibers with a cationic
dyestuff and a disperse dyestuff after shaping the fibers into a
fabric, it is possible to obtain a dyed fabric which is uniformly
dyed and which exhibits excellent appearance quality and excellent
heat resistance and flame resistance.
[0036] According to an embodiment of the present invention, it is
possible to provide a dyed fabric having excellent color uniformity
and having excellent rubbing fastness and excellent heat resistance
and flame resistance. Namely, with respect to the dyed fabric
according to the present invention, both of the dry rubbing
fastness and the wet rubbing fastness defined in JIS L 0849 II
method are preferably grade 3 or more.
[0037] In the present invention, the fastness of the dyed fabric
can be evaluated according to JIS L 0849 II type method. Each of
the dry rubbing fastness (the fastness to rubbing in dry condition)
and the wet rubbing fastness (the fastness to rubbing in wet
condition) is expressed in nine grades, i.e., "I", "1-2", "2",
"2-3", "3", "3-4", "4", "4-5", and "5", according to JIS L 0849 II
method, and grade "5" is the most excellent. Preferably, in the
dyed fabric of the present invention, both of the dry rubbing
fastness and the wet rubbing fastness of the dyed fabric are grade
3 or more, grade 3-4 or more, grade 4 or more, or grade 4-5 or
more.
[0038] In the dyed fabric according to another embodiment of the
present disclosure, at least the polyester fiber is a polyester
fiber ring-dyed with the disperse dyestuff (i.e., the polyester
fiber is dyed with the disperse dyestuff by ring-dyeing).
[0039] By using a polyester fiber ring-dyed with a disperse
dyestuff, it is possible to obtain a dyed fabric which is excellent
in heat resistance and flame resistance and has particularly good
color uniformity of the meta-type wholly aromatic polyamide fiber,
the para-type wholly aromatic polyamide fiber and the polyester
fiber, and which exhibits particularly excellent quality in
appearance.
[0040] Preferably, the dyed fabric is a fabric dyed with a cationic
dyestuff of 20% o.w.f. (on the weight of fiber) or less and then
dyed with a disperse dyestuff of 2% o.w.f. or less. When the dye is
in this range, a dyed fabric having particularly excellent rubbing
fastness while retaining excellent color uniformity is
provided.
[0041] Further, in the dyed fabric, it is preferable that the
weights of the meta-type wholly aromatic polyamide fiber, the
para-type wholly aromatic polyamide fiber and the polyester fiber
are in the ratio of 60 to 90:1 to 15:5 to 30 (more preferably 60 to
80:1 to 10:5 to 20, or 60 to 80:2 to 10:5 to 20, or still more
preferably 70 to 80:5 to 10:10 to 15).
[0042] Further, it is preferable that the dyed fabric is made of a
blended spun yarn comprising the meta-type wholly aromatic
polyamide fiber, the para-type wholly aromatic polyamide fiber and
the polyester fiber.
[0043] In addition, it is preferable that for the dyed fabric, the
water absorption performance defined in AATCC79 prior to washing is
2 seconds or less, 1.5 seconds or less, or 1.0 seconds or less, and
the water absorption performance defined in AATCC79 after 10
washing cycles defined in ISO6330:2012 (6N-F) is 10 seconds or
less, 5 seconds or less, or 1 second or less.
[0044] The present inventor has found that the amount of the
residual dyestuff, in particular the amount of the residual
disperse dyestuff, is important in improving the fastness to
rubbing while ensuring the color uniformity. Thus, for the dyed
fabric, it is preferable that the amount of the residual disperse
dyestuff, in particular the amount of the residual disperse
dyestuff in the polyester fiber, is from 0.01% o.w.f. to 0.5%
o.w.f. (more preferably from 0.01% o.w.f. to 0.1% o.w.f.), and it
is preferable that the residual cationic dyestuff, in particular
the residual cationic dyestuff in the meta-type wholly aromatic
polyamide fiber, is from 0.01% o.w.f. to 16.0% o.w.f. (more
preferably from 0.01% o.w.f. to 10% o.w.f.). When the residual
dyestuff is in this range, a dyed fabric having further improved
rubbing fastness while having excellent color uniformity is
provided.
[0045] The fabric of the present invention may have any shape, and
may be in the form of woven fabric, knitted fabric, nonwoven
fabric, and may be formed into the shape of a fabric by a known
method using the above-described fibers and/or fibers described
later. Further, in addition to the meta-type wholly aromatic
polyamide fiber and the para-type wholly aromatic polyamide fiber
and the polyester fiber, as well as an optional
electrically-conductive fiber described later, it is also possible
to use other fibers in blending, mixed weaving, interlacing, etc.
Examples of the other fibers include a cellulose fiber, a
polyacrylonitrile fiber, wool, and silk.
(Wholly Aromatic Polyamide Fiber)
[0046] The meta-type wholly aromatic polyamide fiber is a fiber in
which aromatic rings constituting a main skeleton are bonded in
meta-position by amide bonds, and which has 85 mol % or more of
metaphenylene isophthalamide units, based on all repeating units of
the polymer. Particularly preferred fiber is a polymetaphenylene
isophthalamide homopolymer. The third component, which can be
copolymerized in 15 mol % or less (preferably 5 mol % or less) of
all the repeating units, includes, as a diamine component, for
example, paraphenylenediamine, 3,4'-diaminodiphenyl ether,
4,4'-diaminodiphenyl ether, paraxylylenediamine,
biphenylenediamine, 3,3'-dichlorobenzidine, 3,3'-dimethylbenzidine,
3,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylmethane, and
1,5-naphthalenediamine, or other aromatic diamines. Further, with
regard to an acid component, examples thereof include terephthalic
acid, naphthalene-2,6-dicarboxylic acid, and
naphthalene-2,7-dicarboxylic acid, and other aromatic dicarboxylic
acids. In addition, in these aromatic diamines and aromatic
dicarboxylic acids, hydrogen atoms of the aromatic ring may be
partly substituted by a halogen atom or an alkyl group such as a
methyl group. It is preferable that 20% or more of the total
terminal of the polymer is blocked with a monovalent diamine such
as aniline or a monovalent carboxylic acid component, since the
decrease in strength of the fiber when held at a high temperature
for a long time is reduced. Incidentally, as such a meta-type
wholly aromatic polyamide fiber, mention may be made to
commercially available products such as Teijinconex (trademark),
Teijinconex Neo (trademark), Nomex (trademark), and the like.
[0047] Such a meta-type wholly aromatic polyamide can be produced
by a known interfacial polymerization method. With regard to the
degree of polymerization of the polymer, it is preferable that an
intrinsic viscosity (I.V.) measured in N-methyl-2-pyrrolidone
solution at a concentration of 0.5 g/100 ml is in the range of 1.3
to 1.9 dl/g.
