DESCRIPTION
TITLE OF THE INVENTION:
COLORED ORGANIC FIBER, CLOTH, AND GARMENTS, AND METHOD FOR
PRODUCING CLOTH
TECHNICAL FIELD
[0001)
The present invention relates to a colored organic fiber
that has a deep color and excellent flame retardancy, a cloth
and garments each composed of the foregoing organic fiber, and
a method for producing a cloth.
BACKGROUND ART
[0002)
As a method of coloring a flame-retardant cloth
containing an organic fiber, such as a meta-type aromatic
polyamide fiber, etc., there have hitherto been knmm a method
of containing a pigment in an organic fiber and a method of
dyeing a cloth with a carrier agent.
[0003)
However, according to the method of containing a pigment
in an organic fiber, it Has difficult to obtain a cloth having
excellent hyperchromicity. Meam1hile, according to the
method of dyeing a cloth with a carrier agent, it could not
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be said that the resulting cloth is sufficient in terms of
flame retardancy.
[0004]
In order to solve those problems, for example, PTLs l
to 3 propose use of a core-sheath structure yarn. However,
the use of a core-sheath structure yarn involved such a problem
that a lot of time and costs are spent; and a problem that since
it is necessary to use a usual synthetic fiber that is poor
in flame retardancy for a sheath yarn, the resulting cloth is
insufficient in terms of flame retardancy. In addition, for
example, PTL 4 proposes that a cloth is dyed with a carrier
agent and then washed. H01vever, it could not be said that the
resulting cloth is sufficient in terms of flame retardancy.
CITATION LIST
PATENT LITERATURE
[ 0005]
PTL 1: JP-A-2009-249758
PTL 2: JP-A-2009-209488
PTL 3: JP-A-2003-147651
PTL 4: JP-A-2012-207348
SUMMARY OF INVENTION
TECHNICAL PROBLEM
[0006]
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In view of the foregoing background, the present
invention has been made, and an object thereof is to provide
a colored organic fiber that has a deep color and excellent
flame retardancy, a cloth and garments each composed of the
foregoing organic fiber, and a method for producing a cloth.
SOLUTION TO PROBLEM
[0007]
In order to solve the foregoing problems, the present
inventors made extensive and intensive investigations. As a
result, they have found that in an organic fiber dyed with a
carrier agent, by reducing the amount of the carrier agent
remaining in the organic fiber, an organic fiber that has a
deep color and excellent flame retardancy is obtained and
further made extensive and intensive investigations, leading
to accomplishment of the present invention.
[0008]
Thus, the present invention provides a "colored organic
fiber having a content of a carrier agent of 1.8% by mass or
less relative to the fiber mass".
[0009]
On that occasion, it is preferred that the content of
the carrier agent is 0. 1 to 1. 8% by mass relative to the fiber
mass. It is preferred that the carrier agent is any one or
more selected from the group consisting of
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DL-~-ethy1phenethyl 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. It is
preferred that the organic fiber is any one selected from the
group consisting of a meta-type wholly aromatic polyamide
fiber, a para-type wholly aromatic polyamide fiber, a
polybenzoxazole ( PBO) fiber, a polybenzimidazole (PBI) fiber,
a polybenzthiazole (PBTZ) fiber, a polyimide (PI) fiber, a
polysulfonamide (PSA) fiber, a polyetheretherketone (PEEK)
fiber, a polyether imide (PEI) fiber, a polyarylate (PAr)
fiber, a melamine fiber, a phenol fiber, a fluorine-based
fiber, and a polyphenylene sulfide (PPS) fiber.
[0010]
It is preferred that the organic fiber is a meta-type
wholly aromatic polyamide fiber having a crystallinity of 15
to 25%. It is preferred that the organic fiber is a meta-type
wholly aromatic polyamide fiber having a content of residual
solvent of 1.0% by mass or less. It is preferred that the
organic fiber is a meta-type wholly aromatic polyamide fiber
having a content of residual solvent of 0.1% by mass or less.
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On that occasion, it is preferred that the residual solvent
is any one selected from the group consisting of
N,N-dimethylformamide, N,N-dimethylacetamide,
N-methyl-2-pyrrolidone, and dimethyl sulfoxide.
[0011]
It is preferred that the organic fiber is a meta-type
wholly aromatic polyamide fiber; and that a meta-type wholly
aromatic polyamide forming the meta-type wholly aromatic
polyamide fiber is an aromatic polyamide in Hhich in an
aromatic polyamide skeleton containing a repeating structural
unit represented by the folloHing formula (1), an aromatic
diamine component or aromatic dicarboxylic acid halide
component that is different from a main structural unit of the
repeating structure is copolymerized as a third component such
that a proportion of the third component is 1 to 10 mol%
relative to the Hhole amount of the repeating structural units
of the aromatic polyamide.
[0012]
-(NH-Ar1-NH-CO-Ar1-CO)- (1)
Here, Ar 1 is a divalent aromatic group having a linking
group in a position other than the meta position or an axially
parallel direction.
[0013]
On that occasion, it is preferred that the third
component is an aromatic diamine represented by the folloHing
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formula (2) or (3), or an aromatic dicarboxylic acid halide
represented by the folloHing formula (4) or (5).
