U.S. patent application number 10/583182 was filed with the patent office on 2007-05-03 for acrylic shrinkable fiber and method for production thereof.
Invention is credited to Kohei Kawamura, Minoru Kuroda, Masahiko Mihoichi, Sohei Nishida.
Application Number | 20070098982 10/583182 |
Document ID | / |
Family ID | 34736647 |
Filed Date | 2007-05-03 |
United States Patent
Application |
20070098982 |
Kind Code |
A1 |
Nishida; Sohei ; et
al. |
May 3, 2007 |
Acrylic shrinkable fiber and method for production thereof
Abstract
An object of the present invention is to provide a dyeable
acrylic shrinkable fiber that only slightly shrinks when dyed and
has a high shrinkage percentage even after dyeing. By spinning an
incompatible spinning solution, the above object can be achieved,
and a dyeable acrylic shrinkable fiber that only slightly shrinks
when dyed and has a high shrinkage percentage even after dyeing can
be provided.
Inventors: |
Nishida; Sohei; (Hyogo,
JP) ; Kawamura; Kohei; (Hyogo, JP) ; Kuroda;
Minoru; (Hyogo, JP) ; Mihoichi; Masahiko;
(Hyogo, JP) |
Correspondence
Address: |
BRINKS HOFER GILSON & LIONE
P.O. BOX 10395
CHICAGO
IL
60610
US
|
Family ID: |
34736647 |
Appl. No.: |
10/583182 |
Filed: |
December 24, 2004 |
PCT Filed: |
December 24, 2004 |
PCT NO: |
PCT/JP04/19725 |
371 Date: |
June 16, 2006 |
Current U.S.
Class: |
428/373 ;
428/359; 428/364 |
Current CPC
Class: |
D01F 6/48 20130101; D01F
6/54 20130101; Y10T 428/2904 20150115; Y10T 428/2929 20150115; Y10T
428/2913 20150115 |
Class at
Publication: |
428/373 ;
428/359; 428/364 |
International
Class: |
D02G 3/00 20060101
D02G003/00 |
Foreign Application Data
Date |
Code |
Application Number |
Dec 26, 2003 |
JP |
2003-435851 |
Claims
1. A dyeable acrylic shrinkable fiber produced from a spinning
solution comprising a polymer composition in which 50 to 99 parts
by weight of a polymer (A) comprising 40 to 80 wt % of
acrylonitrile, 20 to 60 wt % of a halogen-containing monomer and 0
to 5 wt % of a sulfonic acid-containing monomer is mixed with 1 to
50 parts by weight of a polymer (B) comprising 5 to 70 wt % of
acrylonitrile, 20 to 94 wt % of other copolymerizable monomer and 1
to 40 wt % of a sulfonic acid-containing monomer, wherein the
polymer (A) and the polymer (B) are incompatible with each
other.
2. The acrylic shrinkable fiber according to claim 1, wherein the
total content of the sulfonic acid group-containing monomers in the
polymers (A) and (B) is 0.1 to 10 parts by weight based on the
total monomer content in the polymers (A) and (B).
3. The acrylic shrinkable fiber according to claim 1 or 2, wherein
the other copolymerizable monomer in the polymer (B) is an acrylic
acid ester.
4. The acrylic shrinkable fiber according to claims 1 or 2, wherein
the spinning solution is phase separated into particles having a
particle size of 0.1 to 30 .mu.m.
5. The acrylic shrinkable fiber according to claims 1 or 2, having
a dyeing shrinkage percentage at 80.degree. C. or less of 10% or
less.
6. The acrylic shrinkable fiber according to claims 1 or 2, having
a shrinkage percentage of 20% or more when dyed at 80.degree. C. or
less and then treated with dry heat at 130.degree. C. for five
minutes.
7. The acrylic shrinkable fiber according to claims 1 or 2, having
a relative saturation value when dyed at 60.degree. C. or more of
0.1 or more and a relative saturation value at 70.degree. C. or
more of 0.8 or more.
8. A process for producing the acrylic shrinkable fiber according
to claims 1 or 2, comprising carrying out relaxation treatment at 1
to 20%.
9. The acrylic shrinkable fiber according to claim 3, wherein the
spinning solution is phase separated into particles having a
particle size of 0.1 to 30 .mu.m.
10. The acrylic shrinkable fiber according to claim 3, having a
dyeing shrinkage percentage at 80.degree. C. or less of 10% or
less.
11. The acrylic shrinkable fiber according to claim 4, having a
dyeing shrinkage percentage at 80.degree. C. or less of 10% or
less.
12. The acrylic shrinkable fiber according to claim 3, having a
shrinkage percentage of 20% or more when dyed at 80.degree. C. or
less and then treated with dry heat at 130.degree. C. for five
minutes.
13. The acrylic shrinkable fiber according to claim 4, having a
shrinkage percentage of 20% or more when dyed at 80.degree. C. or
less and then treated with dry heat at 130.degree. C. for five
minutes.
14. The acrylic shrinkable fiber according to claim 5, having a
shrinkage percentage of 20% or more when dyed at 80.degree. C. or
less and then treated with dry heat at 130.degree. C. for five
minutes.
15. The acrylic shrinkable fiber according to claim 3, having a
relative saturation value when dyed at 60.degree. C. or more of 0.1
or more and a relative saturation value at 70.degree. C. or more of
0.8 or more.
16. The acrylic shrinkable fiber according to claim 4, having a
relative saturation value when dyed at 60.degree. C. or more of 0.1
or more and a relative saturation value at 70.degree. C. or more of
0.8 or more.
17. The acrylic shrinkable fiber according to claim 5, having a
relative saturation value when dyed at 60.degree. C. or more of 0.1
or more and a relative saturation value at 70.degree. C. or more of
0.8 or more.
18. The acrylic shrinkable fiber according to claim 6, having a
relative saturation value when dyed at 60.degree. C. or more of 0.1
or more and a relative saturation value at 70.degree. C. or more of
0.8 or more.
