U.S. patent application number 10/590089 was filed with the patent office on 2007-08-09 for flame-retardant polyester artificial hair.
This patent application is currently assigned to KANEKA CORPORATION. Invention is credited to Toshiyuki Masuda.
Application Number | 20070184264 10/590089 |
Document ID | / |
Family ID | 34993454 |
Filed Date | 2007-08-09 |
United States Patent
Application |
20070184264 |
Kind Code |
A1 |
Masuda; Toshiyuki |
August 9, 2007 |
Flame-retardant polyester artificial hair
Abstract
It is an object of the present invention to provide a polyester
based artificial hair which has an excellent spinning
processability, maintains fiber properties such as heat resistance,
strength and elongation and the like, and has excellent curl
holding properties and iron setting properties. A flame retardant
polyester based artificial hair which has an excellent spinning
processability, maintains fiber properties such as heat resistance,
strength and elongation and the like, and has excellent curl
holding properties and iron setting properties can be obtained by
melt spinning a composition obtained by melt kneading a polyester,
a phosphorus containing flame retardant and/or a bromine containing
flame retardant and at least one compound selected from the group
consisting of a carbodiimide compound, a bisoxazoline compound and
an isocyanate compound.
Inventors: |
Masuda; Toshiyuki; (Hyogo,
JP) |
Correspondence
Address: |
BRINKS HOFER GILSON & LIONE
P.O. BOX 10395
CHICAGO
IL
60610
US
|
Assignee: |
KANEKA CORPORATION
Osaka
JP
530-8288
|
Family ID: |
34993454 |
Appl. No.: |
10/590089 |
Filed: |
March 16, 2005 |
PCT Filed: |
March 16, 2005 |
PCT NO: |
PCT/JP05/04627 |
371 Date: |
August 21, 2006 |
Current U.S.
Class: |
428/364 ;
252/601; 524/115 |
Current CPC
Class: |
Y10T 428/2913 20150115;
C08L 67/02 20130101; A61L 31/14 20130101; D01F 1/07 20130101; A61L
31/06 20130101; D01F 6/92 20130101; A41G 3/0083 20130101; A61L
31/06 20130101 |
Class at
Publication: |
428/364 ;
252/601; 524/115 |
International
Class: |
D02G 3/00 20060101
D02G003/00 |
Foreign Application Data
Date |
Code |
Application Number |
Mar 19, 2004 |
JP |
2004-079471 |
Claims
1. A flame retardant polyester based artificial hair, formed from a
composition having intrinsic viscosity of 0.5 to 1.4 which is
obtained by melt kneading 100 parts by weight of (A) a polyester
made of one or more of polyalkylene terephthalate or a copolymer
polyester comprising polyalkylene terephthalate as a main
component, 5 to 30 parts by weight of (B) a phosphorus containing
flame retardant and/or a bromine containing flame retardant and
0.05 to 10 parts by weight of (C) at least one compound selected
from the group consisting of a carbodiimide compound, a
bisoxazoline compound and an isocyanate compound.
2. The flame retardant polyester based artificial hair according to
claim 1, wherein the polyalkylene terephthalate is at least one
polymer selected from the group consisting of polyethylene
terephthalate, polypropylene terephthalate and polybutylene
terephthalate.
3. The flame retardant polyester based artificial hair according to
claim 1, wherein the polyester (A) is polyethylene terephthalate
reused by recycling from disposed PET bottles.
4. The flame retardant polyester based artificial hair according to
claim 1, 2 or 3, wherein the phosphorus containing flame retardant
and/or a bromine containing flame retardant (B) is at least one
compound selected from the group consisting of a phosphate
compound, a phophonate compond, a phosphinate comound, a phosphine
oxide compound, a phosphonite compound, a phosphinite compound, a
phosphine compound, and a condensed phosphate compound.
5. The flame retardant polyester based artificial hair according to
claim 1, 2 or 3, wherein the phosphorus containing flame retardant
and/or a bromine containing flame retardant (B) is at least one
compound selected from the group consisting of a bromine-containing
phosphate ester flame retardant, a brominated polystyrene flame
retardant, a brominated benzyl acrylate flame retardant, a
brominated epoxy flame retardant, a brominated phenoxy flame
retardant, a brominated polycarbonate flame retardant, a derivative
of tetrabromobisphenol-A, a bromine-containing triazine compound
and a bromine-containing isocyanuric acid compound
6. The flame retardant polyester based artificial hair according to
claim 1, wherein the at least one compound selected from the group
consisting of a carbodiimide compound, a bisoxazoline compound and
an isocyanate compound (C) is at least one compound selected from
the group consisting of p-phenylene-bis-o-tolylcarbodiimide,
p-phyenylene-bis-p-chlorophenyl carbodiimide, ethylene-bis-diphenyl
carbodiimide, poly(4,4'-methylene-bis-cyclohexyl carbodiimide),
poly(4,4'-diphenylmethane carbodiimide),
poly(3,3'-dimethyl-4,4'-diphenylmethane carbodiimide),
poly(naphtylene carbodiimide), poly(p-phenylene carbodiimide),
poly(m-phenylene carbodiimide), poly(tolylcarbodiimide),
poly(diisopropylphenylene carbodiimide),
poly(methyl-diisopropylphenylene carbodiimide),
poly(triethylphenylene carbodiimide) and poly(triisopropylphenylene
carbodiimide).
