U.S. patent number 10,385,209 [Application Number 15/529,846] was granted by the patent office on 2019-08-20 for polyamide-based fiber for artificial hair having exceptional dripping resistance upon combustion.
This patent grant is currently assigned to Denka Company Limited. The grantee listed for this patent is Denka Company Limited. Invention is credited to Atsushi Horihata, Kouta Nagaoka, Yudai Ogawa, Atsushi Takei, Shigeharu Yoshii.
United States Patent |
10,385,209 |
Ogawa , et al. |
August 20, 2019 |
Polyamide-based fiber for artificial hair having exceptional
dripping resistance upon combustion
Abstract
Polyamide-based fiber for artificial hair that is excellent in
drip resistance, texture, and productivity is provided. According
to the present invention, provided is fiber for artificial hair,
including a resin composition containing: aliphatic polyamide;
semi-aromatic polyamide with a skeleton obtained by
polycondensation of aliphatic diamine and aromatic dicarboxylic
acid; and a bromine-based flame retardant.
Inventors: |
Ogawa; Yudai (Kamakura,
JP), Nagaoka; Kouta (Kamakura, JP),
Horihata; Atsushi (Kamakura, JP), Yoshii;
Shigeharu (Kamakura, JP), Takei; Atsushi
(Kamakura, JP) |
Applicant: |
Name |
City |
State |
Country |
Type |
Denka Company Limited |
Chuo-ku, Tokyo |
N/A |
JP |
|
|
Assignee: |
Denka Company Limited (Chuo-ku,
Tokyo, JP)
|
Family
ID: |
56107118 |
Appl.
No.: |
15/529,846 |
Filed: |
September 9, 2015 |
PCT
Filed: |
September 09, 2015 |
PCT No.: |
PCT/JP2015/075597 |
371(c)(1),(2),(4) Date: |
May 25, 2017 |
PCT
Pub. No.: |
WO2016/092922 |
PCT
Pub. Date: |
June 16, 2016 |
Prior Publication Data
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|
|
Document
Identifier |
Publication Date |
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US 20170260391 A1 |
Sep 14, 2017 |
|
Foreign Application Priority Data
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|
|
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Dec 9, 2014 [JP] |
|
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2014-249015 |
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Current U.S.
Class: |
1/1 |
Current CPC
Class: |
D01F
1/07 (20130101); C08L 63/00 (20130101); A41G
3/00 (20130101); C08L 77/06 (20130101); C08K
3/2279 (20130101); D01F 6/90 (20130101); C08L
77/06 (20130101); C08L 77/06 (20130101); C08L
63/00 (20130101); C08L 77/06 (20130101); C08L
77/06 (20130101); C08L 69/00 (20130101); C08L
77/06 (20130101); C08L 77/06 (20130101); C08L
25/18 (20130101); C08L 77/06 (20130101); C08L
77/06 (20130101); C08L 71/10 (20130101); C08L
77/06 (20130101); C08L 77/06 (20130101); C08L
63/00 (20130101); C08K 3/2279 (20130101); C08L
2201/02 (20130101); C08L 2205/025 (20130101); C08L
2205/22 (20130101); C08L 2205/16 (20130101); C08L
2203/12 (20130101) |
Current International
Class: |
C08L
77/06 (20060101); D01F 1/07 (20060101); C08L
63/00 (20060101); C08K 3/22 (20060101); D01F
6/90 (20060101); A41G 3/00 (20060101) |
References Cited
[Referenced By]
U.S. Patent Documents
Foreign Patent Documents
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|
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|
|
101160069 |
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Apr 2008 |
|
CN |
|
102368919 |
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Mar 2012 |
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CN |
|
103501647 |
|
Jan 2014 |
|
CN |
|
2004-156149 |
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Jun 2004 |
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JP |
|
2007297737 |
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Nov 2007 |
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JP |
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2007-332507 |
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Dec 2007 |
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JP |
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2008-285772 |
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Nov 2008 |
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JP |
|
WO 2010/090191 |
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Aug 2010 |
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JP |
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2011-246844 |
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Dec 2011 |
|
JP |
|
WO 2012/157561 |
|
Nov 2012 |
|
JP |
|
2012-251256 |
|
Dec 2012 |
|
JP |
|
173210 |
|
Sep 2011 |
|
SG |
|
2015/056629 |
|
Apr 2015 |
|
WO |
|
Other References
WO 2010/090191 machine translaton. cited by examiner .
JP 2007332507 machine translation. cited by examiner .
International Search Report dated Dec. 15, 2015, issued in
corresponding International Application No. PCT/JP2015/075597,
filed Sep. 9, 2015, 2 pages. cited by applicant .
First Office Action, dated Jul. 4, 2018, issued in corresponding
Chinese Application No. 201580061024.0, filed Sep. 9, 2015, 17
pages. cited by applicant .
Second Review Notice dated Mar. 11, 2019, issued in corresponding
Chinese Application No. 2015800610240, filed Sep. 9, 2015, 13
pages. cited by applicant .
"Plastic Industry Manual: Polyamide," P. Zhihan and S. Zupei,
National Key Book "15", Chemical Industry Publishing Company,
Bejing, China, 4 pages. cited by applicant .
Notification of Reasons for Refusal dated Mar. 29, 2019, issued in
corresponding Japanese Application No. 2016-563552, filed Sep. 9,
2015, 9 pages. cited by applicant.
|
Primary Examiner: Woodward; Ana L.
Attorney, Agent or Firm: Christensen O'Connor Johnson
Kindness PLLC
Claims
The invention claimed is:
1. Fiber for artificial hair, comprising a resin composition
containing: aliphatic polyamide (A); semi-aromatic polyamide (B)
with a skeleton obtained by polycondensation of aliphatic diamine
and aromatic dicarboxylic acid; and a bromine-based flame retardant
(C), wherein the bromine-based flame retardant (C) is added in
amount of 3 to 40 parts by mass based on a total of 100 parts by
mass of an amount of the aliphatic polyamide (A) and an amount of
the semi-aromatic polyamide (B); wherein the semi-aromatic
polyamide (B) includes at least one selected from polyamide 6T,
polyamide 9T, and polyamide 10T; and the aliphatic polyamide (A)
and the semi-aromatic polyamide (B) are mixed at a ratio ranging
from 50 parts by mass/50 parts by mass to 99 parts by mass/1 part
by mass.
2. The fiber of claim 1, wherein the aliphatic polyamide (A)
includes at least one selected from polyamide 6 and polyamide
66.
3. The fiber of claim 1, wherein the aliphatic polyamide (A) has a
weight average molecular weight Mw from 65 thousand to 150
thousand.