[0014]
H2N-Ar2-Y-Ar2-NH2 • . . (3)
XOC-Ar3-COX ... (4)
XOC-Ar3-Y-Ar3-COX ... (5)
Here, Ar2 is a divalent aromatic group different from
Arl; Ar3 is a divalent aromatic group different from Arl; Y
is at least one atom or functional group selected from the
group consisting of an oxygen atom, a sulfur atom, and an
alkylene group; and X is a halogen atom.
[ 0015]
In addition, the present invention provides a cloth
containing the above-described colored organic fiber. On that
occasion, it is preferred that the cloth contains any one or
more selected from the group consisting of a polyester fiber,
a cellulose fiber, a polyamide fiber, a polyolefin fiber, an
acrylic fiber, a rayon fiber, a cotton fiber, an animal hair
fiber, a polyurethane fiber, a polyvinyl chloride fiber, a
polyvinylidene chloride fiber, an acetate fiber, and a
polycarbonate fiber. It is preferred that any one of fibers
constituting the cloth contains a flame retarder. It is
preferred that any one of fibers constituting the cloth
contains a UV absorber or a UV reflector. It is preferred that
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an areal 1·1eight of the cloth is 300 g/m2 or less. It is
preferred that an LOI is 26 or more. It is preferred that an
afterflame time in the vertical flame test (JIS L1091A-4:
three second flame contact) is 1 second or less. It is
preferred that a brightness index L value is 80 or less.
[0016]
In addition, the present invention provides garments
composed of the above-described cloth.
[0017]
In addition, the present invention provides a method for
producing a cloth containing the above-described colored
organic fiber, including dyeing a cloth containing an organic
fiber 1vith a carrier agent and then 1vashing the cloth 1vith hot
1vater at a temperature of 90 to 140°C for 10 to 30 minutes,
thereby controlling a content of the carrier agent contained
in the organic fiber to 1.8% by mass or less relative to the
fiber mass.
ADVANTAGEOUS EFFECTS OF INVENTION
[0018]
In accordance with the present invention, a colored
organic fiber that has a deep color and excellent flame
retardancy, a cloth and garments each composed of the
foregoing organic fiber, and a method for producing a cloth
are obtained.
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DESCRIPTION OF EMBODIMENTS
[0019]
Embodiments of the present invention are hereunder
described in detail. First of all, a colored organic fiber
is subject to the present invention. In such an organic fiber,
a content of a carrier agent is 1.8% by mass or less relative
to the fiber mass.
[0020]
Here, the carrier agent is a dyeing auxiliary and is also
named a "s1velling agent". The kind of such a carrier agent
is not particularly limited. Specifically, examples thereof
include L-P-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, N-methylformanilide, and the
like.
[0021]
In the colored organic fiber of the present invention,
the kind of the organic fiber is not particularly limited.
HOivever, in obtaining excellent flame retardancy, a meta-type
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\'/holly aromatic polyamide fiber, a para-type \'/holly aromatic
polyamide fiber, a polybenzoxazole (PBO) fiber, a
polybenzimidazole ( PBI) fiber, a polybenzthiazole ( PBTZ)
fiber, a polyimide (PI) fiber, a polysulfonamide (PSA) fiber,
a polyetheretherketone (PEEK) fiber, a polyether imide (PEI)
fiber, a polyarylate (PAr) fiber, a melamine fiber, a phenol
fiber, a fluorine-based fiber, a polyphenylene sulfide (PPS)
fiber, and the like are preferred.
[0022]
Of those, a meta-type wholly aromatic polyamide fiber
is preferred. The meta-type lvholly aromatic polyamide fiber
is a fiber composed of a polymer in which 85 mol% or more of
repeating units thereof is m-phenyleneisophthalamide. Such
a meta-type wholly aromatic polyamide may be a copolymer
containing a third component IYithin a range of less than 15
mol%.
[0023]
Such a meta-type wholly aromatic polyamide fiber can be
produced by a conventionally kn01m interfacial polymerization
method. As for a polymerization degree thereof, it is
preferred to use one having an intrinsic viscosity (I.V.)
1·1ithin a range of 1.3 to 1.9 dL/g, as measured with an
N-methyl-2-pyrrolidone solution having a concentration of 0. 5
g/100 mL.
[0024]
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The meta-type Hholly aromatic polyamide may contain an
alkylbenzenesulfonic acid onium salt. Preferred examples of
the alkylbenzenesulfonic acid onium salt include compounds,
such as a hexylbenzenesulfonic acid tetrabutylphosphonium
salt, a hexylbenzenesulfonic acid tributylbenzylphosphonium
salt, a dodecylbenzenesulfonic acid tetraphenylphosphonium
salt, a dodecylbenzenesulfonic acid
tributyltetradecylphosphonium salt, a
dodecylbenzenesulfonic acid tetrabutylphosphonium salt, a
dodecylbenzenesulfonic acid tributylbenzylammonium salt, etc.
Of those, a dodecylbenzenesulfonic acid
tetrabutylphosphonium salt and a dodecylbenzenesulfonic acid
tributylbenzylammonium salt are especially preferably
exemplified because they are easily available, have good
thermal stability, and also have a high solubility in
N-methyl-2-pyrrolidone.
[0025]
In order to obtain a sufficient dye-affinity-improving
effect, a content proportion of the alkylbenzenesulfonic acid
onium salt is 1vithin a range of preferably 2. 5 mol% or more,
and more preferably 3.0 to 7.0 mol% relative to
poly-m-phenyleneisophthalamide.