[0048] Further, the meta-type wholly aromatic polyamide may contain
alkylbenzenesulfonic acid onium salt. Examples of the
alkylbenzenesulfonic acid onium salt include compounds such as
tetrabutylphosphonium hexylbenzene sulfonate,
tributylbenzylphosphonium hexylbenzene sulfonate,
tetraphenylphosphonium dodecylbenzene sulfonate,
tributyltetradecylphosphonium dodecylbenzene sulfonate,
tetrabutylphosphonium dodecylbenzene sulfonate, and
tributylbenzylammonium dodecylbenzene sulfonate. Among those,
tetrabutylphosphonium dodecylbenzene sulfonate or
tributylbenzylammonium dodecylbenzene sulfonate are preferred,
since they are readily available, have good thermal stability, and
have high solubility in N-methyl-2-pyrrolidone.
[0049] The content ratio of the alkylbenzenesulfonic acid onium
salt is preferably in the range of 2.5 mol % or more, preferably
3.0 mol % to 7.0 mol %, based on the poly-m-phenylene
isophthalamide, in order to obtain an sufficient improvement effect
of dyeability.
[0050] Further, as a method of mixing poly-m-phenylene
isophthalamide and alkylbenzene sulfonic acid onium salt, it is
possible to use a method of mixing and dissolving poly-m-phenylene
isophthalamide in a solvent and then dissolving alkylbenzene
sulfonic onium salt in the solvent. The dope thus obtained is
formed into a fiber by a known method.
[0051] In a polymer used for the meta-type wholly aromatic
polyamide fiber, in order to improve the dyeing performance and the
resistance to discoloration, etc., it is possible to copolymerize,
as the third component, an aromatic diamine component or an
aromatic dicarboxylic acid halide component in an aromatic
polyamide skeleton containing a repeating structural unit
represented by the following formula (1), wherein the aromatic
diamine component and the aromatic dicarboxylic acid halide
component are different from the main constitutional unit of the
repeating structure, and wherein the content of the aromatic
diamine component or the aromatic dicarboxylic acid halide
component is 1 mol % to 10 mol % based on the total amount of the
repeating structural units of the aromatic polyamide:
--(NH-Ar1-NH--CO-Ar1-CO)-- formula (1)
wherein Ar1 is a divalent aromatic group with binding groups in
meta-position or in the direction other than parallel axis.
[0052] Incidentally, as the third component, it is possible to
copolymerize the aromatic diamine or the aromatic dicarboxylic acid
dichloride represented by the following formulas (2), (3), (4), and
(5). Specific examples of the aromatic diamines represented by the
formulas (2) and (3) include, for example, p-phenylenediamine,
chlorophenylenediamine, methylphenylenediamine,
acetylphenylenediamine, aminoanisidine, benzidine,
bis(aminophenyl)ether, bis(aminophenyl)sulfone, diaminobenzanilide,
diaminoazobenzene, and the like. Specific examples of the aromatic
dicarboxylic acid dichloride represented by the formulas (4) and
(5) include, for example, terephthalic acid chloride,
1,4-naphthalenedicarboxylic acid chloride,
2,6-naphthalenedicarboxylic acid chloride,
4,4'-biphenyldicarboxylic acid chloride, 5-chloroisophthalic acid
chloride, 5-methoxyisophthalic acid chloride, and bis
(chlorocarbonylphenyl) Ether.
H.sub.2N-Ar2-NH.sub.2 formula (2)
H.sub.2N-Ar2-Y-Ar2-NH.sub.2 formula (3)
XOC-Ar3-COX formula (4)
XOC-Ar3-Y-Ar3-COX formula (5)
wherein Ar2 is a divalent aromatic group different from Ar1, Ar3 is
a divalent aromatic group different from Ar1, Y is at least an atom
or a functional group selected from the group consisting of oxygen
atom, sulfur atom, and alkylene group, and X represents halogen
atom.
[0053] Further, the crystallinity of the meta-type wholly aromatic
polyamide fiber is preferably 5% to 35%, since a good exhaustion of
dye is obtained and since it is easy to adjust a color to the
target color even under a condition where the amount of dye is low
or even under a weak dyeing condition. In addition, the
crystallinity is more preferably 15% to 25%, since the uneven
distribution of the dye on the surface hardly occurs, the
resistance to discoloration is high, and the dimensional stability
necessary for practical use can be secured.
[0054] Further, the residual solvent content in the meta-type
wholly aromatic polyamide fiber is preferably 1.0% by weight or
less (more preferably 0.3% by weight or less), since the excellent
flame retardant performance of the meta-type wholly aromatic
polyamide fiber is retained, uneven distribution of the dye on the
surface hardly occurs, and the resistance to discoloration becomes
high.
[0055] As a method of polymerizing a meta-type wholly aromatic
polyamide polymer, for example, it is possible to use a solution
polymerization method or an interfacial polymerization method,
which are described for example in JP-S35-14399A, U.S. Pat. No.
3,360,595, JP-S47-10863A.
[0056] As a spinning solution, it is possible to use an amide-based
solvent containing an aromatic copolyamide polymer, which is
obtained by a method such as the solution polymerization or
interfacial polymerization described above. Alternatively, it is
also possible to isolate a polymer from the polymerization solution
and dissolve the polymer in an amide-based solvent.
[0057] Examples of the amide-based solvent used in the
polymerization include N,N-dimethylformamide,
N,N-dimethylacetamide, N-methyl-2-pyrrolidone, dimethyl sulfoxide,
and the like. Among those, N,N-dimethylacetamide is particularly
preferred.
[0058] It is preferable that the copolymerized aromatic polyamide
polymer solution is further stabilized by containing an alkali
metal salt or an alkaline earth metal salt, since this makes it
possible to use the solution at higher concentration and/or at
lower temperature. The alkali metal salt or the alkaline earth
metal salt is preferably 1% by mass or less, more preferably 0.1%
by mass or less, based on the total mass of the polymer
solution.
[0059] In a spinning and coagulation step, a spinning solution (a
solution of meta-type wholly aromatic polyamide polymer) is spun
into a coagulation solution for the coagulation.
[0060] The apparatus for the spinning is not particularly limited,
and a known wet spinning apparatus can be used. Further, as long as
the wet spinning is stably performed, there is no particular
limitation on the number, the arrangement, or the hole shape, etc.,
of the spinning nozzle. For example, it is possible to use a
multi-hole spinning nozzle for staple fiber having 1000 to 30000
pores and/or having a spinning hole diameter of 0.05 mm to 0.2 mm.
Note that the suitable temperature at which the spinning solution
(the solution of meta-type wholly aromatic polyamide polymer)
obtained above is spun out from the spinning nozzle (spinneret) is
in the range of 20.degree. C. to 90.degree. C.
[0061] As a coagulation bath used to obtain the fiber, it is
preferable to use an amide-based solvent substantially free of
inorganic salts. In particular, it is preferable to use an aqueous
solution having 45 to 60% by mass of NMP concentration at a bath
temperature (bath liquid temperature) range of 10.degree. C. to
50.degree. C. When the concentration of the amide-based solvent
(preferably NMP) is less than 45% by mass, the skin may have a
thicker structure, the cleaning efficiency in the cleaning step may
decrease, and it may be difficult to reduce the amount of residual
solvent in the fiber. On the other hand, when the concentration of
the amide-based solvent (preferably NMP) exceeds 60% by mass,
uniform coagulation may not be performed in the core of the fiber,
and therefore it may be difficult to reduce the amount of solvent
remaining in the fiber. Incidentally, the suitable immersion time
of the fiber in the coagulation bath is in the range of 0.1 seconds
to 30 seconds.