4. The fiber of claim 1, wherein the bromine-based flame retardant
(C) is at least one selected from the group consisting of a
brominated phenol condensate, a brominated polystyrene-based flame
retardant, a brominated benzyl acrylate-based flame retardant, a
brominated epoxy-based flame retardant, a brominated phenoxy-based
flame retardant, a brominated polycarbonate-based flame retardant,
and a bromine-containing triazine-based compound.
5. The fiber of claim 1, wherein the bromine-based flame retardant
(C) includes a compound structure represented by a chemical formula
(1) below ##STR00002##
6. The fiber of claim 1, wherein the bromine-based flame retardant
(C) is added in an amount from 3 to 30 parts by mass based on a
total of 100 parts by mass of an amount of the aliphatic polyamide
(A) and an amount of the semi-aromatic polyamide (B).
7. The fiber of claim 1, further comprising an auxiliary flame
retardant (D).
8. The fiber of claim 7, wherein the auxiliary flame retardant (D)
is at least one selected from the group consisting of antimony
trioxide, antimony tetroxide, antimony pentoxide, sodium
antimonate, zinc borate, and zinc stannate.
9. The fiber of claim 7, wherein the auxiliary flame retardant (D)
has an average particle size ranging from 1 to 10 .mu.m.
10. The fiber of claim 7, wherein the auxiliary flame retardant (D)
is added in an amount from 0.1 to 10 parts by mass based on a total
of 100 parts by mass of an amount of the aliphatic polyamide (A)
and an amount of the semi-aromatic polyamide (B).
11. The fiber of claim 1, further comprising organic microparticles
(E).
12. The fiber of claim 11, wherein the organic microparticles (E)
are at least one selected from crosslinked nitrile rubber, a
crosslinked acrylic resin, crosslinked polyester, crosslinked
polyamide particles, a crosslinked silicone resin, a crosslinked
polystyrene resin, and a crosslinked polyethylene resin.
13. The fiber of claim 11, wherein the organic microparticles (E)
are crosslinked nitrile rubber.
14. The fiber of claim 11, wherein the crosslinked nitrile rubber
has an AN ratio ranging from 30 to 50 mass %.
15. The fiber of claim 11, wherein the organic microparticles (E)
are added in an amount from 3 to 30 parts by mass based on a total
of 100 parts by mass of an amount of the aliphatic polyamide (A)
and an amount of the semi-aromatic polyamide (B).
Description
TECHNICAL FIELD
The present invention relates to fiber used for artificial hair,
such as wigs, hairpieces, and hair extensions, allowed to be put on
and off of the head (hereinafter, simply referred to as "fiber for
artificial hair").
BACKGROUND ART
As described in PTL 1, materials making up fiber for artificial
hair include vinyl chloride resins. This is because vinyl chloride
resins in the fiber for artificial hair are excellent in
processability, cost reduction, and the like.
In fiber for artificial hair using a vinyl chloride resin as a
material, such a vinyl chloride resin is poor in heat resistance to
heat from a curling iron and the like. For curling with a curling
iron or the like generally set at a temperature of 100.degree. C.
or more, such fiber may thus be fused and frizzled and sometimes
results in damage and breaking of the fiber. Accordingly, polyamide
based fiber for artificial hair is under development, which is
highly heat resistant.
Polyamide unfortunately has a risk of dropping a molten resin
during combustion and may cause burning due to contact with the
molten resin. It is thus desired to give performance resistant to
melt dripping during combustion (hereinafter, simply referred to as
"drip resistance").
PTL 2 discloses fiber for artificial hair produced by fiberizing a
resin composition containing polyamide and a bromine-based flame
retardant. Addition of the bromine-based flame retardant to
polyamide improves the drip resistance of polyamide, and the
problems of the fiber for artificial hair using polyamide as a
material are solved to some extent.
CITATION LIST
Patent Literature
PTL 1: JP 2004-156149A PTL 2: JP 2011-246844A
SUMMARY OF INVENTION
Technical Problem
The fibers for artificial hair using aliphatic polyamide as a
material provide good texture like human hair while having a risk
of dripping the molten resin during combustion as described above,
and thus it is desired to give drip resistance from the perspective
of the safety of a wearer.
To give drip resistance to polyamide, a flame retardant is
generally added. As the flame retardant, bromine-based flame
retardants, phosphorus-based flame retardants, nitrogen-based flame
retardants, hydrated metal compounds, and the like are commercially
available. Among them, combination of a bromine-based flame
retardant and an auxiliary flame retardant is considered to have
the highest combustion inhibiting effect.
The combination of polyamide and a bromine-based flame retardant is
not, however, compatible and causes insufficient dispersion of the
bromine-based flame retardant in the polyamide resin during melt
kneading. It thus has a problem of causing a defect, such as yarn
breaking, during processing into a fibrous form, leading to
significant reduction in productivity.
Accordingly, there is a need for improvement in the dispersion
state of the bromine-based flame retardant in the polyamide resin
to establish blend formulation of highly productive fiber for
artificial hair.
The present invention has been made in view of such circumstances,
and it is to provide drip-resistant polyamide-based fiber for
artificial hair that provide good texture like human hair, is
excellent in drip resistance, and is excellent in productivity.
Solution to Problem
According to the present invention, fiber for artificial hair is
provided that includes a resin composition containing: at least one
aliphatic polyamide; semi-aromatic polyamide with a skeleton
obtained by polycondensation of aliphatic diamine and aromatic
dicarboxylic acid; and a bromine-based flame retardant.
As a result of intensive examination to solve the above problems,
the present inventors have found that fiber for artificial hair
containing aliphatic polyamide, semi-aromatic polyamide with a
skeleton obtained by polycondensation of aliphatic diamine and
aromatic dicarboxylic acid, and a bromine-based flame retardant
provides polyamide-based fiber for artificial hair having good drip
resistance, excellent texture, and good productivity, and thus have
come to complete the present invention.
DESCRIPTION OF EMBODIMENTS
Descriptions below are given to embodiments of the present
invention.
Fiber for artificial hair of the present invention contains a resin
composition having respectively at least one or more of: aliphatic
polyamide; semi-aromatic polyamide with a skeleton obtained by
polycondensation of aliphatic diamine and aromatic dicarboxylic
acid; and a bromine-based flame retardant. As described in
experimental examples later, the fiber for artificial hair
containing a mixture of the above three materials is understood to
have good drip resistance, texture, and productivity.
The resin composition making up the fiber for artificial hair is
described below in detail.