[0026]
As a method of mixing poly-m-phenyleneisophthalamide
and an alkylbenzenesulfonic acid onium salt, a method in which
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po1y-m-pheny1eneisophthalamide is mixed and dissolved in a
solvent, and an alkylbenzenesulfonic acid onium salt is then
dissolved in the solvent, and other methods may be adopted.
The thus obtained dope is formed to a fiber by a conventionally
known method.
[0027]
For the purpose of improving dyeing affinity and
discoloration/fading resistance, the polymer that is used for
the meta-type wholly aromatic polyamide fiber may also be
obtained by copolymerizing, in an aromatic polyamide skeleton
containing a repeating structural unit represented by the
follmving formula ( 2) , an aromatic diamine component or
aromatic dicarboxylic acid halide component that is different
from a main structural unit of the repeating structure as a
third component such that a proportion of the third component
is 1 to 10 mol% relative to the whole amount of the repeating
structural units of the aromatic polyamide.
[0028]
-(NH-Arl-NH-CO-Arl-CO)- (1)
Here, Ar 1 is a divalent aromatic group having a linking
group in a position other than the meta position or an axially
parallel direction.
[0029]
Specific examples of aromatic diamines represented by
the formulae (2) and (3) copolymerizable as the third
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component include p-phenylenediamine,
chlorophenylenediamine, methylphenylenediamine,
acetylphenylenediamine, aminoanisidine, benzidine,
bis(aminophenyl)ether, bis(aminophenyl)sulfone,
diaminobenzanilide, diaminoazobenzene, and the like.
Specific examples of aromatic dicarboxylic acid dichlorides
represented by the formulae ( 4) and ( 5) include terephthaloyl
chloride, 1,4-naphthalenedicarbonyl chloride,
2,6-naphthalenedicarbonyl chloride, 4,4'-biphenyldicarbonyl
chloride, 5-chloroisophthaloyl chloride,
5-methoxyisophthaloyl chloride,
bis(chlorocarbonylphenyl)ether, and the like.
[0030)
H2N-Ar2-NH2 ( 2)
H2N-Ar2-Y-Ar2-NH2 ••• (3)
XOC-Ar3-COX ... (4)
XOC-Ar3-Y-Ar3-COX ... (5)
Here, Ar2 is a divalent aromatic group different from
Arl; Ar3 is a divalent aromatic group different from Arl; Y
is at least one atom or functional group selected from the
group consisting of an oxygen atom, a sulfur atom, and an
alkylene group; and X is a halogen atom.
[0031)
In addition, from the standpoints that dye exhaustion
properties are good, and even \•/hen dying is performed with a
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small amount of dye or under 1veak dyeing conditions, the color
can be easily adjusted as intended, it is preferred that a
crystallinity of the meta-type wholly aromatic polyamide
fiber is 5 to 35%. Furthermore, from the standpoints that the
dye is less likely to be unevenly distributed on the surface,
the discoloration/fading resistance is high, and the
practically necessary dimensional stability can be ensured,
the crystallinity of the meta-type 1·1holly aromatic polyamide
fiber is more preferably 15 to 25%.
[0032]
In addition, from the standpoint that the excellent
flame retardancy of the meta-type wholly aromatic polyamide
fiber is not impaired; and from the standpoint that the dye
is less likely to be unevenly distributed on the surface, and
the discoloration/fading resistance is high, a content of
residual solvent of the meta-type wholly aromatic polyamide
fiber is preferably 1. 0% by mass or less (more preferably 0.1%
by mass or less, and still more preferably 0.01 to 0.09% by
mass).
[ 0033]
The meta-type aromatic polyamide fiber can be produced
by the following method. In particular, by a method as
described later, the crystallinity and the content of residual
solvent can be made within the above-described ranges.
[0034]
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The polymerization method of the meta-type aromatic
polyamide polymer is not particularly limited. For example,
the solution polymerization method or interfacial
polymerization method described in JP-B-35-14399, U.S. Patent
No. 3,360,595, JP-B-47-10863, and the like may be adopted.
[0035]
A spinning solution is not particularly limited. An
amide-based solvent solution containing an aromatic
copolyamide polymer obtained by the above-described solution
polymerization or interfacial polymerization, or the like may
be used, or a spinning solution obtained by isolating the
foregoing polymer from the above-described polymerization
solution and dissolving it in an amide-based solvent may be
used.
[0036]
Here, examples of the amide-based solvent may include
N,N-dimethylformamide, N,N-dimethylacetamide,
N-methyl-2-pyrrolidone, dimethyl sulfoxide, and the like,
with N,N-dimethylacetamide being especially preferred.
[0037]
When the resulting copolymerized aromatic polyamide
polymer solution further contains an alkali metal salt or an
alkaline earth metal salt, the solution becomes more stable
and can be used in a higher concentration and at a lower
temperature, and hence, such is preferred. A proportion of
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the alkali metal salt or alkaline earth metal salt is
preferably 1% by mass or less, and more preferably 0.1% by mass
or less relative to the whole weight of the polymer solution.
[ 0038]
In a spinning/coagulation step, the resulting spinning
solution (meta-type 1·1holly aromatic polyamide polymer
solution) is spun into a coagulation liquid and coagulated.
[0039]
A spinning apparatus is not particularly limited, and
a conventionally knm-m wet-spinning apparatus can be used.