[0062] The drawing is carried out in an amide-based solvent. In
particular, it is preferable to carry out the process at a drawing
ratio of 3 to 4 times in a plasticizing drawing bath which contains
an aqueous solution having 45% by mass to 60% by mass of NMP
concentration and has a bath liquid temperature of 10.degree. C. to
50.degree. C. After the drawing, thorough washing is performed by
passing the fiber through a 10.degree. C. to 30.degree. C. aqueous
solution with 20% by mass to 40% by mass of NMP concentration,
followed by passing the fiber through a 50.degree. C. to 70.degree.
C. hot water bath.
[0063] After washing, the fiber is subjected to a dry heat
treatment at a temperature of 270.degree. C. to 290.degree. C.,
which makes it possible to obtain a meta-type wholly aromatic
polyamide fiber which satisfies the above range of crystallinity
and residual solvent content. Preferable degree of crystallinity
and preferable residual solvent content can be obtained by the
above-described method.
[0064] Incidentally, the meta-type wholly aromatic polyamide fiber
may be a long fiber (multifilament) or a short fiber. When it is
blended with other fibers, a short fiber having a fiber length of
25 mm to 200 mm is preferred, and it is further preferable that a
single fiber fineness is in a range of 1 dtex to 5 dtex.
[0065] Further, it is preferable that a meta-type wholly aromatic
polyamide fiber is contained in a fabric as a blended spun yarn
with a para-type wholly aromatic polyamide fiber, since the
strength of the fabric is improved.
[0066] As the para-type wholly aromatic polyamide fiber, a
paraphenylene terephthalamide fiber or a
coparaphenylene-3,4'oxydiphenylene terephthalamide fiber is more
preferable. Specific examples thereof include Technora (trademark),
Kevlar (trademark) and Twaron (trademark).
[0067] Further, these fibers may contain additives such as an
antioxidant, an infrared absorber, an ultraviolet absorber, a heat
stabilizer, a flame retardant, titanium oxide, a colorant, and
inert fine particles, as long as the object of the present
invention is not impaired.
<Polyester Fiber>
[0068] The polyester fiber is not particularly limited, and
examples thereof include polyethylene terephthalate,
polytrimethylene terephthalate, polybutylene terephthalate,
polyethylene naphthalate, polycyclohexane terephthalate, and
copolymers thereof, and a fiber in which a part of an acid
component (terephthalic acid) is replaced with isophthalic
acid.
<Electrically-Conductive Fiber>
[0069] Preferably, the fabric contains an electrically-conductive
fiber in addition to the above-described fibers, since it is useful
to prevent static electricity.
[0070] When the fabric contains the electrically-conductive fiber,
the weights of meta-type wholly aromatic polyamide fiber, para-type
wholly aromatic polyamide fiber, polyester fiber and
electrically-conductive fiber are preferably in the ratio of 60 to
80:1 to 10:5 to 20:1 to 4 (more preferably 70 to 80:2 to 10:5 to
20:1 to 5, and still more preferably 75 to 80:3 to 8:10 to 20:1 to
4).
[0071] Further, it is preferable that the fabric is made of a
blended spun yarn comprising a meta-type wholly aromatic polyamide
fiber, a para-type wholly aromatic polyamide fiber, a polyester
fiber and an electrically-conductive fiber.
[0072] Preferably, the electrically-conductive fiber comprises, as
a conductor of a conductive portion thereof, for example, at least
one of the following components: carbon black, metal particles
(silver particles, copper particles, aluminum particles, etc.),
metal oxide (particles mainly contains titanium oxide, tin (IV)
oxide, zinc oxide, indium oxide or the like) and a polymer
containing electrically-conductive particles such as a polymer
having coated particles of an electrically-conductive oxide.
[0073] The form of the electrically-conductive fiber may be a
structure in which the entire fiber is made of a conductive
portion, or a structure in which the non-conductive portion and the
conductive portion have a cross-sectional shape such as a
core-sheath shape, a sandwich shape, or an eccentric shape. The
resin forming the conductive portion and/or non-conductive portion
is not particularly limited, as long as it has fiber-forming
ability. Specifically, examples thereof include, as for a nylon
resin, nylon 6, nylon 11, nylon 12, and nylon 66. Further, examples
of a polyester resin include polyethylene terephthalate,
polytrimethylene terephthalate, polybutylene terephthalate,
polyethylene naphthalate, polycyclohexane terephthalate, and a
copolymer thereof, and a resin in which a part of an acid component
(terephthalic acid) is replaced with isophthalic acid.
[0074] Examples of commercially available electrically-conductive
fibers include "Metalian" (trade name) manufactured by Teijin
Limited, "MEGANA" (trade name) manufactured by Unitika Ltd.,
"Luana" (trade name) manufactured by Toray Industries, Inc.,
"Clacarbo" (trade name) manufactured by Kuraray Co. Ltd. In
particular, a preferable electrically-conductive fiber is a
core-sheath type composite fiber in which a conductive component is
disposed in a sheath portion. As such a core-sheath type composite
fiber, "NO SHOCK" (trademark) manufactured by Solcia Corporation is
preferable.
<Dyestuff>
[0075] The fabric of the present invention is a fabric dyed with
various dyes after being shaped into a fabric. When a plurality of
fiber species are used, a dyeing method suitable for the fiber
species may be selected accordingly. Examples of the dyestuff
include a cationic dyestuff, a Vat dyestuff, and a disperse
dyestuff. The dyed fabric of the present invention is a fabric dyed
with a cationic dyestuff and a disperse dyestuff.
[0076] A cationic dyestuff refers to a water-soluble dye having a
basic functional group, and are commonly used for dyeing a fiber
such as an acrylic fiber, a natural fiber, or a polyester fiber
dyeable with a cationic dyestuff. The cationic dyestuff can be
appropriately selected, and examples thereof include
diacrylmethane-based dyestuff and triacrylmethane-based dyestuff,
quinoneimine-based (azine, oxazine, thiazine) dyestuff,
xanthene-based dyestuff, methine-based (polymethine, azamethine)
dyestuff, heterocyclic azo (thiazole azo, triazole azo,
benzothiazole azo) dyestuff, and anthraquinone dyestuff.
Incidentally, it is possible to use a cationic dyestuff which is
made into a dispersion type by blocking a basic functional group.
As such dyestuffs, an azo dyestuff is desirable, and examples of
the azo dyestuff include C.I. Basic Blue54, C.I. Basic Blue3, C.I.
Basic Red29, C.I. Basic Yellow67.
[0077] A Vat dyestuff is a water-insoluble dye. The Vat dyestuff is
dissolved in an alkaline solution by a reduction action, and is
oxidized by air to be insolubilized again for the dyeing. The Vat
dyestuff may be appropriately selected, and examples thereof
include an indigo-based dye and an anthraquinone-based
dyestuff.