Polyamide
The fiber for artificial hair of the present invention contains a
resin composition having respectively at least one or more of:
aliphatic polyamide; and semi-aromatic polyamide with a skeleton
obtained by polycondensation of aliphatic diamine and aromatic
dicarboxylic acid.
The aliphatic polyamide is polyamide having no aromatic ring.
Examples of the aliphatic polyamide include n-nylon formed by
ring-opening polymerization of lactam and n,m-nylon synthesized by
co-polycondensation reaction of aliphatic diamine and aliphatic
dicarboxylic acid. Lactam preferably has a carbon number from 6 to
12 and more preferably of 6. Aliphatic diamine and aliphatic
dicarboxylic acid respectively preferably have a carbon number from
6 to 12 and more preferably of 6. Aliphatic diamine and aliphatic
dicarboxylic acid preferably have a functional group (amino group
or carboxyl group) at both ends of the carbon chain, while the
functional groups may be in positions other than the both ends. The
carbon chain is preferably linear, while it may be branched.
Examples of such aliphatic polyamide include polyamide 6 and
polyamide 66. From the perspective of heat resistance, polyamide 66
is preferred. Specific examples of such polyamide 6 include CM1007,
CM1017, CM1017XL3, CM1017K, and CM1026 produced by Toray
Industries, Inc. Examples of such polyamide 66 include CM3007,
CM3001-N, CM3006, and CM3301L produced by Toray Industries, Inc.,
Zytel 101 and Zytel 42A produced by Du Pont K.K., and LEONA 1300S,
1500, and 1700 produced by Asahi Kasei Chemicals Corp.
Examples of such semi-aromatic polyamide with a skeleton obtained
by polycondensation of aliphatic diamine and aromatic dicarboxylic
acid include polyamide 6T, polyamide 9T, and polyamide 10T, as well
as modified polyamide 6T, modified polyamide 9T, and modified
polyamide 10T that are produced by copolymerizing a monomer for
modification based thereon. Among them, polyamide 10T is preferred
for ease of melt molding. Aliphatic diamine preferably has a carbon
number from 6 to 10 and more preferably of 10. Aliphatic diamine
preferably has an amino group at both ends of the carbon chain
while the amino groups may be in positions other than the both
ends. The carbon chain is preferably linear while it may be
branched. Examples of such aromatic dicarboxylic acid include
phthalic acid, isophthalic acid, terephthalic acid, and the like.
Among them, terephthalic acid is most preferred.
Specific examples of such polyamide 6T and modified polymers
thereof include VESTAMID HP Plus M1000 produced by Evonik
Industries AG, ARLEN produced by Mitsui Chemicals, Inc., and the
like. Examples of such polyamide 9T and modified polymers thereof
include Genestar produced by Kuraray Co., Ltd. Examples of such
polyamide 10T and modified polymers thereof include VESTAMID HO
Plus M3000 produced by Evonik Japan Co., Ltd., Grivory produced by
EMS-CHEMIE AG, and the like.
The aliphatic polyamide and the semi-aromatic polyamide are mixed
at a ratio preferably ranging from 50 parts by mass/50 parts by
mass to 99 parts by mass/1 part by mass and more preferably ranging
from 70 parts by mass/30 parts by mass to 90 parts by mass/10 parts
by mass. It is understood that a ratio of the semi-aromatic
polyamide less than the above range causes a decrease in the effect
of productivity improvement by adding the semi-aromatic polyamide.
While fiber for artificial hair containing aliphatic polyamide
provides good texture like human hair as described above, it is
understood that a ratio of the semi-aromatic polyamide greater than
the above range causes a decrease in the texture.
The aliphatic polyamide has a weight average molecular weight (Mw),
for example, from 65 thousand to 150 thousand. Mw of more than 65
thousand results in particularly good drip resistance, whereas Mw
of more than 150 thousand causes an increase in melt viscosity of
the material and poor processability for fiberization. Mw is thus
preferably 150 thousand or less. Considering the balance between
the drip resistance and the processability, Mw is more preferably
from 70 thousand to 120 thousand.
Bromine-Based Flame Retardant
The fiber for artificial hair of the present invention contains at
least one or more of bromine-based flame retardants. The flame
retardant is added in an amount preferably from 3 to 30 parts by
mass based on a total of 100 parts by mass of an amount of the
aliphatic polyamide and an amount of the semi-aromatic polyamide
with a skeleton obtained by polycondensation of aliphatic diamine
and aromatic dicarboxylic acid, and more preferably from 10 to 30
parts by mass. This is because the balance between the drip
resistance giving effect and the processability is good within the
above range.
Examples of the bromine-based flame retardant include brominated
phenol condensates, brominated polystyrene resins, brominated
benzil acrylate-based flame retardants, brominated epoxy resins,
brominated phenoxy resins, brominated polycarbonate resins, and
bromine-containing triazine-based compounds. Specific examples of
such brominated phenol condensate include SR-460B produced by DKS
Co. Ltd. Examples of such brominated polystyrene resin include
HP-7010 and HP-3010 produced by Albemarle Corp., PS900 and PL1200
produced by Manac Inc., PDBS-80 and PBS-64HW produced by Chemtura
Japan Ltd., FCP-8000 and FCP-8000ST produced by Suzuhiro Chemical
Co., Ltd., and the like. Examples of such brominated benzil
acrylate-based flame retardant include FR-1025 produced by ICL.
Examples of such brominated epoxy resin include SRT-20000,
SRT-5000, SRT-2000, SRT-7040, and SRT-3040 produced by Sakamoto
Yakuhin Kogyo Co., Ltd., F-2100, F-2300H, F-2400, and F-2400H
produced by ICL Japan Ltd., and the like. Examples of such
brominated phenoxy resin include YPB-43C and YPB-43M produced by
Nippon Steel & Sumikin Chemical Co., Ltd. Examples of such
brominated polycarbonate resin include Fire Guard FG-7000, Fire
Guard FG-7500, and Fire Guard FG-8500 produced by Teijin Ltd.
Examples of such bromine-containing triazine-based compound include
SR-245 produced by DKS Co. Ltd. Among all, considering the balance
between drip resistance, processability, transparency of the yarn,
and the like, a brominated epoxy resin or a brominated phenoxy
resin having a structural formula (1) below is preferred.
##STR00001## Auxiliary Flame Retardant
The fiber for artificial hair of the present invention contains an
auxiliary flame retardant in addition to aliphatic polyamide,
semi-aromatic polyamide with a skeleton obtained by
polycondensation of aliphatic diamine and aromatic dicarboxylic
acid, and a bromine-based flame retardant, for further improvement
in the drip resistance and the self-extinguishing properties, which
is preferred. Examples of the auxiliary flame retardant include
antimony trioxide, antimony tetroxide, antimony pentoxide, sodium
antimonate, zinc borate, and zinc stannate. Among them, for the
balance between the drip resistance and the transparency of the
yarn, antimony trioxide is preferred.