The number of spinning holes of a spinneret and an arrangement
state thereof, a hole shape, and the like are not particularly
limited. For example, a multi-hole spinneret for staple
fibers, having a number of holes of 1,000 to 30,000 and a
spinning hole diameter of 0. 05 to 0. 2 mm, and the like may be
used.
[0040]
In addition, it is preferred that a temperature of the
spinning solution (meta-type wholly aromatic polyamide
polymer solution) upon spinning from the spinneret is within
a range of 20 to 90°C.
[0041]
As a coagulation bath that is used in order to obtain
a fiber, it is preferred to use an aqueous solution containing
substantially no inorganic salt and having a concentration of
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an amide-based solvent (preferably NMP) of 45 to 60% by mass
at a temperature of the bath liquid 1·1ithin a range of 10 to
50°C. When the concentration of the amide-based solvent
(preferably NMP) is less than 45% by mass, the structure of
a skin becomes thick. As a result, there is a concern that
the washing efficiency in a washing step decreases, so that
it becomes difficult to reduce the content of residual solvent
of the fiber. On the other hand, in the case where the
concentration of the amide-based solvent (preferably NMP) is
more than 60% by mass, there is also a concern that uniform
coagulation inside the fiber cannot be achieved, so that it
becomes difficult to reduce the content of residual solvent
of the fiber. It is preferred that a time of immersion of the
fiber in the coagulation bath is within a range of 0.1 to 30
seconds.
[0042]
Subsequently, it is preferred to dra1v the fiber in a dra1v
ratio of 3 to 4 in a plastic drawing bath that is an aqueous
solution of an amide-based solvent, preferably NMP in a
concentration of 45 to 60% by mass at a bath liquid temperature
within a range of 10 to 50°C. After drawing, it is preferred
to thoroughly wash the fiber with an aqueous solution of NMP
at 10 to 30°C in a concentration of 20 to 40% by mass, followed
by passing through a warm 1vater bath at 50 to 70°C.
[ 00 4 3]
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The fiber after washing is subjected to a dry heat
treatment at a temperature of 270 to 290°C, whereby a meta-type
wholly aromatic aramid fiber that satisfies the
above-described ranges of the crystallinity and content of
residual solvent can be obtained.
[0044)
In the colored organic fiber of the present invention,
the fiber may be either a long fiber (multifilament) or a short
fiber. In particular, a short fiber having a fiber length of
25 to 200 mm is preferred in blend-spinning 11ith other fibers.
A single fiber fineness of the organic fiber is preferably
within a range of 1 to 5 dtex.
[0045)
In the colored organic fiber of the present invention,
a dyeing method using a carrier agent is preferred as the
coloring method. In particular, a method of achieving dyeing
11i th a cationic dye is preferred in obtaining excellent
hyperchromicity. Conditions of the dyeing step are not
particularly limited.
[0046)
In such a colored organic fiber, it is important that
a content of the carrier agent is 1. 8% by mass or less
(preferably 0.1 to 1.8% by mass, more preferably 0.1 to 1.0%
by mass, and still more preferably 0. 3 to 0. 9% by mass)
relative to the fiber mass. When the content is more than 1.8%
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by mass, there is a concern that the flame retardancy is
impaired. Conversely, when the content is less than 0.1% by
weight, there is a concern that the excellent hyperchromicity
is not obtained, or a hot water washing step as described later
becomes complicated.
[0047]
As a method of lowering the content of the carrier agent,
for example, there is exemplified a method in \·lhich the dyed
cloth is subjected to reduction \·lashing, if desired and then
subjected to hot water washing Hith hot Hater at a temperature
of 90 to 140°C (more preferably 110 to 140°C) for 10 to 30
minutes.
[0048]
Next, the cloth of the present invention is a cloth
containing the above-described colored organic fiber. Though
such a cloth is composed of only the above-described colored
organic fiber, it may further contain other fibers, such as
a polyester fiber, a cellulose fiber, a polyamide fiber, a
polyolefin fiber, an acrylic fiber, a rayon fiber, a cotton
fiber, an animal hair fiber, a polyurethane fiber, a polyvinyl
chloride fiber, a polyvinylidene chloride fiber, an acetate
fiber, a polycarbonate fiber, etc.
[0049]
On that occasion, \·/hen a proportion of the meta-type
wholly aromatic polyamide fiber contained in the cloth is 50%
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by mass or more relative to the cloth mass, the excellent flame
retardancy is obtained, and hence, such is preferred. The
above-described flame-retardant fiber, synthetic fiber,
regenerated fiber, or natural fiber can be arbitrarily mixed
according to an application or needs of use. As a more specific
example, a mixed fiber in a mixing ratio of 50 to 98% by mass
of a meta-type wholly aromatic polyamide resin, 2 to 50% by
mass of a polyester fiber, and 0 to 50% by mass of a
cellulose-based fiber can be made to have both dye affinity
and comfortableness. The proportions may be adjusted
according to the performance to be emphasized.
[ 0050 l
It is also preferred that any one of fibers constituting
the cloth contains a flame retarder, or a UV absorber or a UV
reflector. On that occasion, in the UV absorber, its
solubility in water is preferably 0. 04 mg/L or less. When the
solubility in 1·1ater is more than 0. 04 mg/L, in dyeing 11i th the
carrier agent, there is also a concern that the UV absorber
elutes, so that light fastness after dyeing decreases.