7. The flame retardant polyester based artificial hair according to
claim 1, wherein the at least one compound selected from the group
consisting of a carbodiimide compound, a bisoxazoline compound and
an isocyanate compound (C) is at least one compound selected from
the group consisting of 2,2'-bis(2-oxazoline),
2,2'-bis(4-methyl-2-oxazoline), 2,2'-bis(4,4-dimethyl-2-oxazoline),
2,2'-bis(4-phenyl-2-oxazoline), 2,2'-bis(4-cyclohexyl-2-oxazoline),
2,2'-bis(4-benzyl-2-oxazoline), 2,2'-p-phenylene-bis(2-oxazoline),
2,2'-m -phenylene-bis(2-oxazoline),
2,2'-o-phenylene-bis(2-oxazoline),
2,2'-p-phenylene-bis(4-methyl-2-oxazoline),
2,2'-p-phenylene-bis(4,4-dimethyl-2-oxazoline),
2,2'-m-phenylene-bis(4-methyl-2-oxazoline),
2,2'-m-phenylene-bis(4,4-dimethyl-2-oxazoline),
2,2'-ethylene-bis(2-oxazoline),
2,2'-tetramethylene-bis(2-oxazoline),
2,2'-tetramethylene-bis(4,4-dimethyl-2-oxazoline),
2,2'-9,9'-diphenoxylethane-bis(2-oxazoline),
2,2'-cyclohexylene-bis(2-oxazoline) and
2,2'-diphenylene-bis(2-oxazoline).
8. The flame retardant polyester based artificial hair according to
claim 1, wherein the at least one compound selected from the group
consisting of a carbodiimide compound, a bisoxazoline compound and
an isocyanate compound (C) is at least one compound selected from
the group consisting of 1,6-hexamethylene diisocyanate,
1,12-dodecamethylene diisocyanate, 2,2,4-trimethylhexamethylene
diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate, isophorone
diisocyanate, 1,4-cyclohexane diisocyanate,
4,4'-dicyclohexylmethane diisocyanate, hydrogenated xylylene
diisocyanate, p-phenylene diisocyanate, tolylene diisocyanate,
xylylene diisocyanate, 4,4'-diphenyl diisocyanate, 1,5-naphthalene
diisocyanate, 4,4'-diphenylmethane diisocyanate (MDI),
triphenylmethane triisocyanate and 4,4'-diphenylether
diisocyanate.
9. The flame retardant polyester based artificial hair according to
any of claim 1, which is in the form of a non-crimped fiber.
10. The flame retardant polyester based artificial hair according
to any of claim 1, which is spun dyed.
11. The flame retardant polyester based artificial hair according
to any of claim 1, which has a monofilament size of 10 to 100 dtex.
Description
TECHNICAL FIELD
[0001] The present invention relates to a flame retardant polyester
based artificial hair. The hair is formed from a composition
obtained by melt kneading a polyester, a flame-retardant comprising
phosphorus and/or a flame-retardant comprising bromine and at least
one compound selected from the group consisting of a carbodiimide
compound, a bisoxazoline compound and an isocyanate compound. More
particularly, the present invention relates to a flame retardant
polyester based artificial hair which has excellent spinning
processability, maintains fiber properties such as heat resistance,
strength and elongation and the like, and also has excellent curl
holding properties and iron setting properties.
BACKGROUND ART
[0002] Fibers made of polyethylene terephthalate or a polyester
comprising polyethylene terephthalate as a main component have a
high melting point, a high modulus of elasticity, excellent heat
resistance and chemical resistance. Thus, they are widely used in
curtains, carpets, clothes, blankets, sheetings, table clothes,
upholstery fabrics, wall coverings, artificial hair, interior
materials for automobiles, outdoor reinforcing materials, and
safety nets.
[0003] On the other hand, human hair or artificial hair (modacrylic
fibers, polyvinyl chloride fibers) or the like have conventionally
been used in hair products such as wigs, hair wigs, extensions,
hair bands, and doll hair. However, because it is now more
difficult to obtain human hair, the use of artificial hair has
become more important. Modacrylic fibers have often been used as
artificial hair materials because of their flame retardance.
However, they have insufficient heat resistance.
[0004] In recent years there has been proposed, as a main component
for artificial hair, a polyester typified by polyethylene
terephthalate which has excellent heat resistance. However, when
using a polyester as an artificial hair material, it has become
necessary to add flame-retardant property for purposes of
safety.
[0005] Since conventional polyester fibers are flammable, various
attempts have been made to improve the flame resistance of
polyester fibers. Known examples include using a fiber made of a
polyester obtained by copolymerizing a flame retardant monomer
containing a phosphorus atom. Examples also include adding a flame
retardant to a polyester fiber.
[0006] As a method which involves copolymerizing a flame retardant
monomer, for example, several methods have been proposed.
Copolymerizing a phosphorus compound with excellent heat stability
having a phosphorus atom as a ring member is disclosed in Japanese
Patent Publication No. 55-41610. Copolymerizing carboxyphosphinic
acid is also disclosed in Japanese Patent Publication No. 53-13479.
Also, copolymerizing or adding a phosphorus compound to a polyester
containing a polyarylate is disclosed in Japanese Laid-open Patent
No. 11-124732.
[0007] As artificial hair to which flame retardant technology is
applied, a polyester fiber copolymerized with a phosphorus compound
has been proposed in Japanese Laid-open Patent No.03-27105, for
example. However, since artificial hair is required to highly flame
resistant, the copolymer polyester fiber used for artificial hair
must have a high copolymerization amount. This results in a
significant decrease in heat resistance of the polyester, and
causes other problems which make it difficult to perform melt
spinning. Also, when a flame approaches, the artificial hair does
not catch fire and burn, but becomes molten and drips.