[0078] A disperse dyestuff refers to a dyestuff which is hardly
soluble in water and is used for dyeing hydrophobic fibers using a
dispersed system in water. The disperse dyestuff is often used for
dyeing a fiber such as a polyester fiber or an acetate fiber. The
disperse dyestuff may be appropriately selected, and examples
thereof include a benzene-based azo (mono azo, disazo, etc.,)
dyestuff, a heterocyclic-based azo (thiazole azo, benzothiazole
azo, quinoline azo, pyrizone azo, imidazole azo, thiophene azo,
etc.,) dyestuff, an anthraquinone-based dyestuff, a
condensation-type (quinophthalone, styryl, coumarin, etc.,)
dyestuff, and the like.
[0079] When dyeing a fabric, a carrier agent may be used.
Preferably, the carrier agent is, for example, at least one
selected from the group consisting of DL-.beta.-ethylphenethyl
alcohol, 2-ethoxybenzyl alcohol, 3-chlorobenzyl alcohol,
2,5-dimethylbenzyl alcohol, 2-nitrobenzyl alcohol,
p-isopropylbenzyl alcohol, 2-methylphenethyl alcohol,
3-methylphenethyl alcohol, 4-methylphenethyl alcohol,
2-methoxybenzyl alcohol, 3-iodobenzyl alcohol, cinnamic alcohol,
p-anisyl alcohol, benzhydrol, benzyl alcohol, propylene glycol
phenyl ether, ethylene glycol phenyl ether and
N-methylformanilide.
[0080] A method for manufacturing the dyed fabric according to the
present disclosure is not particularly limited, but can be
preferably manufactured by the dyeing method according to the
present disclosure described below.
<<Dyeing Method>>
[0081] When dyeing a fabric comprising a meta-type wholly aromatic
polyamide fiber, a para-type wholly aromatic polyamide fiber and a
polyester fiber, or a fabric consisting of these fibers, first, the
fabric is dyed with a cationic dyestuff at a temperature raised
enough to dye the meta-type wholly aromatic polyamide fiber and the
para-type wholly aromatic polyamide fiber, and then the fabric is
dyed in a dyeing bath containing a disperse dyestuff at a
temperature raised enough to dye the polyester fiber. The dyeing
with the cationic dyestuff is preferably performed at a temperature
range of 115.degree. C. to 135.degree. C., preferably at
115.degree. C. to 125.degree. C. The dyeing with the disperse
dyestuff can be performed, for example, at 125.degree. C. to
135.degree. C.
[0082] In this dyeing method, the dyeing with the disperse dyestuff
is performed after the dyeing with the cationic dyestuff has been
completed. In this method, a dyeing bath containing a cationic
dyestuff may be cooled to 80.degree. C. or less, and then a
disperse dyestuff may be added and the temperature may be raised,
or, the dyeing bath containing the cationic dyestuff may be
discarded and a dyeing bath containing a disperse dyestuff may be
newly prepared to perform the dyeing.
[0083] By dyeing the fabric with the cationic dyestuff and then
dyeing the fabric with the disperse dyestuff as described above,
even in the case of a fabric containing a meta-type- and
para-type-wholly aromatic polyamide fibers and a polyester fiber
which are difficult to dye, it is possible to obtain a dyed fabric
and a textile product made thereof which achieve excellent color
uniformity of the meta-type wholly aromatic polyamide fiber, the
para-type wholly aromatic polyamide fiber and the polyester fiber
and which have improved fastness in a darker color range.
[0084] In particular, according to the present invention, there is
provided a method for dyeing a fabric, in which a fabric comprising
a meta-type wholly aromatic polyamide fiber, a para-type wholly
aromatic polyamide fiber and a polyester fiber, or a fabric
consisting of these fibers, is dyed with a dye solution for wholly
aromatic polyamide fiber containing 20% o.w.f. or less of a
cationic dyestuff, and then dyed with a dye solution for polyester
fiber containing 2.0% o.w.f. or less of a disperse dyestuff.
[0085] According to this method, even in the case of a fabric
containing a meta-type- and para-type-wholly aromatic polyamide
fibers and a polyester fiber which are difficult to dye, it is
possible to obtain a dyed fabric and a textile product made thereof
which achieve excellent color uniformity of the meta-type wholly
aromatic polyamide fiber, the para-type wholly aromatic polyamide
fiber and the polyester fiber, and which exhibit particularly
excellent fastness in a darker color range.
[0086] The concentration of the disperse dyestuff at the time of
dyeing is more preferably from 0.01% o.w.f. to 1.0% o.w.f., and
even more preferably from 0.01% o.w.f. to 0.5% o.w.f.
[0087] The concentration of the cationic dyestuff at the time of
dyeing is more preferably from 0.01% o.w.f. to 15% o.w.f., and even
more preferably from 0.1% o.w.f. to 10% o.w.f.
<Thermosol Dyeing>
[0088] According to an embodiment of the dyeing method of the
present disclosure, when dyeing a fabric comprising a meta-type
wholly aromatic polyamide fiber, a para-type wholly aromatic
polyamide fiber and a polyester fiber, or a fabric consisting of
these fibers, first, the fabric is dyed with a cationic dyestuff
which is a dye solution for wholly aromatic polyamide fiber at a
temperature raised enough to dye the meta-type wholly aromatic
polyamide fiber and the para-type wholly aromatic polyamide fiber,
and then a thermosol dyeing is performed using a disperse dyestuff
which is a dyeing solution for polyester fiber. Incidentally, the
dyeing with the cationic dyestuff is preferably performed at
115.degree. C. to 135.degree. C., more preferably 115.degree. C. to
125.degree. C.
[0089] In the thermosol dyeing, in particular, it is preferable to
use a thermosol dyeing machine of a continuous device equipped with
a padder, a dryer and a thermosol machine. In this case, the dyeing
is preferably carried out by impregnating a fabric dyed with a
cationic dyestuff into a disperse dye solution, followed by
squeezing with a mangle at a squeezing ratio of 50% by mass to 70%
by mass, followed by dry-heating at 90.degree. C. to 150.degree. C.
(preferably at 120.degree. C. to 140.degree. C.) for 50 to 70
seconds, followed by drying at 160.degree. C. to 240.degree. C. for
2 to 4 minutes (preferably at 180.degree. C. to 220.degree. C. for
2.5 to 3.5 minutes), and then using an open soaper to perform
reduction cleaning, soaping, and hot-water washing, and then
performing final setting.
[0090] In the dyeing method comprising the thermosol dyeing, since
a polyester fiber is ring-dyed (i.e., a polyester fiber is dyed by
"ring-dyeing"), it is possible to achieve particularly good color
uniformity between the polyester fiber and the above-mentioned
wholly aromatic polyamide fibers. Therefore, even in the case of a
fabric made of different fibers, i.e., wholly aromatic polyamide
fibers and a polyester fiber, a dyed fabric with good quality can
be obtained. in particular, by dyeing the meta-type wholly aromatic
polyamide fiber and the para-type wholly aromatic polyamide fiber
by means of a liquid flow dyeing and further by dyeing the
polyester fiber by means of a continuous dyeing, much better color
uniformity can be achieved. Incidentally, the color uniformity of
the fibers can be evaluated by magnifying the obtained dyed fabric
with a microscope and by evaluating the degree of dyeing of the
fibers with a visual observation and with a color swatch.