The auxiliary flame retardant is preferably added in an amount from
0.1 to 10 parts by mass based on a total of 100 parts by mass of an
amount of the aliphatic polyamide and an amount of the
semi-aromatic polyamide with a skeleton obtained by
polycondensation of aliphatic diamine and aromatic dicarboxylic
acid and more preferably from 1 to 5 parts by mass. This is because
the balance between the drip resistance, the self-extinguishing
properties, the processability, and the transparency of the yarn is
best within the above range. If the auxiliary flame retardant is
added in an amount more than the above range, the transparency of
the yarn and the processability are reduced. If the auxiliary flame
retardant is added in an amount less than the above range, the
effects of improving the drip resistance and the self-extinguishing
properties are reduced.
From the perspective of the transparency of the yarn and the
processability, the auxiliary flame retardant has an average
particle size preferably ranging from 1 to 10 .mu.m and more
preferably ranging from 3 to 8 .mu.m. The "average particle size"
herein means a particle size with an integrated value of 50% in the
particle size distribution obtained by laser diffraction
scattering.
The auxiliary flame retardant may be a combination of plural items
from the group consisting of antimony trioxide, antimony tetroxide,
antimony pentoxide, sodium antimonate, zinc borate, and zinc
stannate or a composite of two or more from the group.
Organic Microparticle
By further addition of organic microparticles, the fiber for
artificial hair of the present invention has more improved low
glossiness and is allowed to have an appearance more like human
hair.
Examples of the organic microparticles include crosslinked nitrile
rubber, a crosslinked acrylic resin, crosslinked polyester,
crosslinked polyamide, a crosslinked silicone resin, a crosslinked
polystyrene resin, and a crosslinked polyethylene resin. Among
them, crosslinked nitrile rubber is preferred. According to
experiments by the present inventors, the resin composition
containing organic or inorganic microparticles or the like for
reduction of glossiness of the fiber tends to cause whitening of
the fiber after drawing. Accordingly, for predetermined coloring of
the resin composition, the amount of colorant to be added sometimes
has to be increased. Crosslinked nitrile rubber is preferred
because, in spite of such tendency, addition of organic
microparticles containing crosslinked nitrile rubber inhibits such
whitening.
The crosslinked nitrile rubber has an AN ratio preferably ranging
from 30 to 50 mass %. This is because addition of crosslinked
nitrile rubber in the above range leads to particularly good
processability of the fiber for artificial hair.
Considering the balance between the glossiness reduction effect by
the organic microparticles and other properties, the organic
microparticles are added in an amount from 3 to 30 parts by mass
based on a total of 100 parts by mass of an amount of the aliphatic
polyamide and an amount of the semi-aromatic polyamide and more
preferably from 5 to 20 parts by mass.
The organic microparticles preferably have an average particle size
from 0.05 to 15 .mu.m, more preferably from 0.05 to 10 .mu.m, and
even more preferably from 0.05 to 5 .mu.m. This is because such a
range has sufficiently large effects of controlling a gloss and a
shine and also does not easily cause reduction in fiber strength
due to addition of the microparticles.
Other Additives
The resin composition used in the present embodiment may contain,
in addition to polyamide, additives such as heat resistant agents,
light stabilizers, fluorescent agents, antioxidants, antistatic
agents, pigments, dyes, plasticizers, and lubricants, as needed.
Such colorants, such as pigments and dyes, may be contained to
produce precolored fiber (so-called spun-dyed fiber).
Production Process
Descriptions are given below to an example of production process of
the fiber for artificial hair, which does not limit the present
invention.
First, the aliphatic polyamide, the semi-aromatic polyamide, and
the bromine-based flame retardant described above are melt kneaded.
As an apparatus for melt kneading, various general kneaders may be
used. Examples of such a melt kneader include a single-screw
extruder, a twin-screw extruder, a roll, a banbury mixer, a
kneader, and the like. Among them, a twin-screw extruder is
preferred in point of control of the degree of kneading and the
ease of operation. The fiber for artificial hair is produced by
general melt spinning in an appropriate temperature condition
depending on the type of polyamide.
When polyamide 66 as the aliphatic polyamide and polyamide 10T as
the semi-aromatic polyamide are used at a ratio of 80 parts by
mass/20 parts by mass, a melt spinning device such as an extruder,
a spinneret, and a gear pump as needed is set at a temperature from
270 to 310.degree. C. for melt spinning. The resin is cooled in a
tank filled with cooling water, and while controlling the fineness,
the take up speed is adjusted to obtain undrawn yarn. The
temperature of the melt spinning apparatus may be controlled as
appropriate for the amount ratio of aliphatic polyamide and
semi-aromatic polyamide. The cooling is not limited to be in a tank
and spinning by cooling with cold air is also applicable. The
temperature of the cooling tank, the temperature of cold air, the
cooling time, and the take up speed may be appropriately controlled
in accordance with the discharge and the number of holes in the
spinneret.
For melt spinning, a spinning nozzle with nozzle holes in a special
shape, not only in a simple circular shape, may be used to produce
artificial hair fiber with a cross section in a deformed shape,
such as an oval shape, a Y shape, an H shape, an X shape, and a
flower shape.
The undrawn yarn thus obtained is subjected to drawing for
improvement in tensile strength of the fiber. The drawing may be in
either method of: the two-step method where the undrawn yarn is
once taken up on a bobbin to be drawn in a step separate from the
melt spinning; and direct spin drawing where drawing is performed
continuously from the melt spinning without taking up on a bobbin.
The drawing is performed by single-stage drawing to draw to the
target draw ratio at a time or multi-stage drawing to draw to the
target draw ratio in drawing at two or more times. A heating
mechanism in a case of hot drawing may be a heating roller, a
heating plate, a steam jet apparatus, a hot water tank, and the
like, and they may be used in combination as appropriate.
The fiber for artificial hair in the present embodiment preferably
has fineness from 10 to 150 dtex, more preferably from 30 to 150
dtex, and even more preferably from 35 to 120 dtex.
EXAMPLES
Then, Examples of the fiber for artificial hair by the present
invention are described in detail with reference to tables in
comparison with Comparative Examples. The present invention is then
described even more specifically based on Examples, which do not
limit the present invention.