Description
TECHNICAL FIELD
[0001] The present invention relates to a dyeable highly shrinkable
acrylic fiber having a high shrinkage percentage even after dyeing,
and to a process for producing the same.
BACKGROUND ART
[0002] Conventionally, acrylic fibers have texture like animal
hair, and are used in artificial fur goods such as toys and clothes
due to their characteristics. In particular, artificial fur
products have a down hair part composed of a shrinkable fiber and a
guard hair part composed of a non-shrinkable fiber in appearance in
many cases, so as to provide the artificial fur products with fur
texture and natural appearance. Since pile fabrics are required to
have appearance characteristics, shrinkable fibers are also
required to have various hues. However, only shrinkable fibers with
limited kinds of hues which are colored in the spinning process
have been provided as shrinkable fibers.
[0003] The acrylic shrinkable fiber of the present invention after
the dyeing process is treated with dry heat in the tentering
process in pile processing to shrink. So far, a highly shrinkable
acrylonitrile synthetic fiber has been obtained from a copolymer
composed of 30 to 58 wt % of acrylonitrile, 70 to 42 wt % of
vinylidene chloride and vinyl chloride and 0 to 10 wt % of one or
more ethylenically unsaturated monomers (Japanese Patent Laid-Open
No. 60-110911). According to the knowledge of the present
inventors, the above shrinkable fiber shrinks when dyed at
70.degree. C. or more, and does not considerably shrinks by heat of
the tentering process in pile processing in which an adhesive is
caused to adhere to the pile back surface and dried. Further, the
shrinkable fiber can be prevented from shrinking when dyed at less
than 70.degree. C. and shrink by heat of the tentering process, but
cannot be sufficiently dyed.
[0004] In order to improve low-temperature dyeability, a dyeable
shrinkable fiber is obtained by mixing 95 to 60 parts by weight of
a polymer (I) comprising 40 wt % or more of acrylonitrile and 20 to
60 wt % of vinylidene chloride and a sulfonic acid-containing
monomer with 5 to 40 parts by weight of a highly dyeable polymer
(II) comprising 30 to 75 wt % of acrylonitrile and 25 to 70 wt % of
methyl acrylate (Japanese Patent No. 2566890). The resulting
shrinkable fiber has improved dyeability at a low temperature to
have a suppressed dyeing shrinkage percentage, and can shrink at
20% or more after dyeing. It is assumed that the polymer (I) and
the polymer (II) are compatible with each other in the shrinkable
fiber. According to the knowledge of the present inventors, when
the polymer (I) and the polymer (II) are compatible with each
other, the polymer (II) having properties to improve dyeability at
a low temperature as well as properties to reduce heat resistance
is continuously present in the fiber. For this reason, the polymer
(II) highly affects the shrinkage behavior of the fiber, and it is
difficult to suppress the dyeing shrinkage percentage even at a low
dyeing temperature. When the fiber highly shrinks when dyed, the
shrinkage percentage after dyeing is made small. When the fiber
shrinks during dyeing, the fiber packing density in a dyeing
machine is made small to generate a by-pass which causes dyeing
nonuniformity. Further, the fiber has drawbacks in that, for
example, it is difficult to stretch crimps generated during
shrinkage in the polishing process in pile processing. Thus a pile
fabric having desired appearance and texture cannot be provided.
These problems are still to be solved, and a dyeable acrylic
shrinkable fiber that only slightly shrinks when dyed and has a
high shrinkage percentage even after dyeing has not been
provided.
DISCLOSURE OF THE INVENTION
[0005] Accordingly, an object of the present invention is to solve
the above problems of the prior art and to provide a dyeable
acrylic shrinkable fiber that only slightly shrinks when dyed and
has a high shrinking percentage even after dyeing.
[0006] As a result of extensive studies, the present inventors have
found that a dyeable acrylic shrinkable fiber that only slightly
shrinks when dyed and has a high shrinkage percentage after dyeing
can be provided by spinning an incompatible spinning solution.
[0007] Specifically, the present invention relates to a dyeable
acrylic shrinkable fiber produced from a spinning solution
comprising a polymer composition in which 50 to 99 parts by weight
of a polymer (A) comprising 40 to 80 wt % of acrylonitrile, 20 to
60 wt % of a halogen-containing monomer and 0 to 5 wt % of a
sulfonic acid-containing monomer is mixed with 1 to 50 parts by
weight of a polymer (B) comprising 5 to 70 wt % of acrylonitrile,
20 to 94 wt % of other copolymerizable monomer and 1 to 40 wt % of
a sulfonic acid-containing monomer, wherein the polymer (A) and the
polymer (B) are incompatible with each other.
[0008] The other copolymerizable monomer in the acrylic shrinkable
fiber is preferably an acrylic acid ester.
[0009] The other copolymerizable monomer in the acrylic shrinkable
fiber is preferably an acrylic acid ester.
[0010] The spinning solution in the acrylic shrinkable fiber is
preferably phase separated into particles having a particle size of
0.1 to 30 .mu.m.
[0011] The acrylic shrinkable fiber preferably has a dyeing
shrinkage percentage at 80.degree. C. or less of 10% or less and a
shrinkage percentage after dyeing of 20% or more.
[0012] The acrylic shrinkable fiber preferably has a relative
saturation value at 60.degree. C. or more of 0.1 or more and a
relative saturation value at 70.degree. C. or more of 0.8 or
more.
[0013] A process for producing the acrylic shrinkable fiber
preferably comprises carrying out relaxation treatment at 1 to
20%.
[0014] The polymer (A) used for producing the acrylic shrinkable
fiber of the present invention is a polymer comprising 40 to 80 wt
% of acrylonitrile, 20 to 60 wt % of a halogen-containing monomer
and 0 to 5 wt % of a sulfonic acid-containing monomer.