[0008] On the other hand, as a method which involves adding a flame
retardant, it has been proposed to add a halogenated cycloalkane
compound as fine particles to a polyester fiber, as disclosed in
Japanese Patent Publication No. 03-57990, or add a
bromine-containing alkylcyclohexane to a polyester fiber, as
disclosed in Japanese Patent Publication No. 01-24913. However, in
the method which involves adding a flame retardant to a polyester
fiber, in order to achieve sufficient flame retardance the addition
treatment temperature must be as high as 150.degree. C. or more,
the addition treatment time must be long, or a large amount of a
flame retardant must be used. This causes problems such as
deteriorated fiber properties, reduced productivity and an
increased production cost.
[0009] On the other hand, recently it has become necessary to
collect and recycle disposed polyester products in the interest of
reuse of material and environmental conservation. For example,
bottles for liquid foods made of polyethylene terephthalate use
polyester in a large amount and consumption of those bottles is
expected to increase in the future. Accordingly it is worthwhile to
collect and recycle those polyethylene terephthalate bottles and,
in fact, all attempts to do so have been launched.
[0010] In a conventional process for producing polyester fibers for
clothes, conditions for drawing are adjusted to produce polyester
fibers having an elongation at break of 30%. When the recycled
polyester is spun to produce fibers having such conditions for
drawing, thread breakages frequently take place due to additives
and foreign bodies in the polyester. This results in substantially
deteriorated operational efficiency. Accordingly, it has been
difficult to spin recycled polyester to produce versatile
multi-filaments for clothes.
[0011] In order to commercially produce polyester fibers while
maintaining fiber properties, polyester fibers must contain
impurities of 5% or less. Therefore, recycled polyester bottles
separated from impurities must be used as raw materials. However,
since bottles for liquid food products are filled with heat
sterilized liquid, the bottle's mouth part is required to be heat
resistant to a certain extent. Therefore materials other than
polyester are often used for the mouth part of the polyester
bottles. When polyester bottles are used as raw materials, it is
difficult to remove these different materials.
[0012] As described above, artificial hair fiber which retains the
fiber properties possessed by conventional polyester fiber; such as
heat resistance, strength and elongation and the like, and also has
excellent setting properties and flame retardance, has not yet been
produced. Furthermore, artificial hair fiber formed from collected
and recycled polyester which has excellent setting properties and
flame retardance has not yet been produced.
DISCLOSURE OF THE INVENTION
[0013] An object of the present invention is to provide a flame
retardant polyester based artificial hair which has excellent
spinning processability, maintains fiber properties such as heat
resistance, strength and elongation and the like and also has
excellent curl holding properties and iron setting properties, is
achieved by solving the aforedescribed existing problems.
[0014] In order to solve the aforedescribed problems, the inventors
have conducted intensive studies. They have found that a flame
retardant polyester based artificial hair which have excellent
spinning processability, maintains fiber properties such as heat
resistance, strength and elongation and the like and also has
excellent curl holding properties and iron setting properties, can
be obtained by melt spinning a composition comprising a polyester,
a phosphorus containing flame retardant and/or a bromine containing
flame retardant and at least one compound selected from the group
consisting of a carbodiimide compound, a bisoxazoline compound and
an isocyanate compound.
[0015] Specifically, the present invention relates to a flame
retardant polyester based artificial hair, formed from a
composition having intrinsic viscosity of 0.5 to 1.4 which is
obtained by melt kneading 100 parts by weight of (A) a polyester
made of one or more of polyalkylene terephthalate or a copolymer
polyester comprising polyalkylene terephthalate as a main
component, 5 to 30 parts by weight of (B) a phosphorus containing
flame retardant and/or a bromine containing flame retardant and
0.05 to 10 parts by weight of (C) at least one compound selected
from the group consisting of a carbodiimide compound, a
bisoxazoline compound and an isocyanate compound.
[0016] Furthermore, the present invention relates to the flame
retardant polyester based artificial hair wherein the fiber is
preferably non-crimped and spun dyed, and the size of a single
fiber is 10 to 100 dtex.
[0017] According to the present invention, flame retardant
polyester based artificial hair can be obtained which has excellent
spinning processability, maintains fiber properties such as heat
resistance, strength and elongation and the like and also has
excellent curl holding properties and iron setting properties.
BEST MODE FOR CARRYING OUT THE INVENTION
[0018] The flame retardant polyester based artificial hair of the
present invention is a fiber obtained by melt spinning a
composition having an intrinsic viscosity of 0.5 to 1.4, which
composition is obtained by melt kneading (A) a polyester made of
one or more of polyalkylene terephthalate or a copolymer polyester
comprising polyalkylene terephthalate as a main component, (B) a
phosphorus containing flame retardant and/or a bromine containing
flame retardant and (C) at least one compound selected from the
group consisting of a carbodiimide compound, a bisoxazoline
compound and an isocyanate compound.
[0019] Examples of the polyalkylene terephthalate or the copolymer
polyester comprising polyalkylene terephthalate as a main
component, which is contained in the polyester (A) used in the
present invention, include polyalkylene terephthalates such as
polyethylene terephthalate, polypropylene terephthalate, and
polybutylene terephthalate, and a copolymer polyester comprising
such polyalkylene terephthalate as a main component and a small
amount of a copolymerization component. Further flakes of disposed
PET bottles can also be reused. The phrase "comprising as a main
component" refers to "comprising in an amount of 80 mol % or
more".