[0091] Further, in another preferred dyeing method, a fabric
containing a meta-type wholly aromatic polyamide fiber, a para-type
wholly aromatic polyamide fiber and a polyester fiber, or a fabric
consisting of these fibers, is dyed with a dye solution for wholly
aromatic polyamide fiber containing 20% o.w.f. or less of a
cationic dyestuff, and then subjected to a thermosol dyeing with a
dye solution for polyester fiber containing 2% o.w.f. or less of a
disperse dyestuff. By performing the dyeing in this range, it is
possible to obtain a dyed fabric and a textile product made thereof
which achieve particularly excellent color uniformity of the
meta-type wholly aromatic polyamide fiber, the para-type wholly
aromatic polyamide fiber and the polyester fiber, and which further
exhibit improved fastness in a darker color range.
[0092] In particular, according to the dyeing method above, it is
possible to avoid a problem that, when an aramid (wholly aromatic
polyamide) and a polyester are dyed by a liquid flow dyeing, it is
usually difficult to obtain color uniformity of the fibers, and a
problem that if the fabric is dyed for a long time in order to
obtain color uniformity, the texture becomes soft.
[0093] With regard to the constitutions of the dyeing method
according to the present invention, such as a fabric, fibers
constituting the fabric, a weight ratio of fibers, and a dye, etc.,
it is possible to refer to the above descriptions regarding the
dyed fabric.
[0094] Incidentally, in the dyeing method according to the present
invention, the fabric may contain an electrically-conductive fiber.
According to the dyeing method of the present invention, even when
an electrically-conductive fiber is contained, it is possible to
obtain a dyed fabric which exhibits excellent color uniformity of
the fibers.
<Other Processing>
[0095] In order to impart various functions to the fabric, it is
possible to apply or add other various processing to the fabric,
such as a water repellent, a heat storage agent, an ultraviolet
shielding agent or an antistatic agent, an antibacterial agent, a
deodorant, an insect repellent, a phosphorescent agent, a
retroreflective agent, etc. For example, as a sweat absorbing
processing agent, it is preferable to use polyethylene glycol
diacrylate, a derivative of polyethylene glycol diacrylate, a
copolymer of polyethylene terephthalate and polyethylene glycol, a
water-soluble polyurethane, or the like. In particular, a copolymer
of polyethylene glycol and aminosilicone is preferred, since it has
good affinity for the wholly aromatic polyamide fiber and thus the
sweat absorption properties with good washing durability are easily
obtained. Further, smaller particle diameter of the sweat absorbing
processing agent is preferable, since in this case it easily
adheres to the wholly aromatic polyamide fiber. The particle
diameter is preferably in the range of 25 nm to 200 nm. The sweat
absorbing processing agent may be applied to the fabric by bath
treatment at the same time as dyeing, or may be applied to the
fabric by padding treatment.
[0096] The textile product of the present invention includes
protective suits, fire resistant suits for firefighting,
firefighter suits, rescue suits, workwear, a police uniform, a
camouflage uniform, and a military uniform which are made of the
dyed fabric described above. Since these textile products are made
of the above-described dyed fabric, they exhibit excellent heat
resistance, flame retardancy, flame resistance and strength, and
further, they exhibit excellent color uniformity, and in particular
they exhibit good dye fastness. Therefore, as an aesthetic fabric
having characteristics of both of the wholly aromatic polyamide
fibers and the polyester fiber, these textile products are suitable
for people who are engaged in work which may be exposed to flames
or the like, such as a firefighter, a pilot, a race driver, and a
worker of a power company or a chemical company.
EXAMPLES
[0097] Next, Examples and Reference Examples of the present
invention will be described in detail in the following, but the
present invention is not limited thereto. Measurements in the
examples and reference examples were performed by the following
methods.
(1) Flame Retardancy
[0098] The limiting oxygen index (LOI) defined in E-2 of
JIS1091:1999 was determined.
(2) Fastness
[0099] The rubbing fastness (fastness to rubbing) as defined in JIS
L 0849 II method was measured in dry condition and wet condition,
respectively.
(3) Flammability
[0100] The afterflame time and afterglow time defined in JIS L 1091
A-1 method (1992) were measured.
(4) Residual Solvent Content
[0101] About 8.0 g of raw fibers were collected, dried at
105.degree. C. for 120 minutes, and then allowed to cool in a
desiccator, and the fiber mass (M1) was weighed. Subsequently, the
reflux extraction was performed for this fiber in methanol for 1.5
hours using a Soxhlet extractor, in order to extract an amide-based
solvent contained in the fiber. The fibers after completion of the
extraction were taken out, dried under vacuum at 150.degree. C. for
60 minutes, and then allowed to cool in a desiccator, and the fiber
mass (M2) was weighed. The amount of the solvent remaining in the
fibers (mass of the amide-based solvent) was calculated from the
obtained M1 and M2 by the following formula:
Residual solvent content (%)=[(M1-M2)/M1].times.100
(5) Crystallinity
[0102] The diffraction profile was measured with an X-ray
diffraction measurement device (RINT TTRIII, manufactured by Rigaku
Corporation) by aligning the raw fibers into a fiber bundle having
a diameter of about 1 mm and mounting it onto a fiber sample table.
The measurement conditions were as follows: Cu-K.alpha. source (50
kV, 300 mA), scanning angle range 10.degree. to 35.degree.,
continuous measurement 0.1.degree. width measurement, and
1.degree./min scanning. Total scattering profile was obtained from
the measured diffraction profile by performing correction of air
scattering and incoherent scattering by a linear approximation.
Subsequently, the crystal scattering profile was obtained by
subtracting the amorphous scattering profile from the total
scattering profile. Crystallinity was determined based on the area
intensity of the crystal scattering profile (crystal scattering
intensity) and the area intensity of the total scattering profile
(total scattering intensity), by the following formula:
Crystallinity (%)=[crystal scattering intensity/total scattering
intensity].times.100
(6) Water Absorption
[0103] The water absorption performance defined in AATCC79 prior to
washing (hereinafter referred to as the "initial water absorption
performance") and the water absorption performance defined in
AATCC79 after 10 washes defined in ISO6330:2012 (6N-F) (hereinafter
referred to as the "water absorption performance after 10 washing
cycles") were measured. Incidentally, the upper limit of the water
absorption performance after 10 washing cycles was set to be 60
seconds.
(7) Darkness of a Color (L Value)
[0104] The L value was measured using a MacBeth spectrophotometer
Color-Eye3100.