[0051)
A method for producing the above-described cloth is not
particularly limited. For example, there may be adopted a
method in which a spun yarn is obtained using the
above-described organic fiber (or the above-described organic
fiber and other fibers), woven or knitted as a single yarn or
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a 2-p1y yarn, and then dyed with a carrier agent, followed by
hot water washing by the above-described method.
[0052]
On that occasion, as for a structure of the cloth, woven
fabric structures, such as a plain weave, a twill weave, a
satin weave, a double weave, etc., are preferred, and a knit
or a nonwoven fabric may also be adopted. The production
method of a cloth is not particularly limited. For example,
a knmm knit-weaving loom, such as a rapier loom, a gripper
loom, etc., can be used.
[0053]
The resulting cloth uses the above-described organic
fiber, and therefore, it is excellent in hyperchromicity and
flame retardancy. On that occasion, the hyperchromicity is
preferably 80 or less (more preferably 52.5 or less, and still
more preferably 10 to 52.3) in terms of a brightness index L
value. The flame retardancy is preferably 26 or more (more
preferably 26 to 40) in terms of LOI. In the vertical flame
test (JIS L1091A-4: three second flame contact), an afterflame
time of the cloth is preferably 25 seconds or less (more
preferably 1 second or less).
[0054]
In the above-described cloth, its areal weight is
preferably 300 g/m2 or less (more preferably 50 to 250 g/m2
) .
When the areal weight is more than 300 g/m2
, there is a concern
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that light1veight properties of the cloth are impaired.
[ 0055]
Next, the garments of the present invention are garments
composed of the above-described cloth. Examples of such
garments include protective clothes, firefighter clothes,
fireproof clothes, rescue clothes, activities clothes, office
clothes, racing suits for motor sports, work clothes, gloves,
hats, bests, and the like. In addition, the above-described
work clothes include work clothes for activities in a steel
plant or steel factory, work clothes for Helding, work clothes
in an explosion-proof area, and the like. In addition, the
above-described gloves include Hork gloves used in the
aircraft industry, the information equipment industry, the
precision machinery industry, and the like 1·1here precision
components are treated.
[0056]
In addition, the above-described cloth may also be used
for fiber products, such as a curtain, a car sheet, a bag, etc.
EXAMPLES
[0057]
The present invention is hereunder described in detail
with reference to Examples, but it should be construed that
the present invention is not limited by these Examples at all.
In addition, various physical properties in the Examples are
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those measured by the foll01ving methods.
(1) Flame Retardancy of Cloth (Vertical Flame Test)
An afterflame time (sec) 1·1as evaluated on the basis of
JIS L1091A-4 (three second flame contact) .
(2) Content of Residual Solvent
About 8. 0 g of a fiber was collected, dried at 105°C for
120 minutes, and then allowed to stand for cooling within a
desiccator, and a fiber mass (M1) 11as 1veighed. Subsequently,
this fiber was subjected to reflux extraction in methanol for
1.5 hours using a Soxhlet extractor, thereby extracting an
amide-based sol vent contained in the fiber. After completion
of the extraction, the fiber was taken out, vacuum-dried at
150°C for 60 minutes, and then allowed to stand for cooling
1vithin a desiccator, and a fiber mass (M2) was weighed. Using
the obtained M1 and M2, a content of the solvent remaining in
the fiber (amide-based solvent mass) 1vas calculated according
to the following equation.
Content of residual solvent(%)= [(M1 - M2)/M1] x 100
(3) Crystallinity
Using an X-ray diffraction apparatus (RINT TTRIII,
manufactured by Rigaku Corporation), raw fibers were bundled
into a fiber bundle of about 1 mm in diameter and mounted on
a fiber sample table to measure a diffraction profile. The
measurement conditions were as follows: Cu-Ka radiation
source (50 kV, 300 rnA), scanning angle range: 10 to 35°,
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continuous measurement, measurement width: 0.1°, scanning at
1° /min. From the measured diffraction profile, air scattering
and incoherent scattering were corrected by linear
approximation to obtain a total scattering profile.
Subsequently, an amorphous scattering profile was subtracted
from the total scattering profile to obtain a crystal
scattering profile. A crystallinity was determined from an
integrated intensity of the crystal scattering profile
(crystal scattering intensity) and an integrated intensity of
the total scattering profile (total scattering intensity)
according to the following equation.
Crystallinity(%)= [(Crystal scattering intensity)/{Total scattering intensity)] x 100
(4) Content of Residual Carrier Agent
Measurement method:
A GC/MS sample made of a fiber sample was charged in a
sample tube and measured by ATD. After confirming a carrier
agent by a qualitative analysis, a quantitative analysis was
performed under the foll01ving conditions.
Calibration curve:
DOWANOL PPH 10. 180 mg/mL (n-hexane) , 0. 50, ·0. 7 5, ·1. 00 IlL
Column: DB-Sms 0.25 mm x 28 m
Carrier: He
Inject:ATD 350°C x 20 min (sample heating), 300°C x 10
min (ejection)
ColdTrap: 10°C
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Interface·val ve·transfer: 250°C Mass Range 94 108 152
Detector: GCMS-QP2010
Ion source: 200°C
Voltage: 1.35 kV (-0.48kV)
Oven: ll0°C x 2 min, 110 to 190°C (l0°C/min)
Gas flow rate: Primary= 10/90, secondary= 1/42.0%
(5) Hyperchromicity (L value)
The color measurement was performed using a MacBeth
spectrophotometer, Color-Eye 3100.