An aliphatic polyamide resin, a semi-aromatic polyamide resin, and
a bromine-based flame retardant that were dried to have a moisture
absorption of less than 1000 ppm were blended at blend ratios for
Examples and Comparative Examples in Tables 1 to 5. The numerical
values of amounts of polyamide, flame retardants, auxiliary flame
retardants, and organic microparticles in Tables 1 to 5 are in
parts by mass. The blended material was kneaded using a .phi. 30 mm
twin-screw extruder to obtain spinning material pellets.
The pellets were then dehumidified and dried to have a moisture
absorption of 1000 ppm or less, followed by spinning using a .phi.
40 mm single spindle melt spinner. The molten resin delivered from
a die with a hole diameter of 0.5 mm was cooled through a water
tank at approximately 30.degree. C. while the discharge and the
take up speed were controlled to prepare undrawn yarn at preset
fineness. The .phi. 40 mm melt spinner was set at a temperature
appropriately controlled in accordance with the ratio of the
amounts of aliphatic polyamide and semi-aromatic polyamide and the
amount of the bromine-based flame retardant.
The undrawn yarn thus obtained was drawn at 100.degree. C.,
followed by annealing from 150.degree. C. to 200.degree. C. to
produce fiber for artificial hair at predetermined fineness. The
draw ratio was 3 and a relaxation rate for annealing was from 0.5%
to 3%. The relaxation rate for annealing is a value calculated by
(rotation speed of take up roller during annealing)/(rotation speed
of feed roller during annealing).
The fiber for artificial hair thus obtained was evaluated for the
glossiness, self-extinguishing properties, drip resistance,
texture, processability, and transparency in accordance with
evaluation methods and criteria described later. Results are shown
in Tables 1 to 5.
TABLE-US-00001 TABLE 1 Examples 1 2 3 4 5 6 7 8 9 10 11 12 13 14
Aliphatic Polyamide Polyamide 66 Weight Average Molecular 80 Resin
Weight of 120000 Weight Average Molecular 80 80 80 99.5 99 90 70 50
40 20 Weight of 90000 Weight Average Molecular 80 Weight of 65000
Weight Average Molecular 80 Weight of 50000 Polyamide 6 Weight
Average Molecular 80 Weight of 90000 Semi-Aromatic Polyamide 10T 20
0.5 1 10 30 50 60 80 20 20 20 20 Polyamide Resin Polyamide 9T 20
Polyamide 6T 20 Bromine-Based Flame Brominated Epoxy Resin 15 15 15
15 15 15 15 15 15 15 15 15 15 15 Retardant Evaluation Glossiness
.largecircle. .largecircle. .largecircle. .largecirc- le.
.largecircle. .largecircle. .largecircle. .largecircle.
.largecircle. - .largecircle. .largecircle. .largecircle.
.largecircle. .largecircle. Transparency .circle-w/dot.
.circle-w/dot. .circle-w/dot. .largecircle. .- largecircle.
.circle-w/dot. .circle-w/dot. .circle-w/dot. .circle-w/dot. .-
circle-w/dot. .circle-w/dot. .circle-w/dot. .circle-w/dot.
.circle-w/dot. Texture .circle-w/dot. .largecircle. .circle-w/dot.
.circle-w/dot. .circl- e-w/dot. .circle-w/dot. .circle-w/dot.
.circle-w/dot. .largecircle. .DELTA- . .circle-w/dot.
.circle-w/dot. .circle-w/dot. .circle-w/dot. Drip Resistance
.largecircle. .DELTA. .DELTA. .largecircle. .largecircle.-
.largecircle. .largecircle. .largecircle. .largecircle.
.largecircle. .la- rgecircle. .largecircle. .DELTA. .largecircle.
Self-Extinguishing Properties .DELTA. .DELTA. .DELTA. .DELTA.
.DELTA. .DELTA. .DELTA. .DELTA- . .DELTA. .DELTA. .DELTA. .DELTA.
.DELTA. .DELTA. Processability .circle-w/dot. .largecircle.
.largecircle. .DELTA. .largec- ircle. .circle-w/dot. .circle-w/dot.
.circle-w/dot. .circle-w/dot. .circle- -w/dot. .circle-w/dot.
.circle-w/dot. .circle-w/dot. .circle-w/dot.
TABLE-US-00002 TABLE 2 Examples 15 16 17 18 19 20 21 22 23 24 25 26
Aliphatic Polyamide Polyamide 66 Weight Average Molecular 80 80 80
80 80 80 80 80 80 80 80 80 Resin Weight of 90000 Semi-Aromatic
Polyamide 10T 20 20 20 20 20 20 20 20 20 20 20 20 Polyamide Resin
Bromine-Based Flame Brominated Epoxy Resin 1 3 10 20 30 40
Retardant Brominated Polystyrene Resin 15 Brominated Phenoxy Resin
15 Brominated Phenol Condensate 15 Brominated Benzil Acrylate-Based
Flame Retardant 15 Brominated Polycarbonate Resin 15
Bromine-Containing Triazine-Based Compound 15 Evaluation Glossiness
.largecircle. .largecircle. .largecircle. .largecirc- le.
.largecircle. .largecircle. .DELTA. .DELTA. .largecircle.
.largecircle- . .largecircle. .largecircle. Transparency
.largecircle. .circle-w/dot. .circle-w/dot. .circle-w/dot. .-
largecircle. .largecircle. .circle-w/dot. .circle-w/dot.
.circle-w/dot. .c- ircle-w/dot. .circle-w/dot. .circle-w/dot.
Texture .circle-w/dot. .circle-w/dot. .circle-w/dot. .circle-w/dot.
.circ- le-w/dot. .circle-w/dot. .circle-w/dot. .circle-w/dot.
.circle-w/dot. .cir- cle-w/dot. .circle-w/dot. .largecircle. Drip
Resistance .largecircle. .largecircle. .largecircle. .largecircle.
.- largecircle. .largecircle. .DELTA. .largecircle. .largecircle.
.largecircl- e. .circle-w/dot. .circle-w/dot. Self-Extinguishing
Properties .DELTA. .DELTA. .DELTA. .DELTA. .DELTA. .DELTA. x
.DELTA. .DEL- TA. .DELTA. .largecircle. .largecircle.
Processability .circle-w/dot. .circle-w/dot. .largecircle.
.largecircle. - .largecircle. .largecircle. .circle-w/dot.
.circle-w/dot. .circle-w/dot. .- circle-w/dot. .largecircle.
.DELTA.