(8) Residual Dyestuff
<Residual Disperse Dyestuff in Polyester Fiber>
[0105] The color (L value) of a dye solution prior to use was
measured using a MacBeth spectrophotometer Color-Eye3100, and the
color (L value) of a dye solution after the dyeing (a residual
solution) was measured again, and the residual dye (% o.w.f.) was
measured from the difference of these values.
<Residual Cationic Dyestuff in Meta-Type Wholly Aromatic
Polyamide Fiber>
[0106] The color (L value) of a dye solution prior to use was
measured using a MacBeth spectrophotometer Color-Eye3100, and the
color of (L value) of a dye solution after the dyeing (a residual
solution) was measured again, and the residual dye (% o.w.f.) was
measured from the difference of these values.
(9) Color Uniformity
[0107] With regard to the color uniformity of the dyed fabric, the
obtained dyed fabric was magnified by a microscopy and the degree
of dyeing of fibers was evaluated by visual observation, according
to the following criteria:
Very good: The fabric exhibited particularly good color uniformity.
Good: The fabric exhibited good color uniformity. Moderate:
Although uneven dyeing was observed in a part of the fabric, the
fabric generally exhibited color uniformity. Poor: Non-uniform
dyeing was observed throughout the fabric.
Examples 1 to 5
[0108] Dyed fabrics according to Examples 1 to 5 were manufactured
and evaluated for quality.
Example 1
[0109] In the spinning process, the following fibers were blended
at a weight ratio of 78:5:15:2, to obtain a single yarn having an
English cotton count of 40 and a twist count of 24 T/inch (twist
factor=3.4), as a spun yarn: [0110] a short fiber consisting of
polymetaphenylene isophthalamide fiber ("Teijinconex neo"
(trademark), manufactured by Teijin Limited) having a single fiber
fineness of 1.7 dtex, a cut length (fiber length) of 51 mm and a
LOI of 26; [0111] a short fiber consisting of polyparaphenylene
terephthalamide (PPTA) fiber ("Twaron" (trademark), manufactured by
Teijin Limited) having a single fiber fineness of 1.7 dtex, a cut
length (fiber length) of 51 mm, and a limiting oxygen index defined
in E-2 of JIS1091:1999 of 25; [0112] a short fiber consisting of
polyester fiber ("eco-PET(RA02)", manufactured by Teijin Limited)
having a single fiber fineness of 2.2 dtex and a fiber length of 38
mm; [0113] a short fiber consisting of an electrically-conductive
fiber ("Corebrid ET10" (trademark), manufactured by Mitsubishi
Chemical Corporation) having a single fiber fineness of 3.3 dtex
and a cut length (fiber length) of 38 mm.
[0114] Two of the obtained spun yarns were combined and twisted by
double twister at a second twist count of 20.9 T/inch, and then
subjected to twist-set at a setting temperature of 120.degree. C.
for a setting time of 20 minutes by using a vacuum steam setting
machine, in order to obtain a flame-retardant doubled and twisted
yarn.
[0115] Then, weaving was performed with the obtained
flame-retardant doubled and twisted yarn, in order to obtain a
woven fabric with a fabric density of 57 ends per inch and 53 picks
per inch and a fabric texture of 1/1 plain weave.
[0116] The woven fabric was subjected to singeing treatment,
scouring treatment, dry treatment, and heat treatment
(temperature:160.degree. C., time:30 seconds) in a conventional
manner, and then dyed with a dye solution for wholly aromatic
polyamide fiber at a temperature of 130.degree. C. for 60 minutes
after raising the temperature from ambient temperature (bath ratio
1:20), wherein the dye solution for wholly aromatic polyamide fiber
contains 16% o.w.f. of a cationic dyestuff (Basacryl Red GL,
manufactured by BASF), 10 g/l of a carrier agent, 3 g/l of acetic
acid, 20 g/l of sodium nitrate, and 1 g/l of a dispersant (Disper
VG, manufactured by Meisei Chemical Works, Ltd.).
[0117] Then, the fabric was dyed with a dye solution for polyester
fiber at a temperature of 130.degree. C. for 30 minutes after
raising the temperature from ambient temperature (bath ratio 1:20),
wherein the dye solution for polyester fiber contains 0.2% o.w.f.
of a disperse dyestuff (Foron Rubine S-2GFL, manufactured by
Sandoz), 3 g/l of acetic acid, and 1 g/l of a dispersant (Disper
VG, manufactured by Meisei Chemical Works, Ltd.).
[0118] The obtained colored fabric was then washed with a reducing
bath (bath ratio 1:20) containing 1 g/L of hydrosulfite and 1 g/L
of soda ash at a temperature of 70.degree. C. for 20 minutes.
Thereafter, after cooling, the dyed fabric was collected, washed
with water, air-dried, and subjected to heat treatment to finish.
The heat treatment was carried out at a temperature of 160.degree.
C. for 1 minutes to obtain a dyed fabric.
[0119] The obtained fabric was treated with a sweat absorbing
processing agent for polyester and a sweat absorbing processing
agent for wholly aromatic polyamide fiber in a conventional
manner.
[0120] In the obtained dyed fabric, the woven fabric density was 63
ends per inch and 55 picks per inch, the limiting oxygen index was
26.0, the dry rubbing fastness was grade 4-5, the wet rubbing
fastness was grade 4-5, the afterflame time and afterglow time were
0 second, the initial water absorption performance was 1.0 seconds,
the water absorption performance after 10 washing cycles was 1.0
seconds, the residual disperse dyestuff in the polyester fiber was
0.03% o.w.f., and the residual cationic dyestuff in the meta-type
wholly-aromatic polyamide fiber was 8.0% o.w.f. Evaluation results
are shown in Table 1.
Example 2
[0121] A dyed fabric was obtained as in Example 1 except that in
the spinning step, instead of "Twaron" which is a para-type wholly
aromatic polyamide, a coparaphenylene.3,4' oxydiphenylene
terephthalamide fiber ("Technora" (trademark) manufactured by
Teijin Limited) having a single fiber fineness of 1.7 dtex, a cut
length (fiber length) of 51 mm, and a limiting oxygen index defined
in E-2 of JIS1091:1999 of 25, was used.
[0122] In the obtained dyed fabric, the woven fabric density was 63
ends per inch and 55 picks per inch, the limiting oxygen index was
26.0, the dry rubbing fastness was grade 4-5, the wet rubbing
fastness was grade 4-5, the afterflame time and afterglow time were
0 second, the initial water absorption performance was 1.0 seconds,
the water absorption performance after 10 washing cycles was 1.0
seconds, the residual disperse dyestuff in the polyester fiber was
0.02% o.w.f., and the residual cationic dyestuff in the meta-type
wholly aromatic polyamide fiber was 8.0% o.w.f. Evaluation results
are shown in Table 1.
Example 3
[0123] A dyed fabric was obtained as in Example 1 except that in
the spinning step, an electrically-conductive fiber ("CoreBrid
ET10" (trademark), manufactured by Mitsubishi Chemical Corporation)
having a single fiber fineness of 3.3 dtex and a cut length (fiber
length) of 38 mm was not contained, and a weight ratio of the
fibers was set to 80:5:15.