[0020] Examples of the copolymerization component include:
polycarboxylic acids such as isophthalic acid, orthophthalic acid,
naphthalenedicarboxylic acid, paraphenylenedicarboxylic acid,
trimellitic acid, pyromellitic acid, succinic acid, glutaric acid,
adipic acid, suberic acid, azelaic acid, sebacic acid, and
dodecanedioic acid, and their derivatives; dicarboxylic acids
having sulfonic acid salt such as 5-sodium sulfoisophthalic acid,
dihydroxyethyl 5-sodium sulfoisophthalate, and their derivatives;
1,2-propanediol, 1,3-propanediol, 1,4-butanediol, 1,6-hexanediol,
neopentyl glycol, 1,4-cyclohexanedimethanol, diethylene glycol,
polyethylene glycol, trimethylolpropane, pentaerythritol,
4-hydroxybenzoic acid, and .epsilon.-caprolactone.
[0021] Typically, the copolymer polyester is preferably produced by
adding a small amount of a copolymerization component to a main
component which is a polymer of terephthalic acid and/or its
derivative (for example, methyl terephthalate) and alkylene glycol,
and reacting these components with a view toward stability and
convenience for handling. However, the copolymer polyester may be
produced by adding a small amount of a monomer or oligomer
component as a copolymerization component to a main component which
is a mixture of terephthalic acid and/or its derivative (for
example, methyl terephthalate) and alkylene glycol, and
polymerizing the components.
[0022] The copolymer polyester may be any copolymer polyester in
which the copolymerization component is polycondensed with the main
chain and/or the side chain of polyalkylene terephthalate as a main
component. There are no particular limitations to the manner of
copolymerization and the like.
[0023] Examples of the copolymer polyester comprising polyalkylene
terephthalate as a main component include: a polyester obtained by
copolymerizing polyethylene terephthalate as a main component with
ethylene glycol ether of bisphenol A; a polyester obtained by
copolymerizing polyethylene terephthalate as a main component with
1,4-cyclohexanedimethanol; and a polyester obtained by
copolymerizing polyethylene terephthalate as a main component with
dihydroxyethyl 5-sodium sulfoisophthalate. The polyalkylene
terephthate and its copolymer polyester may be used singly or in a
combination of two or more.
[0024] Preferable examples thereof include polyethylene
terephthalate, polypropylene terephthalate, polybutylene
terephthalate, and a copolymer polyester (a polyester obtained by
copolymerizing polyethylene terephthalate as a main component with
ethylene glycol ether of bisphenol A; a polyester obtained by
copolymerizing polyethylene terephthalate as a main component with
1,4-cyclohexanedimethanol; a polyester obtained by copolymerizing
polyethylene terephthalate as a main component with dihydroxyethyl
5-sodium sulfoisophthalate; or the like). A mixture of two or more
of these is also preferable.
[0025] The phosphorus containing flame retardant and/or a bromine
containing flame retardant (B) used in the present invention is not
particularly limited, and generally used phosphorus containing
flame retardants can be used.
[0026] Examples of the phosphorus containing flame retardant used
for the phosphorus containing flame retardant and/or the bromine
containing flame retardant (B) used in the present invention
include a phosphate compound, a phosphonate compound, a phosphinate
compound, a phosphine oxide compound, a phosphonite compound, a
phosphinite compound, a phosphine compound and a condensed
phosphate compound represented by the general formula (1).
##STR1##
[0027] wherein R.sup.1 groups represent a monovalent aromatic
hydrocarbon group or aliphatic hydrocarbon group, and may be the
same or different; R.sup.2 represents a divalent aromatic
hydrocarbon group, and when two or more R.sup.2 groups are present,
the groups may be the same or different; and n is 0 to 15.
[0028] These may be used alone or as a mixture of two or more
thereof.
[0029] Specific examples of the phosphorus containing flame
retardant include trimethyl phosphate, triethyl phosphate, tributyl
phosphate, tri(2-ethylhexyl) phosphate, triphenyl phosphate,
tricresyl phosphate, trixylenyl phosphate, tris(isopropylphenyl)
phosphate, tris(phenylphenyl) phosphate, trinephthyl phosphate,
cresylphenyl phosphate, xylenyl diphenyl phosphate, triphenyl
phosphine oxide, tricresyl phosphine oxide, diphenyl
methanephosphonate and diethyl phenylphosphonate, as well as
resorcinol polyphenyl phosphate, resorcinol poly(di-2,6-xylyl)
phosphate, bisphenol A polycresyl phosphate, hydroquinone
poly(2,6-xylyl) phosphate, and condensed phosphate compounds
represented by the following formulas: ##STR2##
[0030] Among these compounds, the condensed phosphate compounds
represented by the general formula (1) are preferable.
[0031] The bromine containing flame retardant used for the
phosphorus containing flame retardant and/or the bromine containing
flame retardant (B) used in the present invention is not
particularly limited, and generally used bromine containing flame
retardants can be employed.
[0032] Specific examples of the bromine containing flame retardant
used for the phosphorus containing flame retardant and/or the
bromine containing flame retardant (B) used in the present
invention include pentabromotoluene, hexabromobenzene,
decabromobiphenyl, decabromodiphenyl ether,
bis(tribromophenoxy)ethane, tetrabromophthalic anhydride, ethylene
bis(tetrabromophthalimide), ethylene bis(pentabromophenyl),
octabromotrimethylphenylindane, bromine-containing phosphate esters
such as tris(tribromoneopentyl)phosphate, brominated polystyrenes,
brominated polybenzyl acrylates, brominated epoxy oligomers,
brominated phenoxy resins, brominated polycarbonate oligomers,
derivatives of tetrabromobisphenolA such as tetrabromobisphenolA,
tetrabromobisphenolA-bis(2,3-dibromopropyl ether),
tetrabromobisphenolA-bis(allylether),
tetrabromobisphenolA-bis(hydroxyethyl ether), bromine-containing
triazine based compounds such as tris(tribromophenoxy) triazine and
bromine-containing isocyanuric acid based compound such as
tris(2,3-dibromopropyl) isocyanurate. These may be used alone or at
least two kinds thereof may be used in combination.