TABLE-US-00003 TABLE 3 Examples 27 28 29 30 31 32 33 34 Aliphatic
Polyamide Polyamide 66 Weight Average Molecular 80 80 80 80 80 80
80 80 Resin Weight of 90000 Semi-Aromatic Polyamide 10T 20 20 20 20
20 20 20 20 Polyamide Resin Bromine-Based Flame Brominated Epoxy
Resin 15 15 15 15 15 15 15 15 Retardant Auxiliary Flame Antimony
Trioxide Average Particle Size of 0.5 .mu.m 1.5 Retardant Average
Particle Size of 1.2 .mu.m 1.5 Average Particle Size of 3 .mu.m 1.5
Average Particle Size of 8 .mu.m Average Particle Size of 10 .mu.m
Average Particle Size of 12 .mu.m Antimony Tetroxide Average
Particle Size of 3 .mu.m 1.5 Antimony Pentoxide Average Particle
Size from 3 to 5 .mu.m 1.5 Sodium Antimonate Average Particle Size
of 4 .mu.m 1.5 Zinc Borate Average Particle Size of 3 .mu.m 1.5
Zinc Stannate Average Particle Size of 3 .mu.m 1.5 Evaluation
Glossiness .largecircle. .largecircle. .largecircle. .largecirc-
le. .largecircle. .largecircle. .largecircle. .largecircle.
Transparency .circle-w/dot. .largecircle. .largecircle.
.largecircle. .la- rgecircle. .largecircle. .DELTA. .largecircle.
Texture .circle-w/dot. .circle-w/dot. .circle-w/dot. .circle-w/dot.
.circ- le-w/dot. .circle-w/dot. .circle-w/dot. .circle-w/dot. Drip
Resistance .circle-w/dot. .circle-w/dot. .circle-w/dot.
.circle-w/do- t. .largecircle. .largecircle. .circle-w/dot.
.circle-w/dot. Self-Extinguishing Properties .largecircle.
.largecircle. .largecircle. .largecircle. .large- circle.
.largecircle. .largecircle. .largecircle. Processability
.circle-w/dot. .circle-w/dot. .circle-w/dot. .circle-w/dot- .
.circle-w/dot. .circle-w/dot. .circle-w/dot. .circle-w/dot. 35 36
37 38 39 40 41 42 Aliphatic Polyamide Polyamide 66 Weight Average
Molecular 80 80 80 80 80 80 80 80 Resin Weight of 90000
Semi-Aromatic Polyamide 10T 20 20 20 20 20 20 20 20 Polyamide Resin
Bromine-Based Flame Brominated Epoxy Resin 15 15 15 15 15 15 15 15
Retardant Auxiliary Flame Antimony Trioxide Average Particle Size
of 0.5 .mu.m Retardant Average Particle Size of 1.2 .mu.m Average
Particle Size of 3 .mu.m 0.1 3 5 10 13 Average Particle Size of 8
.mu.m 1.5 Average Particle Size of 10 .mu.m 1.5 Average Particle
Size of 12 .mu.m 1.5 Antimony Tetroxide Average Particle Size of 3
.mu.m Antimony Pentoxide Average Particle Size from 3 to 5 .mu.m
Sodium Antimonate Average Particle Size of 4 .mu.m Zinc Borate
Average Particle Size of 3 .mu.m Zinc Stannate Average Particle
Size of 3 .mu.m Evaluation Glossiness .largecircle. .largecircle.
.largecircle. .largecirc- le. .largecircle. .largecircle.
.largecircle. .largecircle. Transparency .circle-w/dot.
.largecircle. .DELTA. .circle-w/dot. .largeci- rcle. .largecircle.
.largecircle. .DELTA. Texture .circle-w/dot. .circle-w/dot.
.circle-w/dot. .circle-w/dot. .circ- le-w/dot. .circle-w/dot.
.circle-w/dot. .largecircle. Drip Resistance .circle-w/dot.
.circle-w/dot. .circle-w/dot. .largecircle- . .circle-w/dot.
.circle-w/dot. .circle-w/dot. .circle-w/dot. Self-Extinguishing
Properties .largecircle. .largecircle. .largecircle. .largecircle.
.circl- e-w/dot. .circle-w/dot. .circle-w/dot. .circle-w/dot.
Processability .circle-w/dot. .circle-w/dot. .largecircle.
.circle-w/dot.- .circle-w/dot. .circle-w/dot. .largecircle.
.largecircle.
TABLE-US-00004 TABLE 4 Examples 43 44 45 46 47 48 49 50 51
Aliphatic Polyamide Polyamide 66 Weight Average Molecular 80 80 80
80 80 80 80 80 80 Resin Weight of 90000 Semi-Aromatic Polyamide 10T
20 20 20 20 20 20 20 20 20 Polyamide Resin Auxiliary Flame Antimony
Trioxide Average Particle Size of 3 .mu.m 1.5 1.5 1.5 1.5 1.5 1.5
1.5 1.5 1.5 Retardant Organic Microparticles Crosslinked Nitrile AN
Ratio of 25 mass % 20 Rubber AN Ratio of 35 mass % 20 AN Ratio of
45 mass % 20 1 3 30 35 Crosslinked Silicone Resin 20 Crosslinked
Acrylic Resin 20 Evaluation Glossiness .circle-w/dot.
.circle-w/dot. .circle-w/dot. .circle- -w/dot. .circle-w/dot.
.largecircle. .circle-w/dot. .circle-w/dot. .circle- -w/dot.
Transparency .circle-w/dot. .circle-w/dot. .circle-w/dot.
.circle-w/dot. - .largecircle. .circle-w/dot. .circle-w/dot.
.circle-w/dot. .circle-w/dot. Texture .circle-w/dot. .circle-w/dot.
.circle-w/dot. .circle-w/dot. .circ- le-w/dot. .circle-w/dot.
.circle-w/dot. .circle-w/dot. .circle-w/dot. Drip Resistance
.circle-w/dot. .circle-w/dot. .circle-w/dot. .circle-w/do- t.
.circle-w/dot. .circle-w/dot. .circle-w/dot. .circle-w/dot.
.largecircl- e. Self-Extinguishing Properties .largecircle.
.largecircle. .largecircle. .largecircle. .large- circle.
.largecircle. .largecircle. .largecircle. .DELTA. Processability
.circle-w/dot. .circle-w/dot. .largecircle. .largecircle. -
.circle-w/dot. .circle-w/dot. .circle-w/dot. .circle-w/dot.
.largecircle.