[0124] In the obtained dyed fabric, the woven fabric density was 63
ends per inch and 55 picks per inch, the limiting oxygen index was
26.0, the dry rubbing fastness was grade 4-5, the wet rubbing
fastness was 4-5 grade, the afterflame time and afterglow time were
0 second, the initial water absorption performance was 1.0 seconds,
the water absorption performance after 10 washing cycles was of 1.0
seconds, the residual disperse dyestuff in the polyester fiber was
0.02% o.w.f., and the residual cationic dyestuff in the meta-type
wholly aromatic polyamide fiber was 8.0% o.w.f. Evaluation results
are shown in Table 1.
Example 4
[0125] A dyed fabric was obtained as in Example 1 except that the
sweat absorbing processing agent for polyester was not used in the
dispersion dyeing condition. In the obtained fabric, the woven
fabric density was 63 ends per inch and 55 picks per inch, the
limiting oxygen index was 26.0, the dry rubbing fastness was grade
4 and the wet rubbing fastness was grade 4, the afterflame time and
afterglow time were 0 second, the initial water absorption
performance was 10.0 seconds, the water absorption performance
after 10 washing cycles was 15.0 seconds, the residual disperse
dyestuff in the polyester fiber was 0.06% o.w.f., and the residual
cationic dyestuff in the meta-type wholly aromatic polyamide fiber
was 8.0% o.w.f. Evaluation results are shown in Table 1.
Example 5
[0126] A dyed fabric was obtained as in Example 1 except that the
concentration of the disperse dyestuff was changed to 3.0% o.w.f.
in the dyeing condition.
[0127] In the obtained dyed fabric, the woven fabric density was 63
ends per inch and 55 picks per inch, the limiting oxygen index was
26.0, the dry rubbing fastness was grade 2-3 and the wet rubbing
fastness was grade 2-3, the afterflame time and afterglow time were
0 second, the initial water absorption performance was 1.0 seconds,
the water absorption performance after 10 washing cycles was 1.0
seconds, the residual disperse dyestuff in the polyester fiber was
0.05% o.w.f., and the residual cationic dyestuff in the meta-type
wholly aromatic polyamide fiber was 9.0% o.w.f. Evaluation results
are shown in Table 1.
Reference Example 1 (Ref. Ex. 1)
[0128] A dyed fabric was obtained as in Example 1 except that
although the dyeing with the dye solution for wholly aromatic
polyamide fiber was performed, the dyeing with the dye solution for
polyester fiber was not performed. The dyed fabric thus obtained
was evaluated for color uniformity. Evaluation result is shown in
Table 1.
Reference Example 2 (Ref. Ex. 2)
[0129] A dyed fabric was obtained as in Example 1 except that
although the dyeing with the dye solution for polyester fiber was
performed, the dyeing with the dye solution for wholly aromatic
polyamide fiber was not performed. The dyed fabric thus obtained
was evaluated for color uniformity. Evaluation result is shown in
Table 1.
Reference Example 3 (Ref. Ex. 3)
[0130] A dyed fabric was obtained as in Example 1 except that a
dyeing of a fabric was performed with a mixed dye solution
containing a cationic dyestuff and a disperse dyestuff, instead of
the dyeing with the dye solution for polyester fiber and the dyeing
with the dye solution for wholly aromatic polyamide fiber. The dyed
fabric thus obtained was evaluated for color uniformity. Evaluation
result is shown in Table 1.
TABLE-US-00001 TABLE 1 Example Example Example Example Example Ref.
Ref. Ref. 1 2 3 4 5 Ex. 1 Ex. 2 Ex. 3 Flame retardancy (LOI) 26 26
26 26 26 -- -- -- Fastness dry condition grade 4-5 4-5 4-5 4 2-3 --
-- -- wet condition grade 4-5 4-5 4-5 4 2-3 -- -- -- Flammability
afterflame time sec 0 0 0 0 0 -- -- -- afterglow time sec 0 0 0 0 0
-- -- -- Crystallinity % 25 25 25 25 25 -- -- -- Water absorption
Initial sec 1.0 1.0 1.0 10.0 1.0 -- -- -- performance after 10
washings sec 1.0 1.0 1.0 15.0 1.0 -- -- -- Residual dyestuff
disperse dyestuff % owf 0.03 0.02 0.02 0.06 0.05 -- -- -- cationic
dyestuff % owf 8.0 8.0 8.0 8.0 9.0 -- -- -- L value 25 27 26 28 27
-- -- -- Color uniformity Good Good Good Good Good Poor Poor
Moderate
Examples 6 to 10
[0131] The dyed fabrics according to Examples 6 to 10 were
manufactured and the evaluation was carried out for their
quality.
Example 6
[0132] In the spinning process, the following fibers were blended
at a weight ratio of 78:5:15:2 to obtain a single yarn having an
English cotton count of 40 and a twist count of 24 T/inch (twist
factor=3.4), as a spun yarn: [0133] a short fiber consisting of
polymetaphenylene isophthalamide fiber ("Teijinconex neo"
(trademark), manufactured by Teijin Limited) having a single fiber
fineness of 1.7 dtex, a cut length (fiber length) of 51 mm and a
LOI of 26; [0134] a short fiber consisting of polyparaphenylene
terephthalamide (PPTA) fiber ("Twaron" (trademark), manufactured by
Teijin Limited) having a single fiber fineness of 1.7 dtex and a
cut length (fiber length) of 51 mm and a limiting oxygen index
defined in E-2 of JIS1091:1999 of 25; [0135] a short fiber
consisting of a polyester fiber ("eco-PET (RA02)", manufactured by
Teijin Limited) having a single fiber fineness of 2.2 dtex and a
fiber length of 38 mm; [0136] a short fiber consisting of an
electrically-conductive fiber ("Corebrid ET10" (trademark),
manufactured by Mitsubishi Chemical Corporation) having a single
fiber fineness of 3.3 dtex and a cut length (fiber length) of 38
mm.
[0137] Two of the obtained spun yams were combined and twisted by
double twister at a second twist count of 20.9 T/inch, and then
subjected to twist-set by using a vacuum steam setting machine at a
setting temperature of 120.degree. C. for a setting time of 20
minutes, in order to obtain a flame retardant doubled and twisted
yarn.
[0138] Then, a weaving was performed with the obtained flame
retardant doubled and twisted yarn, in order to obtain a fabric
with a fabric density of 57 ends per inch and 53 picks per inch and
a fabric texture of 1/1 plain weave.
[0139] The woven fabric was subjected to singeing treatment,
scouring treatment, and setting treatment (temperature:160.degree.
C., time:30 seconds) in a conventional manner, and then dyed with a
dye solution for wholly aromatic polyamide fiber at a temperature
of 130.degree. C. for 60 minutes after raising the temperature from
the ambient temperature (bath ratio 1:20), wherein the dye solution
for wholly aromatic polyamide fiber contains 16% o.w.f. of a
cationic dyestuff (Basacryl Red GL, manufactured by BASF), 10 g/l
of a carrier agent, 3 g/l of acetic acid, 20 g/l of sodium nitrate,
and 1 g/l of a dispersant (Disper VG, manufactured by Meisei
Chemical Works, Ltd.).