[0015] In the polymer (A), acrylonitrile is preferably used in an
amount of 40 to 80 wt %. If the acrylonitrile content is less than
40 wt %, the resulting fiber has too low heat resistance. If the
acrylonitrile content is more than 80 wt %, the fiber has too high
heat resistance, and thus cannot have sufficient dyeability and
shrinkage percentage. The halogen-containing monomers in the
polymer (A) of the present invention are preferably vinyl halides
and vinylidene halides typified by vinyl chloride, vinylidene
chloride, vinyl bromide and vinylidene bromide. These may be used
singly or in a mixture of two or more. The halogen-containing
monomer is preferably used in the polymer (A) in an amount of 20 to
60 wt %. If the content of the halogen-containing monomer is more
than 60 wt %, the fiber is too hydrophobic, and thus cannot have
sufficient dyeability. If less than 20 wt %, the fiber of rough
touch giving uncomfortable feeling is produced.
[0016] The sulfonic acid-containing monomer in the polymer (A) of
the present invention is preferably allylsulfonic acid,
methallylsulfonic acid, styrenesulfonic acid, isoprenesulfonic
acid, 2-acrylamido-2-methylpropanesulfonic acid, or a metal salt or
amine salt thereof. These may be used singly or in a mixture of two
or more. In the polymer (A) of the present invention, the content
of the sulfonic acid-containing monomer is preferably 0 to 5 wt %.
If the content is more than 5 wt %, voids or agglutination are
formed in the fiber, and the fiber has decreased strength.
[0017] The polymer (B) used for producing the acrylic shrinkable
fiber of the present invention is a polymer comprising 5 to 70 wt %
of acrylonitrile, 20 to 94 wt % of another copolymerizable monomer
and 1 to 40 wt % of a sulfonic acid-containing monomer.
[0018] In the polymer (B), acrylonitrile is preferably used in an
amount of 5 to 70 wt %. If the acrylonitrile content is more than
70 wt %, the fiber has too high heat resistance, and thus cannot
have sufficient dyeability and shrinkage percentage.
[0019] Preferable examples of the other copolymerizable monomer in
the polymer (B) of the present invention include acrylic acid,
methacrylic acid and their lower alkyl esters, N- or N,N-alkyl
substituted aminoalkyl esters or glycidyl esters; acrylamide,
methacrylamide and their N- or N,N-alkyl substituted products;
anionic vinyl monomers such as carboxyl group-containing vinyl
monomers typified by acrylic acid, methacrylic acid and itaconic
acid and their sodium, potassium or ammonium salts; cationic vinyl
monomers typified by quaternary aminoalkyl esters of acrylic acid
or methacrylic acid; vinyl group-containing lower alkyl ethers;
vinyl group-containing lower carboxylic acid esters typified by
vinyl acetate; vinyl halides and vinylidene halides typified by
vinyl chloride, vinylidene chloride, vinyl bromide and vinylidene
bromide; and styrene. These monomers may be used singly or in a
mixture of two or more. The content of the other copolymerizable
monomer is preferably 20 to 94 wt %. If the content is less than 20
wt %, the fiber has too high heat resistance, and thus cannot have
sufficient dyeability. It is preferable to use an acrylic acid
ester as the other copolymerizable monomer particularly in terms of
dyeability. Preferable examples of the acrylic acid ester include
methyl acrylate, ethyl acrylate and butyl acrylate. These monomers
may be used singly or in a mixture of two or more.
[0020] The sulfonic acid-containing monomer in the polymer (B) is
preferably allylsulfonic acid, methallylsulfonic acid,
styrenesulfonic acid, isoprenesulfonic acid,
2-acrylamido-2-methylpropanesulfonic acid, or a metal salt or amine
salt thereof. These may be used singly or in a mixture of two or
more. In the polymer (B) of the present invention, the content of
the sulfonic acid-containing monomer is preferably 1 to 40 wt %. If
the content is more than 40 wt %, voids or agglutination are formed
in the fiber, and the fiber has decreased strength.
[0021] In the acrylic shrinkable fiber of the present invention, in
order to improve dyeability, the total content of the sulfonic acid
group-containing monomers in the polymers (A) and (B) contained in
the fiber is preferably 0.1 to 10 parts by weight, and more
preferably 0.2 to 5 parts by weight based on the total monomer
content in the polymers (A) and (B). If the content is less than
0.1 part by weight, the fiber cannot have sufficient dyeability. If
more than 10 parts by weight, voids or agglutination are formed in
the fiber, and the fiber has decreased strength, undesirably. When
the polymer (B) comprises 10 wt % or more of a sulfonic
acid-containing monomer, the polymer (A) and the polymer (B) tend
to be incompatible with each other.
[0022] The polymers (A) and (B) of the present invention can be
obtained by a conventional vinyl polymerization method such as
emulsion polymerization, suspension polymerization or solution
polymerization, using a known compound as initiator, for example,
peroxide compound, azo compound, or various redox compounds.
[0023] The polymers (A) and (B) of the present invention are
dissolved in an organic solvent, for example, acetone,
acetonitrile, dimethylformamide, dimethylacetamide or dimethyl
sulfoxide, or in an inorganic solvent, for example, zinc chloride,
nitric acid or rhodan salt to prepare a spinning solution.
Inorganic and/or organic pigment such as titanium oxide or coloring
pigment, stabilizer effective for anti-corrosion, coloring spinning
or weather resistance, or the like can be used for the spinning
solution, insofar as spinning can be carried out without
problems.
[0024] If the polymers (A) and (B) of the present invention are
mixed so that the polymer (B) is less than 1 wt %, the fiber cannot
have sufficient dyeability. If the polymer (B) is more than 50 wt
%, voids or agglutination are formed on the fiber, and the fiber
has decreased strength and dyeability, undesirably.
[0025] The term "incompatible" in the present invention preferably
refers to a state in which the spinning solution is phase separated
into particles having a particle size of 0.1 to 30 .mu.m, and more
preferably refers to a state in which the spinning solution is
phase separated into particles having a particle size of 6 to 12
.mu.m. In a phase separation state of particles having a particle
size of less than 0.1 .mu.m, the fiber has a high shrinkage
percentage when dyed, due to the properties of the polymer (B). In
a phase separation state of particles having a particle size of
more than 30 .mu.m, voids or agglutination are formed in the fiber,
and the fiber has decreased strength and dyeability,
undesirably.