(6) Areal Weight
An areal weight (g/m2
) was measured in conformity 1vith
JIS L1096.
[0058]
[Example 1]
A meta-type wholly aromatic aramid fiber was prepared
by the following method.
[0059]
20. 0 parts by mass of a poly-m-phenyleneisophthalamide
pmvder having an intrinsic viscosity (I. V.) of 1. 9 as produced
by interfacial polymerization in accordance with the method
described in JP-B-47-10863 was suspended in 80.0 parts by mass
of N-methyl-2-pyrrolidone (NMP) cooled to -l0°C, thereby
forming a slurry. Subsequently, the suspension liquid was
heated for dissolution to 60°C, thereby obtaining a
transparent polymer solution. A UV absorber made of a
24
P160607WO
2-[2H-benzotriazo1-2-yl]-4-6-bis(1-methyl-1-phenylethyl)ph
enol pm1der (solubility in water: 0. 01 mg/L) in an amount of
3. 0% by mass relative to the polymer 1vas mixed loJi th and
dissolved in the polymer solution, and the mixture was
defoamed under reduced pressure to prepare a spinning solution
(spinning dope) .
[Spinning/Coagulation Step]
The spinning dope 1·1as discharged and spun from a
spinneret having a hole diameter of 0.07 mm and a number of
holes of 500 into a coagulation bath at a bath temperature of
30°C. A composition of the coagulation liquid 1•1as water/NMP
~ 45/55 (parts by mass). The spinning dope was discharged and
spun into the coagulation bath at a yarn speed of 7 m/min.
[Plastic-DraloJing-Bath Drawing Step]
Subsequently, dra1ving was performed to a dral'l ratio of
3. 7 in a plastic drawing bath at a temperature of 40°C having
a composition of water/NMP ~ 45/55.
[Washing Step]
After dra1ving, washing was performed in a bath of
water/NMP ~ 70/30 at 20°C (immersion length: 1. 8 m) and then
in a 1vater bath at 20°C (immersion length: 3. 6 m), and further
thoroughly \'lashed through a hot \'later bath at 60°C (immersion
length: 5.4 m).
[Dry Heat Treatment Step]
The fiber after washing \'las subjected to a dry heat
25
Pl60607WO
treatment using a hot roller having a surface temperature of
280"C, thereby obtaining a meta-type wholly aromatic aramid
fiber.
[Cutting Step]
The meta-type wholly aromatic aramid fiber was crimped
and cut into staple fibers having a length of 51 mm (ra1v stock) .
[Physical Properties of Raw Stock]
The resulting meta-type wholly aromatic aramid fiber
had the following properties: single fiber fineness: 1. 7 dtex,
content of residual sol vent: 0. 08% by mass, and crystallinity:
19%.
[0060]
Meanwhile, as other fiber raw stocks, a para-type aramid
fiber: "TWARON (registered trademark)", manufactured by
Teij in Aramid and a conductive yarn (nylon) : "NO SHOCK
(registered trademark)", manufactured by Solutia Inc. (nylon
conductive yarn having conductive carbon fine particles
kneaded thereinto) were prepared.
[0061]
Subsequently, respective staple fibers of a meta-type
wholly aromatic aramid fiber (MA) (length: 51 mm), a para-type
wholly aromatic polyamide ( PA) (length: 50 mm) , and a nylon
conductive yarn (AS) (length: 51 mm) were blend-spun in a ratio
of MA/PA/AS of 93/5/2 into a spun yarn (40 count, 2-ply yarn),
and woven at a 1-1eaving density of warp: 65 yarns/25. 4 mm and
26
Pl60607WO
\oJeft: 55 yarns/25. 4 mm, thereby giving a plain-woven fabric
having an areal \·Ieight of 170 g/m2
•
[0062)
Subsequently, the cloth was treated \oJi th a dyeing
prescription and a hot water washing prescription.
(Dyeing Prescription)
First of all, the cloth was dyed with the following
dyeing prescription.
· Cationic dye: Trade name: Kayacryl Red GL-ED, manufactured
by Nippon Kayaku Co., Ltd., 6. 0% moJf
· Carrier agent: Propylene glycol phenyl ether (DOWANOL PPH,
manufactured by The Dow Chemical Company), 40 g/L
The term "40 g/L" means "40 g is contained based on one
liter of \•later".
Acetic acid: 0.3 cc/L
Dispersant: 0.5 cc/L
Sodium nitrate: 25 g/L
Bath ratio: 1/20
Temperature x time: 135°C x 60 min
Subsequently, the resulting colored cloth \vas washed in
the following reduction bath.
Bath ratio: 1/20
Temperature x time: 90°C x 20 min
Reduction bath: Hydrosulfite, lg/L, soda ash, 1 g/L
(Hot Water Washing Prescription)
27
P160607WO
Subsequently, the cloth was subjected to hot water
washing 1·li th hot 1vater at a temperature of 130°C for 20 minutes.
Subsequently, the cloth was subjected to dry heat setting at
a temperature of 180°C for 2 minutes.
[0063]
The evaluation results of the resulting cloth are shown
in Table 1.
[0064]
[Example 2]
The same operation as in Example 1 \vas performed, except
that the one-time hot water washing prescription treatment of
130°C x 20 min was changed to a tlvo-time treatment of 130°C x
20 min. The evaluation results are shown in Table 1.