[0140] After the dyeing described above, a dyeing was carried out
using a thermosol dyeing machine of a continuous device equipped
with a padder, a dryer, and a thermosol machine. In this dyeing
procedure, the fabric dyed with the cationic dyestuff was
impregnated into a dye solution for polyester fiber containing 0.2%
o.w.f. of a disperse dyestuff (Sumikaron Red S-3BFL, manufactured
by Sumika Chemtex Co., Ltd.), 3 g/l of sodium alginate (anti
migration agent), and 1 g/l of a dispersant (Disper VG,
manufactured by Meisei Chemical Works, Ltd.), and then squeezed
with a mangle at a squeezing ratio of 60% by mass, and then dried
at 130.degree. C. for 60 seconds, and subjected to a dry heat
treatment at 230.degree. C. for 3 minutes. Subsequently, an open
soaper was used to perform reduction cleaning, soaping, and
hot-water washing, and then drying was performed for a final set
(30 seconds at 160.degree. C.), in order to obtain a dyed
fabric.
[0141] The obtained fabric was treated with a sweat absorbing
processing agent for polyester and a sweat absorbing processing
agent for wholly aromatic polyamide fiber in a conventional
manner.
[0142] In the obtained dyed fabric, the woven fabric density was 63
ends per inch and 55 picks per inch, the dry rubbing fastness was
grade 3 and the wet rubbing fastness was grade 3, the afterflame
time and afterglow time were 0 second, the initial water absorption
performance was 1.0 seconds, the water absorption performance after
10 washing cycles was 1.0 seconds, the residual disperse dyestuff
in the polyester fiber was 0.1% o.w.f., and the residual cationic
dyestuff in the meta-type wholly aromatic polyamide fiber was 4.5%
o.w.f. Evaluation results are shown in Table 2.
[0143] The obtained dyed fabric was excellent in heat resistance
and flame resistance, and had particularly good color uniformity of
fibers, excellent appearance quality, and excellent fastness.
Example 7
[0144] The dyed fabric was manufactured as in Example 6 except
that, in the spinning step, coparaphenylene 3,4' oxydiphenylene
terephthalamide fiber ("Technora" (trademark), manufactured by
Teijin Limited) having a single fiber fineness of 1.7 dtex, a cut
length (fiber length) of 51 mm, and an LOI of 25, was used instead
of "Twaron" (Trademark) manufactured by Teijin Limited which is a
para-type wholly aromatic polyamide.
[0145] In the obtained dyed fabric, the woven fabric density was 63
ends per inch and 55 picks per inch, the limiting oxygen index was
26.0, the dry rubbing fastness was grade 3 and the wet rubbing
fastness was grade 3, the afterflame time and afterglow time were 0
second, the initial water absorption performance was 1.0 seconds,
the water absorption performance after 10 washing cycles was 1.0
seconds, the residual disperse dyestuff in the polyester fiber was
0.1% o.w.f., and the residual cationic dyestuff in the meta-type
wholly aromatic polyamide fiber was 4.5% o.w.f. Evaluation results
are shown in Table 2.
[0146] The obtained dyed fabric was excellent in heat resistance
and flame resistance, and had particularly good color uniformity of
fibers, excellent appearance quality, and excellent fastness.
Example 8
[0147] The dyed fabric was manufactured as in Example 6 except that
in the spinning process, an electrically-conductive fiber
("Corebrid ET10" (trademark) manufactured by Mitsubishi Chemical
Corporation) having a single fiber fineness of 3.3 dtex and a cut
length (fiber length) of 38 mm was not used, and a weight ratio of
fibers was changed to 80:5:15
[0148] In the obtained dyed fabric, the woven fabric density was 63
ends per inch and 55 picks per inch, the limiting oxygen index was
26.0, the dry rubbing fastness was grade 3 and the wet rubbing
fastness was grade 3, the afterflame time and afterglow time were 0
second, the initial water absorption was 1.0 seconds, the water
absorption performance after 10 washing cycles was 1.0 seconds, the
residual disperse dyestuff in the polyester fiber was 0.1% o.w.f.,
and the residual cationic dyestuff in the meta-type wholly aromatic
polyamide fiber was 4.6% o.w.f. Evaluation results are shown in
Table 2.
[0149] The obtained dyed fabric was excellent in heat resistance
and flame resistance, and had particularly good color uniformity of
fibers, excellent appearance quality, and excellent fastness.
Example 9
[0150] The dyed fabric was manufactured as in Example 6 except that
a sweat absorbing processing agent for polyester was not used in
the disperse dyeing condition.
[0151] In the obtained dyed fabric, the woven fabric density was 63
ends per inch and 55 picks per inch, the limiting oxygen index was
26.0, the dry rubbing fastness was grade 3, the wet rubbing
fastness was grade 3, the afterflame time and afterglow time were 0
second, the initial water absorption was 10.0 seconds, the water
absorption performance after 10 washing cycles was 15.0 seconds,
the residual disperse dyestuff in the polyester fiber was 0.18%
o.w.f., and the residual cationic dyestuff in the meta-type wholly
aromatic polyamide fiber was 4.6% o.w.f. Evaluation results are
shown in Table 2.
[0152] The obtained dyed fabric was excellent in heat resistance
and flame resistance, and had particularly good color uniformity of
fibers, excellent appearance quality, and excellent fastness.
Example 10
[0153] The dyed fabric was manufactured as in Example 6 except that
the concentration of the disperse dyestuff was changed to 3.0%
o.w.f. in the dyeing condition. In the obtained dyed fabric, the
woven fabric density was 63 ends per inch and 55 picks per inch,
the limiting oxygen index was 26.0, the dry rubbing fastness was
grade 2 and the wet rubbing fastness was grade 2, the afterflame
time and afterglow time were 0 second, the initial water absorption
performance was 1.0 seconds, the water absorption performance after
10 washing cycles was 1.0 seconds, the residual disperse dyestuff
in the polyester fiber was 2.5% o.w.f, and the residual cationic
dyestuff in the meta-type wholly aromatic polyamide fiber was 4.5%
o.w.f. Evaluation results are shown in Table 2.
TABLE-US-00002 TABLE 2 Example Example Example Example Example 6 7
8 9 10 Flame retardancy (LOI) 26 26 26 26 26 Fastness dry condition
grade 3 3 3 3 2 wet condition grade 3 3 3 3 2 Flammability
afterflame time sec 0 0 0 0 0 afterglow time sec 0 0 0 0 0
Crystallinity % 25 25 25 25 25 Water absorption Initial sec 1.0 1.0
1.0 10.0 1.0 performance after 10 washings sec 1.0 1.0 1.0 15.0 1.0
Residual dyestuff disperse dyestuff % owf 0.1 0.1 0.1 0.18 2.5
cationic dyestuff % owf 4.5 4.5 4.5 4.6 4.5 L value 25 27 26 28 27
Color uniformity Very Very Very Very Very Good Good Good Good
Good
* * * * *