[0033] Among these, a bromine-containing phosphate ester based
flame retardant, a brominated polystyrene based flame retardant, a
brominated benzyl acrylate based flame retardant, a brominated
polycarbonate based flame retardant, a derivative of tetrabromobis
phenol-A, a bromine-containing triazine based compound and a
bromine-containing isocyanuric acid based compound are
preferable.
[0034] The amount of the phosphorus containing flame retardant
and/or the bromine containing flame retardant (B) is preferably 5
to 30 parts by weight, more preferably 6 to 25 parts by weight,
and, further more preferably 7 to 20 parts by weight based on 100
parts by weight of the polyester (A). If the amount of the
phosphorus containing flame retardant and/or the bromine containing
flame retardant (B) is less than 5 parts by weight, the effect of
flame resistance tends to hardly be obtained, and if more than 30
parts by weight, mechanical properties, heat resistance and drip
resistance tend to be damaged.
[0035] The carbodiimide compound used as (C) component in the
present invention is a compound having at least two carbodiimide
groups represented by (--N.dbd.C.dbd.N--) and is not particularly
limited. Examples of carbodiimide compound include mono- or
di-carbodiimide compounds such as diphenyl carbodiimide,
dicyclohexyl carbodiimide, di-2,6-dimethylphenyl carbodiimide,
diisopropyl carbodiimide, dioctyldecyl carbodiimide,
di-o-tolylcarbodiimide, N-tolyl-N'-phenyl carbodiimide,
N-tolyl-N'-cyclohexyl carbodiimide, di-p-tolylcarbodiimide,
di-p-nitrophenyl carbodiimide, di-p-aminophenyl carbodiimide,
di-p-hydroxyphenyl carbodiimide, di-p-chlorophenyl carbodiimide,
di-o-chlorophenyl carbodiimide, di-3,4-dichlorophenyl carbodiimide,
di-2,5-dichlorophenyl carbodiimide,
p-phenylene-bis-o-tolylcarbodiimide, p-phenylene-bis-dicyclohexyl
carbodiimide, p-phyenylene-bis-di-p-chlorophenyl carbodiimide,
hexamethylene-bis-di-cyclohexyl carbodiimide, ethylene-bis-diphenyl
carbodiimide and ethylene-bis-di-cyclohexyl carbodiimide;
polycarbodiimides such as poly(1,6-hexamethylene carbodiimide),
poly(4,4'-methylene-bis-cyclohexyl carbodiimide),
poly(1,3-cyclohexylene carbodiimide, and poly(1,4-cyclohexylene
carbodiimide); and aromatic polycarbodiimides such as
poly(4,4'-diphenylmethane carbodiimide),
poly(3,3'-dimethyl-4,4'-diphenylmethane carbodiimide),
poly(naphtylene carbodiimide), poly(p-phenylene carbodiimide),
poly(m-phenylene carbodiimide), poly(tolylcarbodiimide),
poly(diisopropylphenylene carbodiimide),
poly(methyl-diisopropylphenylene carbodiimide),
poly(triethylphenylene carbodiimide) and poly(triisopropylphenylene
carbodiimide). As commercial available products, there are Bayer
AG's STABAXOL I and STABAXOL P (both registered trade names). The
aforementioned carbodiimide compounds may be used either alone or
in combination of two or more.
[0036] The bisoxazoline compound used as component (C) in the
present invention is not particularly limited. Examples of the
oxazoline compound include 2,2'-methylene-bis(2-oxazoline),
2,2'-ethylene-bis(2-oxazoline), 2,2'-ethylene-bis
(4-methyl-2-oxazoline), 2,2'-propylene-bis(2-oxazoline),
2,2'-tetramethylene-bis(2-oxazoline),
2,2'-hexamethylene-bis(2-oxazoline),
2,2'-octamethylene-bis(2-oxazoline),
2,2'-p-phenylene-bis(2-oxazoline),
2,2'-p-phenylene-bis(4-methyl-2-oxazoline),
2,2'-p-phenylene-bis(4,4'-dimethyl-2-oxazoline),
2,2'-p-phenylene-bis(4-phenyl-2-oxazoline),
2,2'-m-phenylene-bis(2-oxazoline),
2,2'-m-phenylene-bis(4-methyl-2-oxazoline),
2,2'-m-phenylene-bis(4,4'-dimethyl-2-oxazoline),
2,2'-m-phenylene-bis(4-phenyl-2-oxazoline),
2,2'-o-phenylene-bis(2-oxazoline), 2,2'-bis(2-oxazoline),
2,2'-bis(4-methyl-2-oxazoline), 2,2'-bis(4-phenyl-2-oxazoline), and
the like. The aforementioned bisoxazoline compounds may be used
either alone or in combination of two or more.
[0037] The isocyanate compound used as component (C) in the present
invention may be various aliphatic diisocyanates or aromatic
diisocyanates. The alkylene group in the aliphatic diisocyanates is
not limited to a straight structure but may be branched structure
or alicyclic structure. The alkylene group may contain oxygen atom.
The aromatic diisocyanates is not particularly limited provided
that divalent aromatic hydrocarbon group is contained in the
molecule.