[0026] The acrylic shrinkage fiber of the present invention is made
of a spinning solution in which the polymers (A) and (B) are
incompatible with each other. Thus, the fiber is assumed to have a
sea-island structure in which the polymer (B) present in a lower
proportion in the polymer (A) present in a higher proportion forms
like islands in the sea. Therefore, since the polymer (B) is not
continuously present in the fiber, the fiber has low heat
resistance but its shrinkage behavior is not remarkably affected by
the polymer (B). Accordingly, a fiber made of an incompatible
spinning solution can have a low dyeing shrinkage percentage as
compared with a fiber made of a compatible spinning solution. Since
the shrinkage percentage of the shrinkable fiber is determined
according to the resin composition and the spinning method, when
the fiber considerably shrinks in the dyeing process, the shrinkage
percentage in the subsequent pile processing process is small.
Therefore, the shrinkage percentage after dyeing can be increased
by decreasing the dyeing shrinkage percentage.
[0027] Further, in the present invention, when the polymer (A)
contains vinyl chloride, compatibility between the polymer (A) and
the polymer (B) can be decreased.
[0028] The dyeing shrinkage percentage in the present invention is
an index showing how much the fiber shrinks by dyeing, and is
determined in the following manner. A fiber with a length Lo is
treated with a water bath at any temperature for 60 minutes, and
then the length L of the resulting fiber is measured. The dyeing
shrinkage percentage is determined by the following formula.
[0029] Dyeing shrinkage percentage (%)=((Lo-L)/Lo).times.100
[0030] The shrinkage percentage after dyeing in the present
invention is an index showing how much the fiber shrinks after
dyeing by the tentering process, and is determined in the following
manner. A fiber after dyeing with a length Ldo is treated with a
holding oven at 130.degree. C. for five minutes, and then the
length Ld of the resulting fiber is measured. The shrinkage
percentage after dyeing is determined by the following formula.
[0031] Shrinkage percentage after dyeing
(%)=((Ldo-Ld)/Ldo).times.100
[0032] In the process for producing the acrylic shrinkable fiber of
the present invention, the spinning solution is spun through a
nozzle by a conventional wet or dry spinning method, drawn, and
dried. The spinning solution may be further drawn or treated with
heat as necessary. Further, the resulting fiber can be drawn at a
ratio of 1.3 to 4.0 at 70 to 140.degree. C. to obtain a shrinkable
fiber.
[0033] When the acrylic shrinkable fiber of the present invention
has a high dyeing shrinkage percentage, it is preferable to carry
out relaxation treatment at 1% or more in the fiber production
process to suppress shrinkage. The relaxation treatment is
preferably carried out with wet heat or dry heat at 70.degree. C.
to 140.degree. C. The dyeing shrinkage percentage can be suppressed
by increasing the treatment temperature and making the relaxation
percentage higher. However, since the shrinkage percentage after
dyeing is also suppressed in relaxation treatment under extreme
conditions, the relaxation treatment is preferably carried out at a
temperature of about 110.degree. C. at 20% or less.
[0034] The acrylic shrinkable fiber of the present invention is
caused to shrink in the tentering process in pile processing. The
tentering process is carried out with dry heat preferably at 110 to
150.degree. C., and typically at about 130.degree. C. Thus, the
shrinkage percentage after dyeing is measured under conditions
where the fiber shrinks with dry heat at 130.degree. C. for five
minutes.
[0035] The acrylic shrinkable fiber of the present invention has a
high dyeing shrinkage percentage at a high dyeing temperature.
Therefore, a dyeing temperature of more than 90.degree. C. is not
preferable, because the dyeing shrinkage percentage is high.
Further, when the fiber considerably shrinks by dyeing, the room
for shrinkage in the fiber is made small, and thus it is difficult
to make the shrinkage percentage after dyeing 20% or more. If the
dyeing shrinkage percentage is more than 10%, the fiber packing
density in a dyeing machine is made small to generate a by-pass
which tends to cause dyeing nonuniformity. Further, the fiber has
drawbacks in that, for example, it is difficult to stretch crimps
generated during shrinkage in the polishing process in pile
processing. Thus, a pile fabric having desired appearance and
texture cannot be provided. If the acrylic shrinkable fiber of the
present invention has a shrinkage percentage after dyeing of less
than 20%, the fiber processed into a pile fabric has a small step
from the non-shrinking raw cotton, and thus the pile step
(two-tone) cannot be distinguishable. Accordingly, a pile fabric
having natural or well-designed appearance characteristics cannot
be obtained.
[0036] The relative saturation value in the present invention is an
index of dyeability of the fiber. The fiber is dyed with a
supersaturation amount of Malachite Green at any temperature for 60
minutes to determine the saturation concentration of dye. The
relative saturation value was determined by the saturation
concentration of dye. The saturation concentration of dye and the
relative saturation value were determined by the following
formulas. Saturation concentration of dye=((Ao-A)/Ao).times.2.5) A:
Absorbance of dye bath after dyeing (wavelength: 618 nm) Ao:
Absorbance of dye bath before dyeing (618 nm) Relative saturation
value=Saturation concentration of dye.times.400/463
[0037] The acrylic shrinkable fiber of the present invention can be
lightly dyed at a relative saturation value of 0.1 or more.
Further, since the fiber can be dyed to light to dark colors, or
even black at a relative saturation value of 0.8 or more, the
relative saturation value is preferably 0.8 or more.
[0038] The performance evaluation methods of test fibers will be
described below in detail prior to description of examples.
(1) Phase Separation State
[0039] A base dope was mixed with a blend polymer at any ratio to
prepare a spinning solution. The spinning solution was observed
with a phase contrast microscope (manufactured by Ario Techno Co.,
Ltd., ANS30). Particle sizes of ten separated blend polymer
particles randomly selected were measured to determine an average.
The phase separation state was evaluated based on the average.