TABLE-US-00005 TABLE 5 Comparative Examples 1 2 3 4 5 6 7 8 9
Aliphatic Polyannide Polyamide 66 Weight Average Molecular 100 100
100 100 80 Resin Weight of 90000 Weight Average Molecular 100
Weight of 50000 Semi-Aromatic Polyamide Polyannide 10T 100 Resin
Polyannide 9T 100 Polyannide 6T 100 Polyannide MXD6 20
Bromine-Based Flame Brominated Epoxy Resin 15 15 Retardant
Brominated Polystyrene Resin 15 Brominated Phenoxy Resin 15
Evaluation Glossiness xx xx xx xx xx .largecircle. .largecircle.
.largecir- cle. .largecircle. Transparency .circle-w/dot.
.circle-w/dot. .circle-w/dot. .circle-w/dot. - .circle-w/dot.
.largecircle. .largecircle. .largecircle. .largecircle. Texture
.circle-w/dot. .circle-w/dot. x x x .largecircle. .largecircle. .-
largecircle. .largecircle. Drip Resistance x xx x x x .largecircle.
.largecircle. .largecircle. .lar- gecircle. Self-Extinguishing
Properties x xx x x x .DELTA. .DELTA. .DELTA. .DELTA.
Processability .circle-w/dot. .circle-w/dot. .circle-w/dot.
.circle-w/dot- . .circle-w/dot. xx xx xx x
Regarding the materials in Tables 1 to 5, the followings were
employed. Polyamide 66 (weight average molecular weight of 50000):
AMILAN CM3001-N produced by Toray Industries, Inc. Polyamide 66
(weight average molecular weight of 65000): LEONA 1500 produced by
Asahi Kasei Chemicals Corp. Polyamide 66 (weight average molecular
weight of 90000): Zytel 42A produced by Du Pont K.K. Polyamide 66
(weight average molecular weight of 120000): product of the
applicant Polyamide 6 (weight average molecular weight of 90000):
product of the applicant Polyamide 10T: VESTAMID HO Plus M3000
produced by Daicel-Evonik Ltd. Polyamide 9T: Genestar N1000A-M42
produced by Kuraray Co., Ltd. Polyamide 6T: VESTAMID HP Plus M1000
produced by Daicel-Evonik Ltd. Polyamide MXD6: 56007 produced by
Mitsubishi Gas Chemical Co, Inc. Brominated epoxy resin: SRT-20000
produced by Sakamoto Yakuhin Kogyo Co., Ltd. Brominated polystyrene
resin: HP-7020 produced by Albemarle Corp. Brominated phenoxy
resin: YPB-43C produced by Nippon Steel & Sumikin Chemical Co.,
Ltd. Brominated phenol condensate: PYROGUARD SR-460B produced by
DKS Co. Ltd. Brominated benzil acrylate-based flame retardant:
FR-1025 produced by ICL-IP Ltd. Bromine-containing triazine-based
compound: PYROGUARD SR-245 produced by DKS Co. Ltd. Antimony
trioxide (average particle size of 0.5 .mu.m): PATOX-M produced by
Nihon Seiko Co., Ltd. Antimony trioxide (average particle size of
1.2 .mu.m): PATOX-K produced by Nihon Seiko Co., Ltd. Antimony
trioxide (average particle size of 3 .mu.m): PATOX-P produced by
Nihon Seiko Co., Ltd. Antimony trioxide (average particle size of 8
.mu.m): PATOX-L produced by Nihon Seiko Co., Ltd. Antimony trioxide
(average particle size of 10 .mu.m): product of the applicant
Antimony trioxide (average particle size of 12 .mu.m): product of
the applicant Antimony tetroxide (average particle size of 4
.mu.m): ATE-S produced by Yamanaka & Co., Ltd. Antimony
pentoxide (average particle size from 3 to 5 .mu.m): Sun Epoch
NA-1030 produced by Nissan Chemical Industries, Ltd. Sodium
antimonite (average particle size of 4 .mu.m): SA-A produced by
Nihon Seiko Co., Ltd. Zinc borate (average particle size of 3
.mu.m): product of the applicant Zinc stannate (average particle
size of 3 .mu.m): product of the applicant Crosslinked nitrile
rubber (AN ratio of 25 mass %): N240S produced by JSR Corp.
Crosslinked nitrile rubber (AN ratio of 35 mass %): Napo VP-402
produced by China Petrochemical Corp. Crosslinked nitrile rubber
(AN ratio of 45 mass %): BAYMOD N XL38.43 produced by Lanxess AG
Crosslinked silicone resin: EP5500 produced by Dow Corning Toray
Co., Ltd. Crosslinked acrylic resin: KMR-3TA produced by Soken
Chemical & Engineering Co., Ltd.
The weight average molecular weight (Mw) in Tables 1 to 5 was
measured by the following method.
Weight Average Molecular Weight Mw
The weight average molecular weight Mw was obtained by measurement
using the following equipment in the conditions below. Apparatus
used: Pump--shodex DS-4 Column--shodex GPC
HFIP-806M.times.2+HFIP-803 Detector--shodex RI-71 Eluate:
hexafluoroisopropanol (+additive CF3COONa (5 mmol/L)) Pretreatment:
filtration with a membrane filter (0.2 .mu.m) Concentration: 0.2
w/v % Injection volume: 100 .mu.L Column temperature: 40.degree. C.
Flow rate: 1.0 ml/min. Standard material: standard polymethyl
methacrylate (PMMA) Calibration curve was prepared using the
standard PMMA to represent the weight average molecular weight as
PMMA conversion value.
The evaluation items in Tables 1 to 5 were evaluated in the
respective methods and criteria as below.
Glossiness
The glossiness was visually observed for evaluation.
Three thousand fibers for artificial hair were prepared in a bundle
with a length of 20 cm to be observed in the sunlight for
determination in accordance with the following evaluation criteria.
.circle-w/dot.: Glossiness similar to human hair .largecircle.:
Glossiness not the same as but roughly close to human hair .DELTA.:
Glossiness not the same as human hair but roughly available for use
as fiber for artificial hair .times.: Glossiness apparently
different from human hair .times..times.: Glossiness apparently
different from human hair and noticeable glossiness typical of
synthetic fiber Flammability (Self-Extinguishing Properties, Drip
Resistance)
The flammability was evaluated in the aspects of
"self-extinguishing properties" and "drip resistance". For both
aspects of evaluation, the fiber for artificial hair was cut with a
length of 30 cm and the number of fibers with a weight of 2 g was
separated to prepare a fiber bundle sample. An end of the fiber
bundle was fixed to be vertically hung, and the lower end was in
contact with a flame with a length of 20 mm for 5 seconds, followed
by respective measurement of fire spread time after removal from
the flame and the number of dripping during the time for
determination as follows. For the result of measurement, an average
of three measurements was used.