[0038] Examples of aliphatic diisocyanetes include 1,3-trimethylene
diisocyanate, 1,4-tetramethylene diisocyanate, 1,6-hexamethylene
diisocyanate, 1,9-nonamethylene diisocyanate, 1,10-decamethylene
diisocyanate, 1,12-dodecamethylene diisocyanate, hexamethylene
diisocyanate-biuret, 2,2,4-trimethylhexamethylene diisocyanate,
2,4,4-trimethylhexamethylene diisocyanate, isophorone diisocyanate,
1,4-cyclohexane diisocyanate, 4,4'-dicyclohexylmethane
diisocyanate, hydrogenated xylylene diisocyanate, 2,2'-diethylether
diisocyanate and the like.
[0039] Examples of aromatic diisocyanetes include p-phenylene
diisocyanate, tolylene diisocyanate, xylylene diisocyanate,
4,4'-diphenyl diisocyanate, 1,5-naphthalene diisocyanate,
4,4'-diphenylmethane diisocyanate,
3,3'-methyleneditolylene-4,4'-diisocyanate,
tolylenediisocyanate-trimethylolpropane adduct, triphenylmethane
triisocyanate, 4,4'-diphenylether diisocyanate,
tetrachlorophenylene diisocyanate,
3,3'-dichloro-4,4'-diphenylmethane diisocyanate and triisocyanate
phenylthiophosphate. The aforementioned isocyanate compounds may be
used either alone or in combination of two or more.
[0040] The amount of the at least one compound selected from the
group consisting of a carbodiimide compound, a bisoxazoline
compound and an isocyanate compound (C) to be used in the present
invention is 0.05-10 parts by weight, preferably 0.1-8 parts by
weight, more preferably 0.2-6 parts by weight based on 100 parts by
weight of the polyester (A). If the amount of the at least one
compound selected from the group consisting of a carbodiimide
compound, a bisoxazoline compound and an isocyanate compound (C) to
be used is less than 0.05 parts by weight, the advantageous effects
that the flowability is lowered and bleeding is prevented tend to
be insufficient. If it exceeds 10 parts by weight, flame retardance
and mechanical strength of the flame retardant polyester based
artificial hair tend to be deteriorated.
[0041] The composition of the present invention obtained by melt
kneading the components (A), (B) and (C) can have a excellent
spinning property by controlling the amount of component (C) and
adjusting the intrinsic viscosity to 0.5 to 1.4. The composition
has an intrinsic viscosity of preferably 0.5 to 1.4, and more
preferably 0.6 to 1.2. If the intrinsic viscosity is less than 0.5,
the resulting fiber tends to have reduced mechanical strength. If
more than 1.4, the melt viscosity is increased as the molecular
weight is increased, and thus the fiber tends to be melt spun only
with difficulty, and to have a non-uniform size.
[0042] The flame retardant polyester composition used in the
present invention can be produced by, for example, dry blending the
components (A), (B) and (C) in advance and then melt kneading the
components in various conventional kneading machines. Examples of
the kneading machines include a single-screw extruder, twin-screw
extruder, roll, Banbury mixer and kneader. Of these, a twin-screw
extruder is preferable in terms of adjustment of the kneading
degree and convenience of operation.
[0043] The composition for the present invention can be obtained
by, for example, melt-kneading at a barrel temperature of 260 to
300.degree. C., a discharge mount of 50 to 150 kg/hr, and a screw
rotational speed of 150 to 200 rpm with a twin screw extruder
having a screw diameter of 45 mm, taking up a strand out of dies,
and after cooling with water, pelletizing the strand with a strand
cutter.
[0044] The flame retardant polyester based artificial hair of the
present invention can be produced by melt spinning the
above-described polyester composition by a typical melt spinning
process. Specifically, a spun yam can be obtained by, for example:
melt spinning the composition while setting an extruder, gear pump,
spinneret, and the like at a temperature of 270 to 310.degree. C.;
allowing the spun yarn to pass through a heat sleeve; then cooling
the yarn to a glass transition temperature or lower; and taking off
the yarn at a rate of 50 to 5,000 m/min. The size of the spun yarn
can also be controlled by cooling the yarn in a tank filled with
cooling water. The temperature or length of the heat sleeve, the
temperature or spraying amount of cooling air, the temperature of
the cooling tank, the cooling time, and the take-off rate can be
appropriately adjusted according to the discharge amount and the
number of holes in the spinneret.
[0045] The resulting spun yarn may be hot drawn by either a
two-step process comprising winding up the spun yam once and then
drawing the yarn, or a direct spinning and drawing process
comprising successively drawing the spun yarn without winding. Hot
drawing is carried out by a one-stage drawing process or a
multistage drawing process. As a heating means in hot drawing, a
heat roller, heat plate, steam jet apparatus, hot water tank, or
the like can be used. These can be appropriately used in
combination.
[0046] The polyester based artificial hair of the present invention
may contain various additives such as a heat resistant agent, a
photostabilizer, a fluorescent agent, an antioxidant, an antistatic
agent, a pigment, a plasticizer, and a lubricant as required. The
fiber containing a pigment can be provided as a spun dyed
fiber.
[0047] When the polyester based artificial hair of the present
invention thus obtained is a fiber in the form of a non-crimped
fiber, and has a size of usually 10 to 100 dtex, and furthermore 20
to 90 dtex, it is suitable for artificial hair. Preferably, the
artificial hair has heat resistance sufficient to allow a thermal
beauty appliance (hair iron) to be used thereon at 160 to
200.degree. C. Preferably, the artificial hair catches fire only
with difficulty, and has self-extinguishing properties.