(2) High Pile Test Production
[0040] A shrinkable fiber was blended with a non-shrinkable fiber,
and the blend fiber was humidity conditioned. The fiber was
prepared into a card sliver through an opener and a card. Next, the
carded sliver was subjected to sliver knitting in a high pile
knitting machine, and the pile part was cut by shearing to make the
pile part length uniform. Then, the pile back surface was back
coated with an acrylic acid ester adhesive. Next, the adhesive was
dried at 130.degree. C. for five minutes and, at the same time, the
shrinkable fiber was caused to shrink. Thereafter, the pile part
was finished into a high pile by carrying out polish finishing and
shearing.
(3) High Pile Appearance Evaluation
[0041] For the step pile fabric prepared in the manner described in
(2), four-grade sensory evaluation of the degree of appearance
characteristics, in which the step between the long pile part and
the short pile part is emphasized, was carried out from the visual
and sensory points of view in the following standards.
Very good: The step pile fabric has appearance characteristics in
which the step between the long pile part and the short pile part
is greatly emphasized.
Good: The step pile fabric has appearance characteristics in which
the step between the long pile part and the short pile part is
emphasized.
Fair: The step between the long pile part and the short pile part
is not much emphasized in the step pile fabric. Poor: The step
between the long pile part and the short pile part almost cannot be
observed in the step pile fabric.
[0042] Examples will be described below. "Part(s)" in the examples
refers to "part(s) by weight" unless otherwise indicated.
EXAMPLES
Production Example 1
[0043] A pressure polymerization reactor having an internal volume
of 20 L was charged with 200 parts of ion exchange water, 0.9 part
of sodium lauryl sulfate, 0.43 part of sulfurous acid, 0.22 part of
sodium hydrogensulfite, 0.001 part of iron sulfate, 4.9 parts of
acrylonitrile (hereinafter referred to as AN) and 52.5 parts of
vinyl chloride (hereinafter referred to as VC), and the internal
atmosphere was replaced with nitrogen. The polymerization reactor
was adjusted to an internal temperature of 50.degree. C., and
charged with 0.035 part of ammonium persulfate as an initiator to
initiate polymerization. Polymerization was carried out for a
polymerization time of 5 hours and 10 minutes while adding 42.1
parts of AN, 0.5 part of sodium styrenesulfonate (hereinafter
referred to as 3S) and 0.23 part of ammonium persulfate.
[0044] Then, the unreacted VC was recovered, and the latex was
removed from the polymerization reactor, salted out, treated with
heat, filtered, washed with water, dehydrated, and dried to obtain
a polymer 1.
[0045] Next, a pressure polymerization reactor having an internal
volume of 5 L was charged with 187 parts of acetone, 47 parts of
water, 40 parts of AN, 45 parts of methyl acrylate (hereinafter
referred to as MA), and 15 parts of sodium
2-acrylamido-2-methylpropanesulfonate (hereinafter referred to as
SAM), and the internal atmosphere was replaced with nitrogen. The
polymerization reactor was adjusted to an internal temperature of
65.degree. C., and charged with 0.5 part of
2,2'-azobis(2,4-dimethylvaleronitrile) as an initiator to initiate
polymerization. The components were polymerized for two hours while
adding 1.0 part of azobis in the middle of the polymerization.
Then, the components were heated to 70.degree. C. and polymerized
for two hours to obtain a solution of a polymer 2 having a polymer
concentration of 30 wt %. The polymer 1 was dissolved in acetone to
prepare a polymer 1 solution having a polymer 1 concentration of 30
wt %. The polymer 1 solution was mixed with the polymer 2 solution
at a ratio of the polymer 1 to the polymer 2 of 9:1 to prepare a
spinning solution. The resulting spinning solution was discharged
through a spinneret with 8,500 holes having a diameter of 0.08 mm
into a 30 wt % aqueous acetone solution at 25.degree. C., then
drawn at a ratio of 2.0 in a 20 wt % aqueous acetone solution at
25.degree. C., and thereafter washed with water at 60.degree. C.
Then, the spinning solution was dried at 130.degree. C. and further
drawn at a ratio of 1.8 at 105.degree. C. to obtain a 4.4 dtex
drawn yarn.
[0046] Subsequently, the resulting shrinkable fiber was crimped,
cut into a 32 mm fiber, and then dyed with 0.2% omf of Maxilon Red
GRL (manufactured by Ciba Specialty Chemicals, Inc.) as a dye and
0.5 g/L of UltraMT #100 (manufactured by Mitejima Chemical Co.,
Ltd.) as a dyeing aid at 60.degree. C., 70.degree. C. and
80.degree. C. for 60 minutes. 70 wt % of the dyed fiber was blended
with 30 wt % of a non-shrinkable raw fiber "Kanecaron (R)" RCL 12.2
dtex, 44 mm (manufactured by Kaneka Corporation) to prepare a high
pile. At that time, the pile part was cut into a pile length of 15
mm by shearing after sliver knitting, and cut into a pile length of
18 mm after polish finishing to obtain the high pile.
Production Example 2
[0047] The drawn yarn obtained in Production Example 1 was relaxed
at 5% at 110.degree. C. Further, a high pile was prepared from the
relaxed fiber in the same manner as in Production Example 1.