[0065]
[Example 3]
The same operation as in Example 1 ~1as performed, except
that the one-time hot Hater washing prescription treatment of
130°C x 20 min \vas changed to a two-time treatment of 120°C x
20 min. The evaluation results are shown in Table 1.
[ 0066]
[Example 4]
The same operation as in Example 1 \vas performed, except
that 40 g/L of DOWANOL PPH in the dyeing prescription was
changed to 60 g/L of benzyl alcohol. The evaluation results
are shown in Table 1.
28
"l
Pl60607WO
[ 0 0 67]
[Example 5]
The same operation as in Example 1 was performed, except
that 40 g/L of DOWANOL PPH in the dyeing prescription \vas
changed to 60 g/L of benzyl alcohol, and that the hot water
washing prescription treatment of 130°C x 20 min was changed
to a two-time treatment of 120°C x 20 min. The evaluation
results are shown in Table 1.
[0068]
[Example 6]
The same operation as in Example 1 was performed, except
that 40 g/L of DOWANOL PPH in the dyeing prescription 1-1as
changed to 60 g/L of benzyl alcohol, and that the hot 1-1ater
\-lashing prescription treatment of 130°C x 20 min was changed
to a t1w-time treatment of 120°C x 20 min. The evaluation
results are shown in Table 1.
[0069]
[Example 7]
The same operation as in Example 1 1·1as performed, except
that 40 g/L of DOWANOL PPH in the dyeing prescription was
changed to 60 g/L of benzyl alcohol, and that the hot water
1·1ashing prescription treatment of 130°C x 20 min was changed
to a two-time treatment of 120°C x 20 min. The evaluation
results are shown in Table 1.
[0070]
29
Pl60607WO
[Comparative Example 1]
The same operation as in Example 1 was performed, except
that the hot water washing prescription treatment of 130°C x
20 min was changed to a one-time treatment of 90°C x 20 min.
The evaluation results are shown in Table 1.
[0071]
[Example 8]
The same operation as in Example 1 was performed, except
that the hot water \vashing prescription treatment of 130°C x
20 min vias changed to a five-time treatment of 90°C x 20 min.
The evaluation results are shown in Table 1.
[0072]
[Example 9]
The same operation as in Example 1 was performed, except
that the hot water v1ashing prescription treatment of 130°C x
20 min was changed to a ten-time treatment of 90°C x 20 min.
The results are shown in Table 1.
[0073]
[Example 10]
The same operation as in Example 1 was performed, except
that the amount of DOWANOL PPH in the dyeing prescription was
changed to 30 g/L. The evaluation results are shown in Table
1.
[0074]
[Example 11]
30
P160607WO
The same operation as in Example 1 was performed, except
that the amount of DOWANOL PPH in the dyeing prescription was
changed to 20 g/L. The evaluation results are shmm in Table
1.
[0075]
[Example 12]
The same operation as in Example 1 1·1as performed, except
that the amount of DOWANOL PPH in the dyeing prescription was
changed to 10 g/L. The evaluation results are shmm in Table
1.
[0076]
Table 1
Material mixing Meta-type wholly aromatic polyamide fiber ratio{%) Flame retardancy Hyperchromicity {MAl
Content of Content of Afterflame time
Crystallinity residual residual carrier
according to JIS
(%) solvent agent L1091A-4: three L value (%by mass) (%by mass) second flame contact {sec)
Example 1 MA93/PA5/AS2 19 0.08 0.8 1 52.0
Example2 MA93/PA5/AS2 19 0.08 0.5 0 52.3
Example3 MA93/PA5/AS2 19 0.08 0.9 1 52.0
Example4 MA93/PA5/AS2 19 0.08 0.8 1 51.9
ExampleS MA93/PA5/AS2 19 0.08 0.4 0 52.2
Example6 MA93/PA5/AS2 19 0.08 0.9 1 52.1
Example 7 MA93/PA5/AS2 19 0.08 0.5 0 52.1
Comparative MA93/PA5/AS2 19 0.08 2.5 Entirely burnt 51.8
Example 1
ExampleS MA93/PA5/AS2 19 0.08 1.5 25 51.9
Example9 MA93/PA5/AS2 19 0.08 1.0 12 52.0
Example 10 MA93/PA5/AS2 19 0.08 0.8 1 52.7
Example 11 MA93/PA5/AS2 19 0.08 0.8 1 53.5
Example 12 MA93/PA5/AS2 19 0.08 0.8 1 54.0
INDUSTRIAL APPLICABILITY
31
P160607WO
[0077]
In accordance with the present invention, a colored
organic fiber that has a deep color and excellent flame
retardancy, a cloth and garments each composed of the
foregoing organic fiber, and a method for producing a cloth
are provided, and its industrial value is extremely large.

CLAIMS
[Claim 1]
A colored organic fiber having a content of a carrier
agent of 1.8% by mass or less relative to the fiber mass.
[Claim 2]
The colored organic fiber according to claim 1, 1-1herein
the content of the carrier agent is 0. 1 to 1. 8% by mass relative
to the fiber mass.