[0048] When the polyester based artificial hair of the present
invention is spun dyed, the artificial hair can be used as is. When
the artificial hair is not spun dyed, it can be dyed under the same
conditions as with a common flame retardant polyester fiber. The
pigment, dye, adjuvant, or the like used for dyeing preferably
exhibits excellent weather resistance and flame retardance.
[0049] The polyester based artificial hair of the present invention
exhibits excellent curl setting properties when a thermal beauty
appliance (hair iron) is used, and also exhibits excellent curl
holding properties. The artificial hair can be appropriately matted
with irregularities on the fiber surface and can be used for
artificial hair. Further, an oil agent such as a fiber surface
treating agent or a softening agent can provide the fiber with
feeling and texture closer to human hair.
[0050] The flame retardant polyester besed artificial hair of the
present invention may be used in combination with another material
for artificial hair, such as a modacrylic fiber, a polyvinyl
chloride fiber, or a nylon fiber, or it may be used in combination
with human hair.
[0051] Next, the present invention will be described in more detail
with reference to Examples. However, it should be understood that
the present invention is not limited thereto.
EXAMPLES
[0052] Properties values in the present invention are measured as
follows.
[0053] (Intrinsic Viscosity of Polyester)
[0054] A solution at a concentration of 0.5 g/dl in a mixed solvent
of equal weights of phenol and tetrachloroethane is measured for
its relative viscosity at 25.degree. C. with an Ubbellohde
viscometer, and the intrinsic viscosity is calculated from the
following formula: [ n ] = lim C .fwdarw. 0 .times. .times. .eta.
sp / C = lim C .fwdarw. 0 .times. ( .eta. rel - 1 ) / C = lim C
.fwdarw. 0 .times. ( .eta. - .eta. 0 ) / .eta. 0 .times. C
##EQU1##
[0055] wherein .eta. is the viscosity of the solution, .eta..sub.0
is the viscosity of the solvent, .eta..sub.rel is relative
viscosity, .eta..sub.sp is specific viscosity, [.eta.] is intrinsic
viscosity, and C is the concentration of the solution.
[0056] (Strength and Elongation)
[0057] Tensile strength and elongation of a filament are measured
using INTESCO Model 201 manufactured by INTESCO Co., Ltd. Both 10
mm-long ends of one 40 mm-long filament are sandwiched in a board
(thin paper) to which a two-sided tape applied with an adhesive is
bonded, and are air-dried overnight to prepare a sample with a
length of 20 mm. The sample is mounted on a test machine, and a
test is carried out at a temperature of 24.degree. C., at a
humidity of 80% or less, at a load of 1/30 gF.times. size (denier)
and at a tensile rate of 20 mm/min to measure strength and
elongation. The test is repeated ten times under the same
conditions, and the average values are defined as strength and
elongation of the filament.
[0058] (Heat Resistance)
[0059] A thermal shrinkage ratio of filaments is used as an index
of heat resistance. A thermal shrinkage ratio is measured by using
a SC5200H thermal analyzer TMA/SS150C manufactured by Seiko
Instruments Inc. Ten pieces of filaments having a length of 10 mm
are adopted, and a load of 5.55 mg/dtex is applied thereto. The
thermal shrinkage ratio of the filaments is measured at a speed of
temperature increase of 3.degree. C./min in a range of 30 to
280.degree. C.
[0060] (Flame Retardance)
[0061] A filament having a size of 50 dtex is cut into filaments
with a length of 150 mm each. Filaments with a weight of 0.7 g are
bundled, with one end of the bundle sandwiched by a clamp, and the
bundle is fixed on a stand and hung vertically. The fixed filaments
with an effective length of 120 mm are brought into contact with a
20 mm-long flame for 3 seconds and burned. Flammability is
evaluated as follows.
[0062] Very good: After-flame time is 0 second (Filaments do not
catch fire)
[0063] Good: After-flame time is less than 3 seconds
[0064] Fair: After-flame time is 3 to 10 seconds
[0065] Bad: After-flame time is more than 10 seconds Drip
resistance is evaluated as follows.
[0066] Very good: The number of drips is 0
[0067] Good: The number of drips is 5 or less
[0068] Fair: The number of drips is 6 to 10
[0069] Bad: The number of drips is 11 or more
[0070] (Curl Setting Properties)
[0071] Straw-haired filaments are wound around a pipe with a
diameter of 32 mm. Curl setting is performed by steam under
conditions at 120.degree. C. and relative humidity of 100% for 60
minutes, and aging is performed at room temperature for 60 minutes.
Then, one end of the curled filaments is fixed, and the filaments
are hung down to visually evaluate curling state. Curling state is
regarded as an indication of the ease of curling. A state with a
smaller length and with curl in sufficient form is preferable.
[0072] Good: curl in sufficient form
[0073] Fair: curl relaxed a little
[0074] Bad: curl loosened and form collapsed
[0075] (Iron Setting Properties)
[0076] Iron setting properties are an index of the extent to which
a hair iron can perform curl setting easily and hold the curl
shape. Filaments are loosely sandwiched in a hair iron heated to
180.degree. C., and pre-heated three times by rubbing. Adhesion
among the filaments, combing, crimping and end breakage of the
filaments are visually evaluated at this time. Next, the pre-heated
filaments are wound around the hair iron and held for 10 seconds,
after which the iron is withdrawn. The degree of ease with which
the iron is withdrawn (rod withdrawal properties), and curl holding
properties when the iron is withdrawn are visually evaluated.