Production Example 3
[0048] A pressure polymerization reactor having an internal volume
of 20 L was charged with 200 parts of ion exchange water, 1.1 parts
of sodium lauryl sulfate, 0.13 part of sulfurous acid, 0.17 part of
sodium hydrogensulfate, 0.002 part of iron sulfate, 10.7 parts of
acrylonitrile and 4.4 parts of vinylidene chloride, and the
internal atmosphere was replaced with nitrogen. The polymerization
reactor was adjusted to an internal temperature of 55.degree. C.,
and charged with 0.012 part of ammonium persulfate as an initiator
to initiate polymerization. Polymerization was carried out for a
polymerization time of 6 hours and 10 minutes while adding 42.7
parts of acrylonitrile, 41.0 parts of vinylidene chloride, 1.2
parts of sodium styrenesulfonate and 0.135 part of ammonium
persulfate. Then, the latex was removed from the polymerization
reactor, salted out, treated with heat, filtered, washed with
water, dehydrated, and dried to obtain a polymer 3. The polymer 3
was dissolved in acetone to prepare a polymer 3 solution having a
polymer 3 concentration of 30 wt %. The polymer 3 solution was
mixed with the polymer 2 solution prepared in Production Example 1
at a ratio of the polymer 3 to the polymer 2 of 9:1 to prepare a
spinning solution. The resulting spinning solution was discharged
through a spinneret with 8,500 holes having a diameter of 0.08 mm
into a 30 wt % aqueous acetone solution at 25.degree. C., drawn at
a ratio of 2.0 in a 20 wt % aqueous acetone solution at 25.degree.
C., and then washed with water at 60.degree. C. Then, the spinning
solution was dried at 130.degree. C. and further drawn at a ratio
of 1.8 at 105.degree. C. to obtain a 4.4 dtex drawn yarn. The drawn
yarn was relaxed at 5% at 110.degree. C. Further, a high pile was
prepared from the relaxed fiber in the same manner as in Production
Example 1.
Production Example 4
[0049] A pressure polymerization reactor having an internal volume
of 5 L was charged with 187 parts of acetone, 47 parts of water, 40
parts of AN, 55 parts of MA and 5 parts of SAM. The components were
polymerized in the same manner as in Production Example 1 for the
polymer 2 to obtain a solution of a polymer 4. The polymer 1
obtained in Production Example 1 was dissolved in acetone to
prepare a polymer 1 solution having a polymer 1 concentration of 30
wt %. The polymer 1 solution was mixed with the polymer 4 solution
at a ratio of the polymer 1 to the polymer 4 of 7:3 to prepare a
spinning solution. The resulting spinning solution was spun in the
same manner as in Production Example 1 to obtain a drawn yarn. A
high pile was prepared from the resulting drawn yarn in the same
manner as in Production Example 1.
Production Example 5
[0050] The drawn yarn obtained in Production Example 4 was relaxed
at 5% at 110.degree. C. Further, a high pile was prepared from the
relaxed fiber in the same manner as in Production Example 1.
Production Example 6
[0051] The polymer 3 prepared in Production Example 3 was dissolved
in acetone to prepare a polymer 3 solution having a polymer 3
concentration of 30 wt %. The polymer 3 solution was mixed with the
polymer 4 solution prepared in Production Example 4 at a ratio of
the polymer 3 to the polymer 4 of 7:3 to prepare a spinning
solution. A relaxed fiber was prepared from the resulting spinning
solution in the same manner as in Production Example 3. Next, a
high pile was prepared from the relaxed fiber in the same manner as
in Production Example 1.
Production Example 7
[0052] A pressure polymerization reactor having an internal volume
of 5 L was charged with 187 parts of acetone, 47 parts of water, 30
parts of AN, 55 parts of MA and 15 parts of SAM. The components
were polymerized in the same manner as in Production Example 1 for
the polymer 2 to obtain a solution of a polymer 5. The polymer 1
obtained in Production Example 1 was dissolved in acetone to
prepare a polymer 1 solution having a polymer 1 concentration of 30
wt %. The polymer 1 solution was mixed with the polymer 5 solution
at a ratio of the polymer 1 to the polymer 5 of 9:1 to prepare a
spinning solution. The resulting spinning solution was spun in the
same manner as in Production Example 1 to obtain a drawn yarn. A
high pile was prepared from the resulting drawn yarn in the same
manner as in Production Example 1.
Production Example 8
[0053] The drawn yarn obtained in Production Example 7 was relaxed
at 5% at 110.degree. C. Further, a high pile was prepared from the
relaxed fiber in the same manner as in Production Example 1.
Production Example 9
[0054] A pressure polymerization reactor having an internal volume
of 5 L was charged with 187 parts of acetone, 47 parts of water, 60
parts of AN, 25 parts of MA and 15 parts of SAM. The components
were polymerized in the same manner as in Production Example 1 for
the polymer 2 to obtain a solution of a polymer 6. The polymer 1
obtained in Production Example 1 was dissolved in acetone to
prepare a polymer 1 solution having a polymer 1 concentration of 30
wt %. The polymer 1 solution was mixed with the polymer 6 solution
at a ratio of the polymer 1 to the polymer 6 of 9:1 to prepare a
spinning solution. The resulting spinning solution was spun in the
same manner as in Production Example 1 to obtain a drawn yarn. A
high pile was prepared from the resulting drawn yarn in the same
manner as in Production Example 1.
Production Example 10
[0055] The drawn yarn obtained in Production Example 9 was relaxed
at 5% at 110.degree. C. Further, a high pile was prepared from the
relaxed fiber in the same manner as in Production Example 1.
Production Example 11
[0056] A pressure polymerization reactor having an internal volume
of 5 L was charged with 140 parts of acetone, 94 parts of water, 10
parts of AN, 60 parts of methyl acrylate (hereinafter referred to
as MA) and 30 parts of SAM. The components were polymerized in the
same manner as in Production Example 1 for the polymer 2 to obtain
a solution of a polymer 7. The polymer 1 obtained in Production
Example 1 was dissolved in acetone to prepare a polymer 1 solution
having a polymer 1 concentration of 30 wt %. The polymer 1 solution
was mixed with the polymer 7 solution at a ratio of the polymer 1
to the polymer 7 of 96:4 to prepare a spinning solution. The
resulting spinning solution was spun in the same manner as in
Production Example 1 to obtain a drawn yarn. A high pile was
prepared from the resulting drawn yarn in the same manner as in
Production Example 1.
Production Example 12
[0057] The drawn yarn obtained in Production Example 11 was relaxed
at 5% at 110.degree. C. Further, a high pile was prepared from the
relaxed fiber in the same manner as in Production Example 1.