Self-Extinguishing Properties
.circle-w/dot.: Fire spread time within 1 second .largecircle.:
Fire spread time of 2 seconds or more and less than 5 seconds
.DELTA.: Fire spread time of 6 seconds or more and less than 10
seconds .times.: Fire spread time of 10 seconds or more and less
than 20 seconds .times..times.: Fire spread time of 20 seconds or
more Drip Resistance .circle-w/dot.: No drippings found
.largecircle.: 1 or more and less than 2 drippings found .DELTA.: 3
or more and less than 5 drippings found .times.: 6 or more and less
than 10 drippings found .times..times.: 10 or more drippings found
Texture
The texture was evaluated by the evaluation criteria below,
bundling each fiber for artificial hair in Examples and Comparative
Examples with a length of 200 mm and a weight of 1.0 g to be
touched with the hand of 10 artificial hair fiber treatment
engineers (with 5 years or more of practical experience) for
determination. .circle-w/dot.: Evaluated as good texture by all 10
engineers .largecircle.: Evaluated as good texture by 8 or 9
engineers .DELTA.: Evaluated as good texture by 5 or more and 7 or
less engineers .times.: Evaluated as good texture by 2 or more and
4 or less engineers .times..times.: Evaluated as good texture by 1
or less engineer Processability
A bundle of 100 fibers of undrawn yarn was drawn at a draw ratio of
3 and the number of yarn breaking during the drawing was determined
for evaluation by the following evaluation criteria.
.circle-w/dot.: 0 yarn breakings/30 min. .largecircle.: 1 or more
and less than 3 yarn breakings/30 min. .DELTA.: 3 or more and less
than 10 yarn breakings/30 min. .times.: 10 or more and less than 20
yarn breakings/30 min. .times..times.: 20 or more yarn breakings/30
min. Transparency
The transparency was evaluated by the evaluation criteria below,
bundling each fiber for artificial hair in Examples and Comparative
Examples with a length of 200 mm and a weight of 1.0 g to be
visually observed by 10 artificial hair fiber treatment engineers
(with 5 years or more of practical experience) for comparison with
human hair. .circle-w/dot.: Transparency similar to human hair
.largecircle.: Transparency not the same as but roughly close to
human hair .DELTA.: Transparency containing opacity slightly more
than human hair but roughly available for use as fiber for
artificial hair .times.: Apparent opacity with difference from
human hair .times..times.: Apparent opacity and not available for
use as fiber for artificial hair Discussion
As described in Examples and Comparative Examples above, it was
found that use of a resin composition, as a material, containing
aliphatic polyamide, semi-aromatic polyamide with a skeleton
obtained by polycondensation of aliphatic diamine and aromatic
dicarboxylic acid, and a bromine-based flame retardant enabled
production of fiber for artificial hair having both drip resistance
during combustion and excellent texture and productivity.
It was also found that addition of the auxiliary flame retardant in
an appropriate amount allowed even more improvement in drip
resistance and self-extinguishing properties during combustion and
even more. It was further found that addition of the organic
microparticles in an appropriate amount allowed the glossiness to
be even more like human hair.
Examples and Comparative Examples are analyzed in more detail
below.
Comparing Examples 1 to 3, it was found that the cases of using
polyamide 10T or polyamide 6T, among semi-aromatic polyamides,
provided particularly good texture and the case of using polyamide
10T provided particularly good drip resistance and
processability.
Comparing Examples 1 and 4 to 10, it was found that the cases of
using 50 parts by mass or more of aliphatic polyamide provided
particularly good texture and the cases of using 10 parts by mass
or more of semi-aromatic polyamide provided particularly good
processability.
Comparing Examples 1 and 11 to 13, it was found that the cases of
using aliphatic polyamide with a weight average molecular weight of
65 thousand or more provided particularly good drip resistance.
Comparing Examples 1 and 14, it was found that either case of using
polyamide 66 or polyamide 6 as aliphatic polyamide provided the
same evaluation results.
Comparing Examples 1 and 15 to 20, it was found that the case of
using the brominated epoxy resin, the brominated polystyrene resin,
or the brominated phenoxy resin as the bromine-based flame
retardant provided particularly good processability. It was also
found that the case of using the brominated epoxy resin, the
brominated phenoxy resin, the brominated phenol condensate, or the
brominated benzil acrylate-based flame retardant provided
particularly good transparency. It was also found that the case of
using the brominated epoxy resin or the brominated phenoxy resin
provided particularly good processability and transparency. Since
both the brominated epoxy resin and the brominated phenoxy resin
used in Examples had the structural formula represented by the
chemical formula (1), it was found that a bromine-based flame
retardant having the structure of chemical formula (1) was most
preferred.
Comparing Examples 21 to 26, it was found that the cases of using 3
parts by mass or more of the bromine-based flame retardant provided
good self-extinguishing properties and the cases of 30 parts by
mass or more provided particularly good self-extinguishing
properties. It was also found that the cases of using 10 parts by
mass or more of the bromine-based flame retardant provided
particularly good glossiness. It was also found that the cases of
using 30 parts by mass or less of the bromine-based flame retardant
provided good processability and the cases of using 20 parts by
mass or less provided particularly good processability.
Comparing Examples 27 to 32, it was found that the case of using
antimony trioxide as the auxiliary flame retardant provided
particularly good transparency and drip resistance. Comparing
Examples 27 and 33 to 37, it was further found that the cases of
using the auxiliary flame retardant with an average particle size
from 1 to 10 .mu.m provided good transparency and the cases from 3
to 8 .mu.m provided particularly good transparency. Comparing
Examples 27 and 38 to 42, it was further found that the cases of
using from 0.1 to 10 parts by mass of the auxiliary flame retardant
provided good texture and transparency and the cases from 1 to 5
parts by mass provided particularly good processability and drip
resistance.
Comparing Examples 43 to 47, it was found that the case of using
crosslinked nitrile rubber with an AN ratio from 30 to 50 mass % as
the organic microparticles provided particularly good transparency
and processability. Comparing Examples 43 and 48 to 51, it was
found that the cases of using from 3 to 30 parts by mass of the
organic microparticles provided particularly good glossiness,
processability, and self-extinguishing properties.
Comparative Examples 1 to 5 containing no bromine-based flame
retardant had poor drip resistance. Comparative Examples 6 to 8
containing no semi-aromatic polyamide had poor processability.
Further, Comparative Example 9 containing polyamide MXD6, as
semi-aromatic polyamide, with a skeleton obtained by
polycondensation of aliphatic dicarboxylic acid and aromatic
diamine did not have good processability. From these results, it
was found that semi-aromatic polyamide with the specific skeleton
was essential for improvement in processability.
* * * * *