Examples (No. 1 to 8)
[0077] Compositions having components ratios shown in Table 1 below
were dried so as to have a moisture content of 100 ppm or less. To
each of these compositions, 2 parts of a coloring polyester pellet
PESM6100 BLACK (manufactured by Dainichiseika Color & Chemicals
Mfg. Co., Ltd., carbon black content: 30%, polyester contained in
the component (A)) were added. The compositions were dry blended.
The blend was fed into a twin-screw extruder and melt kneaded at
280.degree. C. to form a pellet. Then, the pellet was dried to a
moisture content of 100 ppm or less. Next, the pellet was put into
a melt spinning machine, and the molten polymer was discharged from
a spinneret having round cross-sectional nozzle holes with a nozzle
diameter of 0.5 mm and each nozzle at 280.degree. C. The discharged
polymer was air cooled with cooling wind of 20.degree. C. and
rolled up at a rate of 100 m/min to obtain un-drawn yarns. The
obtained un-drawn yarn was drawn to form a four-fold drawn yarn by
using a heat roll heated at 85.degree. C., heat treated by using a
heat roll heated at 200.degree. C. and rolled up at a speed of 30
m/min to obtain polyester based fibers (multi-filament) with a size
of around 50 dtex. TABLE-US-00001 TABLE 1 Comparative Example
Example 1 2 3 4 5 6 7 8 1 2 (A) EFG-10 *1 100 100 100 100 100 100
100 collected PET flake *2 100 100 100 (B) PX-202 *3 15 15 15 15 15
15 SR-T5000 *4 12 12 12 12 (C) Stabaxol P *5 4 2 4
2,2-(1,3-phenylene)- 1 0.5 2 bis(2-oxazoline) p-phenylene 0.5 0.3
diisocyanate *1: Polyethylene terephthalate, IV value = 0.60,
manufactured by Kanebo Gohsen, Ltd. *2: Polyethylene terephthalate
broken into flakes after washing collected PET bottle, IV value =
0.65 *3: Condensed phosphate ester, manufactured by Daihachi
Chemical Industry Co., Ltd. *4: Brominated epoxy based flame
retardant, manufactured by Sakamoto Yakuhin Kogyo Co., Ltd. *5:
Aromatic polycarbodiimide, manufactured by Bayer AG
[0078] Strength and elongation, thermal shrinkage ratio, flame
retardance, curl holding properties, iron setting properties of the
resulting fiber were evaluated. The results are shown in Table 2
below. TABLE-US-00002 TABLE 2 Example 1 2 3 4 5 6 7 8 Intrinsic
viscosity of composition (IV) 0.73 0.73 0.73 0.73 0.73 0.73 0.73
0.73 Spinning processability Good Good Good Good Good Good Good
Good Size (dtex) 50 51 52 49 52 50 52 50 Strength (cN/dtex) 2.5 2.4
2.2 2.8 2.7 2.5 2.4 2.6 Elongation (%) 58 61 65 54 58 60 52 53
Thermal shrinkage ratio at 180.degree. C. (%) 2.5 2.2 2.3 2.3 1.9
2.2 2.4 2.4 Frame Flammability Good Good Good Good Good Good Good
Good retardance Drip resistance Good Good Good Good Good Good Good
Good Curl setting properties Good Good Good Good Good Good Good
Good Iron setting Adhesion Good Good Good Good Good Good Good Good
properties Shrinkage/thread Good Good Good Good Good Good Good Good
(180.degree. C.) breakage Rod withdrawal Good Good Fair Good Good
Good Good Good Curl holding Good Good Good Good Good Good Good
Good
Comparative Example 1 and 2
[0079] The compositions having component ratios shown in Table 1
were dried so as to have a moisture content of 100 ppm or less and
polyester fibers (multi-filament) having a single fiber size of
around 50 dtex were obtained in the same manner as Examples.
[0080] Strength and elongation, thermal shrinkage ratio, flame
retardance, curl holding properties, iron setting properties of the
resulting fiber were evaluated. The results are shown in Table 3
below. TABLE-US-00003 TABLE 3 Comparative Example 1 2 Intrinsic
viscosity of composition (IV) 0.73 0.73 Spinning processability
Fair Bad Size (dtex) 49 48 Strength (cN/dtex) 1.8 1.5 Elongation
(%) 69 72 Thermal shrinkage ratio at 180.degree. C. (%) 4.1 4.6
Frame retardance Flammability Fair Fair Drip resistance Bad Bad
Curl setting properties Fair Fair Iron setting Adhesion Good Good
properties Shrinkage/thread Good Good (180.degree. C.) breakage Rod
withdrawal Bad Bad Curl holding Fair Fair
[0081] As shown in Tables 2 and 3, excellent heat resistance, curl
holding properties and iron setting properties were observed in
Examples when compared to Comparative Examples. It is also observed
that the intrinsic viscosity can be controlled resulting in
excellent spinning processabilty by using a carbodiimide compound,
a bis-oxazoline compound or an isocyanate compound.
[0082] Accordingly, it was confirmed that the present artificial
hair using a carbodiimide compound, a bis-oxazoline compound or an
isocyanate compound can be utilized effectively for an artificial
hair which maintains mechanical and thermal properties of polyester
and has improved heat resistance and iron setting properties and
the like, compared with conventional artificial hair.
INDUSTRIAL APPLICABILITY
[0083] According to the present invention, it is possible to
provide a flame retardant polyester based artificial hair which has
an excellent spinning processability, curl holding properties and
iron setting properties while maintaining fiber properties such as
heat resistance, strength and elongation and the like.
* * * * *