[Claim 3]
The colored organic fiber according to claim 1, \•/herein
the carrier agent is any one or more selected from the group
consisting of DL-p-ethylphenethyl alcohol, 2-ethoxybenzyl
alcohol, 3-chlorobenzyl alcohol, 2, 5-dimethylbenzyl alcohol,
2-nitrobenzyl alcohol, p-isopropylbenzyl
2-methylphenethyl alcohol, 3-methylphenethyl
4-methylphenethyl alcohol, 2-methoxybenzyl
alcohol,
alcohol,
alcohol,
3-iodobenzyl alcohol, cinnamic alcohol, p-anisyl alcohol,
benzhydrol, benzyl alcohol, propylene glycol phenyl ether,
ethylene glycol phenyl ether, and N-methylformanilide.
[Claim 4]
The colored organic fiber according to claim 1, wherein
the organic fiber is any one selected from the group consisting
of a meta-type wholly aromatic polyamide fiber, a para-type
1·1holly aromatic polyamide fiber, a polybenzoxazole (PBO)
33
P160607WO
fiber, a polybenzimidazole (PBI) fiber, a polybenzthiazole
(PBTZ) fiber, a polyimide (PI) fiber, a polysulfonamide (PSA)
fiber, a polyetheretherketone (PEEK) fiber, a polyether imide
(PEI) fiber, a polyarylate (PAr) fiber, a melamine fiber, a
phenol fiber, a fluorine-based fiber, and a polyphenylene
sulfide (PPS) fiber.
[Claim 5]
The colored organic fiber according to claim 1, wherein
the organic fiber is a meta-type wholly aromatic polyamide
fiber having a crystallinity of 15 to 25%.
[Claim 6]
The colored organic fiber according to claim 1, wherein
the organic fiber is a meta-type wholly aromatic polyamide
fiber having a content of residual solvent of 1. 0% by mass or
less.
[Claim 7]
The colored organic fiber according to claim 1, wherein
the organic fiber is a meta-type wholly aromatic polyamide
fiber having a content of residual solvent of 0. 1% by mass or
less.
[Claim 8]
The organic fiber according to claim 6 or 7, wherein the
residual solvent is any one selected from the group consisting
of N,N-dimethylformamide, N,N-dimethylacetamide,
N-methyl-2-pyrro1idone, and dimethyl sulfoxide.
34
Pl60607WO
[Claim 9]
The colored organic fiber according to claim 1, 1·1herein
the organic fiber is a meta-type wholly aromatic polyamide
fiber; and a meta-type wholly aromatic polyamide forming the
a meta-type 1·1holly aromatic polyamide fiber is an aromatic
polyamide in which in an aromatic polyamide skeleton
containing a repeating structural unit represented by the
follm1ing formula ( 1) , an aromatic diamine component or
aromatic dicarboxylic acid halide component that is different
from a main structural unit of the repeating structure is
copolymerized as a third component such that a proportion of
the third component is 1 to 10 mol% relative to the whole amount
of the repeating structural units of the aromatic polyamide:
-(NH-Arl-NH-CO-Arl-CO)- ... (1)
1vherein Ar 1 is a divalent aromatic group having a
linking group in a position other than the meta position or
an axially parallel direction.
[Claim 10]
The colored organic fiber according to claim 9, wherein
the third component is an aromatic diamine represented by the
following formula (2) or (3) or an aromatic dicarboxylic acid
halide represented by the following formula (4) or (5):
H2N-Ar2-NH2 ••• (2)
H2N-Ar2-Y-Ar2-NH2 ••• (3)
XOC-Ar3-COX ... (4)
35
~ P160607WO
XOC-Ar3-Y-Ar3-COX ... (5)
wherein Ar2 is a divalent aromatic group different from
Arl; Ar3 is a divalent aromatic group different from Arl; Y
is at least one atom or functional group selected from the
group consisting of an oxygen atom, a sulfur atom, and an
alkylene group; and X is a halogen atom.
[Claim 11]
A cloth comprising the colored organic fiber according
to claim 1.
[Claim 12]
The cloth according to claim 11, 1vherein the cloth
contains any one or more selected from the group consisting
of a polyester fiber, a cellulose fiber, a polyamide fiber,
a polyolefin fiber, an acrylic fiber, a rayon fiber, a cotton
fiber, an animal hair fiber, a polyurethane fiber, a polyvinyl
chloride fiber, a polyvinylidene chloride fiber, an acetate
fiber, and a polycarbonate fiber.
[Claim 13]
The cloth according to claim 11, wherein any one of
fibers constituting the cloth contains a flame retarder.
[Claim 14]
The cloth according to claim 11, wherein any one of
fibers constituting the cloth contains a UV absorber or a UV
reflector.
[Claim 15]
36
t'_lbUbU/WU
The cloth according to claim 11, wherein an areal weight
of the cloth is 300 g/m2 or less.
[Claim 16)
The cloth according to claim 11, wherein an LOI is 26
or more.
[Claim 17)
The cloth according to claim 11, wherein an afterflame
time in the vertical flame test (JIS L1091A-4: three second
flame contact) is 1 second or less.
[Claim 18)
The cloth according to claim 11, wherein a brightness
index L value is'86 or less.
[Claim 19)
Garments comprising the cloth according to claim 11.
[Claim 20)
A method for producing the cloth containing the colored
organic fiber according to claim 11, comprising
dyeing a cloth containing an . organic fiber with a
carrier agent and then washing the cloth 1-1i th hot 1-1ater at a
temperature of 90 to 140°C for· 10 to 30 minutes, thereby
controlling a content of the carrier agent contained in the
organic fiber to 1.8% by mass or less relative to the fiber
mass.