Production Example 13
[0058] A pressure polymerization reactor having an internal volume
of 5 L was charged with 187 parts of acetone, 47 parts of water, 50
parts of AN, 35 parts of ethyl acrylate (hereinafter referred to as
EA) and 15 parts of SAM. The components were polymerized in the
same manner as in Production Example 1 for the polymer 2 to obtain
a solution of a polymer 8. The polymer 1 obtained in Production
Example 1 was dissolved in acetone to prepare a polymer 1 solution
having a polymer 1 concentration of 30 wt %. The polymer 1 solution
was mixed with the polymer 8 solution at a ratio of the polymer 1
to the polymer 8 of 9:1 to prepare a spinning solution. The
resulting spinning solution was spun in the same manner as in
Production Example 1 to obtain a drawn yarn. A high pile was
prepared from the resulting drawn yarn in the same manner as in
Production Example 1.
Production Example 14
[0059] The drawn yarn obtained in Production Example 11 was relaxed
at 5% at 110.degree. C. Further, a high pile was prepared from the
relaxed fiber in the same manner as in Production Example 1.
Production Example 15
[0060] A pressure polymerization reactor having an internal volume
of 5 L was charged with 187 parts of acetone, 47 parts of water, 50
parts of AN, 35 parts of methyl methacrylate (hereinafter referred
to as MMA) and 15 parts of SAM. The components were polymerized in
the same manner as in Production Example 1 for the polymer 2 to
obtain a solution of a polymer 9. The polymer 1 obtained in
Production Example 1 was dissolved in acetone to prepare a polymer
1 solution having a polymer 1 concentration of 30 wt %. The polymer
1 solution was mixed with the polymer 9 solution at a ratio of the
polymer 1 to the polymer 9 of 9:1 to prepare a spinning solution.
The resulting spinning solution was spun in the same manner as in
Production Example 1 to obtain a drawn yarn. A high pile was
prepared from the resulting drawn yarn in the same manner as in
Production Example 1.
Production Example 16
[0061] The drawn yarn obtained in Production Example 13 was relaxed
at 5% at 110.degree. C. Further, a high pile was prepared from the
relaxed fiber in the same manner as in Production Example 1.
Production Example 17
[0062] A pressure polymerization reactor having an internal volume
of 5 L was charged with 187 parts of acetone, 47 parts of water, 50
parts of AN, 25 parts of MA, 10 parts of vinylidene chloride
(hereinafter referred to as VD) and 15 parts of SAM. The components
were polymerized in the same manner as in Production Example 1 for
the polymer 2 to obtain a solution of a polymer 10. The polymer 1
obtained in Production Example 1 was dissolved in acetone to
prepare a polymer 1 solution having a polymer 1 concentration of 30
wt %. The polymer 1 solution was mixed with the polymer 10 solution
at a ratio of the polymer 1 to the polymer 10 of 9:1 to prepare a
spinning solution. The resulting spinning solution was spun in the
same manner as in Production Example 1 to obtain a drawn yarn. A
high pile was prepared from the resulting drawn yarn in the same
manner as in Production Example 1.
Production Example 18
[0063] The drawn yarn obtained in Production Example 17 was relaxed
at 5% at 110.degree. C. Further, a high pile was prepared from the
relaxed fiber in the same manner as in Production Example 1.
[0064] The production processes of the fibers obtained in
Production Examples 1 to 18 are shown in Table 1. TABLE-US-00001
TABLE 1 Blend Composition Blend Relaxation Base polymer composition
Blend polymer composition polymer/Base polymer treatment Pro. Ex. 1
Polymer 1 AN.sup.50-VC.sup.49.5-3S.sup.0.5 Polymer 2
AN.sup.40-MA.sup.45-SAM.sup.15 10/90 0% Pro. Ex. 2 Polymer 1
AN.sup.50-VC.sup.49.5-3S.sup.0.5 Polymer 2
AN.sup.40-MA.sup.45-SAM.sup.15 10/90 5% Pro. Ex. 3 Polymer 3
AN.sup.50-VD.sup.49.5-3S.sup.0.5 Polymer 2
AN.sup.40-MA.sup.45-SAM.sup.15 10/90 5% Pro. Ex. 4 Polymer 1
AN.sup.50-VC.sup.49.5-3S.sup.0.5 Polymer 4
AN.sup.40-MA.sup.55-SAM.sup.5 30/70 0% Pro. Ex. 5 Polymer 1
AN.sup.50-VC.sup.49.5-3S.sup.0.5 Polymer 4
AN.sup.40-MA.sup.55-SAM.sup.5 30/70 5% Pro. Ex. 6 Polymer 3
AN.sup.50-VD.sup.49.5-3S.sup.0.5 Polymer 4
AN.sup.40-MA.sup.55-SAM.sup.5 30/70 5% Pro. Ex. 7 Polymer 1
AN.sup.50-VC.sup.49.5-3S.sup.0.5 Polymer 5
AN.sup.30-MA.sup.55-SAM.sup.15 10/90 0% Pro. Ex. 8 Polymer 1
AN.sup.50-VC.sup.49.5-3S.sup.0.5 Polymer 5
AN.sup.30-MA.sup.55-SAM.sup.15 10/90 5% Pro. Ex. 9 Polymer 1
AN.sup.50-VC.sup.49.5-3S.sup.0.5 Polymer 6
AN.sup.60-MA.sup.25-SAM.sup.15 10/90 0% Pro. Ex. 10 Polymer 1
AN.sup.50-VC.sup.49.5-3S.sup.0.5 Polymer 6
AN.sup.60-MA.sup.25-SAM.sup.15 10/90 5% Pro. Ex. 11 Polymer 1
AN.sup.50-VC.sup.49.5-3S.sup.0.5 Polymer 7
AN.sup.10-MA.sup.60-SAM.sup.30 4/96 0% Pro. Ex. 12 Polymer 1
AN.sup.50-VC.sup.49.5-3S.sup.0.5 Polymer 7
AN.sup.10-MA.sup.60-SAM.sup.30 4/96 5% Pro. Ex. 13 Polymer 1
AN.sup.50-VC.sup.49.5-3S.sup.0.5 Polymer 8
AN.sup.50-EA.sup.35-SAM.sup.15 10/90 0% Pro. Ex. 14 Polymer 1
AN.sup.50-VC.sup.49.5-3S.sup.0.5 Polymer 8
AN.sup.50-EA.sup.35-SAM.sup.15 10/90 5% Pro. Ex. 15 Polymer 1
AN.sup.50-VC.sup.49.5-3S.sup.0.5 Polymer 9
AN.sup.50-MA.sup.35-SAM.sup.15 10/90 0% Pro. Ex. 16 Polymer 1
AN.sup.50-VC.sup.49.5-3S.sup.0.5 Polymer 9
AN.sup.50-MA.sup.35-SAM.sup.15 10/90 5% Pro. Ex. 17 Polymer 1
AN.sup.50-VC.sup.49.5-3S.sup.0.5 Polymer 10
AN.sup.50-MA.sup.25-VD.sup.10-SAM.sup.15 10/90 0% Pro. Ex. 18
Polymer 1 AN.sup.50-VC.sup.49.5-3S.sup.0.5 Polymer 10
AN.sup.50-MA.sup.25-VD.sup.10-SAM.sup.15 10/90 5%
Examples 1 to 16
[0065] The shrinkable fibers obtained in Production Examples 1, 2,
4, 5, 7 to 18 were dyed at 60.degree. C., 70.degree. C. and
80.degree. C. for 60 minutes. The relative saturation values,
dyeing shrinkage percentages and shrinkage percentages after dyeing
at that time are shown in Table 2. When the spinning solution is
incompatible, the dyeing shrinkage percentage is 10% or less and
the shrinkage percentage after dyeing is 20% or more in dyeing at
60 to 80.degree. C.; the relative saturation value is 0.1 or more
in dyeing at 60.degree. or more; and the relative saturation value
is 0.8 or more in dyeing at 70.degree. C. or more.
[0066] Further, appearance of the high piles obtained in Production
Examples 1, 2, 4, 5, 7 to 18 was evaluated. The results are shown
in Table 2. When the shrinkage percentage after dyeing is 20% or
more, a high pile having appearance characteristics in which the
step between the long pile part and the short pile part is
emphasized can be obtained.
Comparative Examples 1 and 2
[0067] The shrinkable fibers obtained in Production Examples 3 and
6 were dyed at 60.degree. C., 70.degree. C. and 80.degree. C. for
60 minutes. The relative saturation values, dyeing shrinkage
percentages and shrinkage percentages after dyeing at that time are
shown in Table 2.
[0068] When the spinning solution is compatible, it is difficult to
make the dyeing shrinkage percentage 10% or less in dyeing at 70 to
80.degree. C.
[0069] Further, appearance of the high piles obtained in Production
Examples 3 and 6 was evaluated. The results are shown in Table 2.
When the shrinkage percentage after dyeing is 20% or less, the step
between the long pile part and the short pile part almost cannot be
observed. TABLE-US-00002 TABLE 2 Relative Dyeing shrinkage
Shrinkage percentage High pile appearance saturation value
percentage (%) after dyeing (%) evaluation Phase Dyeing temperature
Dyeing temperature Dyeing temperature Dyeing temperature Production
separation (.degree. C.) (.degree. C.) (.degree. C.) (.degree. C.)
process state (.mu.m) 60 70 80 60 70 80 60 70 80 60 70 80 Ex. 1
Pro. Ex. 1 10 0.2 1.0 -- 2 7 -- 36 30 -- VG VG -- Ex. 2 Pro. Ex. 2
10 -- -- 2.2 -- -- 7 -- -- 24 -- -- G Com. Pro. Ex. 3 compatible
0.3 1.0 2.3 8 19 30 30 21 10 VG G P Ex. 1 Ex. 3 Pro. Ex. 4 7 0.3
1.1 -- 3 9 -- 37 32 -- VG VG -- Ex. 4 Pro. Ex. 5 7 -- -- 2.4 -- --
8 -- -- 26 -- -- G Com. Pro. Ex. 6 compatible 0.4 1.3 2.5 9 20 35
28 18 5 VG P P Ex. 2 Ex. 5 Pro. Ex. 7 9 0.3 1.0 -- 2 8 -- 36 31 --
VG VG -- Ex. 6 Pro. Ex. 8 9 -- -- 2.1 -- -- 8 -- -- 24 -- -- G Ex.
7 Pro. Ex. 9 11 0.2 0.8 -- 2 6 -- 35 30 -- VG VG -- Ex. 8 Pro. Ex.
10 11 -- -- 1.9 -- -- 6 -- -- 24 -- -- G Ex. 9 Pro. Ex. 11 12 0.1
0.8 -- 2 6 -- 36 31 -- VG VG -- Ex. 10 Pro. Ex. 12 12 -- -- 2.2 --
-- 7 -- -- 24 -- -- G Ex. 11 Pro. Ex. 13 11 0.2 0.9 -- 2 5 -- 34 29
-- VG VG -- Ex. 12 Pro. Ex. 14 11 -- -- 1.8 -- -- 7 -- -- 23 -- --
G Ex. 13 Pro. Ex. 15 6 0.1 0.8 -- 2 5 -- 34 29 -- VG VG -- Ex. 14
Pro. Ex. 16 6 -- -- 1.8 -- -- 6 -- -- 22 -- -- G Ex. 15 Pro. Ex. 17
6 0.1 0.8 -- 1 6 -- 34 28 -- VG VG -- Ex. 16 Pro. Ex. 18 6 -- --
1.7 -- -- 6 -- -- 21 -- -- G
INDUSTRIAL APPLICABILITY
[0070] The acrylic shrinkable fiber of the present invention only
slightly shrinks when dyed, and has a high shrinkage percentage
even after drying. As a result, new goods in wide range of
applications such as clothes, toys (such as stuffed toys) and
interior goods using the fiber can be planned.
* * * * *