Technical Field
[0001] The invention relates to an easily alkali soluble polyester fiber having high etching
finish properties, etching finished woven and knitted fabrics which contain said fiber
and a method for producing the woven and knitted fabrics.
Background Art
[0002] In general, etching finishing which includes: printing an etching paste on a woven
or knitted fabric composed of two or more types of fibers including a fiber having
high etching finish properties and a fiber hard to be etched in a patterned manner;
and embrittling and removing the fiber having high etching finish properties; is also
called opal finishing. The etching finishing has been widely known as processing for
forming a watermark pattern or a highly stretchable part. A chemical reaction in the
etching finishing varies depending on types of fibers. For example, a method for removing
a polyester fiber is also referred to as alkali weight reduction. The method is alkaline
hydrolysis which uses sodium hydroxide, potassium hydroxide and the like. On the other
hand, in order to remove a cellulosic fiber such as cotton and acetate, acid hydrolysis,
dissolution by carbonization or a hot organic solvent and the like have been utilized.
[0003] As etching finishing for a woven or knitted fabric made of a polyester fiber, a method
which includes: printing an etching paste on a woven or knitted fabric composed of
a modified polyester fiber having high etching finish properties and an unmodified
polyester fiber having low etching finish properties in a patterned manner; and removing
the modified polyester fiber having high etching finish properties; has been known.
As such a method, a method which includes: printing a paste liquid containing sodium
hydroxide or potassium hydroxide as an etching finish agent; and performing heat treatment;
has been known.
[0004] However, the method, which uses sodium hydroxide or potassium hydroxide when performing
etching finishing by utilizing a difference in hydrolyzability between the modified
polyester fiber having high etching finish properties and the unmodified polyester
fiber having low etching finish properties, may even embrittle the unmodified polyester
fiber. Accordingly, the method has a problem which may cause reduction in strength
and etching defect. In addition, sodium hydroxide and potassium hydroxide are strong
alkaline substances, and therefore, they have high toxicity and irritancy to human,
and also have high influence on aquatic environment.
[0005] On the other hand, in order to improve dyeability of a polyethylene terephthalate
fiber, which has been dyed under high temperature and high pressure by a disperse
dye, such that the fiber is capable of being dyed by dyeing under normal pressure
by using a disperse dye and a cationic dye, a modified polyester fiber which is obtained
by copolymerizing a polyethylene terephthalate with 0.4 to 5 mol% of 5-sodium sulfoisophthalic
acid and 2 to 15 mol% of adipic acid has been known, for example, by
JP S61-239015 A (Patent Document 1),
JP H08-269820 A (Patent Document 2),
JP 2013-18802 A (Patent Document 3) and the like.
[0006] Such a modified polyester fiber has been diversified from the point of view of dyeing,
because types of dyes which can be applied to the fiber increase. In addition, the
modified polyester fiber has been also used for combined use of a polyethylene terephthalate
fiber having high chemical resistance and a fiber having low chemical resistance in
opal finishing. However, a conventional modified polyester fiber has been not sufficiently
satisfied yet in terms of etching removal properties by an alkali when performing
opal finishing. Accordingly, a modified polyester fiber, which maintains physical
properties of the fiber as much as possible and which is etching removed more easily,
has been required in order to diversify opal finished products.
[0007] In addition, for example, according to
JP 2000-096439 A (Patent Document 4), with regard to etching finishing of a modified polyester fiber
in a woven or knitted fabric in which a fabric is composed of the modified polyester
fiber and an unmodified polyester fiber, etching finishing which uses an etching finish
agent containing guanidine carbonate has been proposed. However, etching finishing
by using guanidine carbonate is good in etching finish properties of the modified
polyester, but there has been a problem that the unmodified polyester tends to embrittle,
which causes the reduction in strength.
[0008] Further, according to
JP 2000-282377 A (Patent Document 5), in etching finishing of a modified polyester fiber in a woven
or knitted fabric which contains an normal pressure cation-dyeable polyester fiber
as an essential component, a method which includes: printing a paste liquid containing
a quaternary ammonium salt; performing heat treatment; and after that, performing
alkali weight reduction to remove the modified polyester fiber; has been proposed.
However, since the method is alkali weight reductionprocessing which uses sodium hydroxide,
there has been a problem that strength of the modified polyester fiber and an unmodified
polyester fiber cannot be maintained.
[0009] Furthermore, for example, according to
JP 2008-038332 A (Patent Document 6), in etching finishing of a modified polyester fiber in a woven
or knitted fabric composed of the modified polyester fiber and an unmodified polyester
fiber, it has been proposed to perform etching finishing by a method which includes
making an etching finish agent containing at least one of guanidine carbonate, sodium
hydroxide, and potassium hydroxide adhere to the fabric by inkjet textile printing.
In the method, etching finishing is performed by controlling an adhesion amount of
the etching finish agent by inkjet textile printing. However, in order to maintain
strength of the unmodified polyester fiber, fineness of the unmodified polyester fiber
has been made larger. Alternatively, a bicomponent filament yarn in which a core part
is an unmodified polyester fiber and a sheath part is a modified polyester fiber has
been used such that the etching finish agent adheres only to the modified polyester
fiber, or other methods have been used. In any case, there has been a problem that
embrittlement of the unmodified polyester fiber cannot be prevented.
[0010] In addition, for example, according to
WO 2007/086593 A (Patent Document 7), a method in which a fabric to which etching finishing is performed
is composed of a non-elastic fiber and an elastic fiber has been proposed. In the
fabric, a cation dyeable polyester fiber, which is a fiber capable of being etched,
and a nylon fiber, which is a fiber not capable of being etched, are used as the non-elastic
fiber, and an ether-based polyurethane fiber is used as the elastic fiber. There has
been a problem that the cation dyeable polyester fiber and the polyurethane fiber,
which are not the subjects of etching tend to be etched when sodium hydroxide is used
as the etching finish agent, which causes reduction in elasticity and strength.
Citation List
Patent Document
Summary of Invention
Technical Problem
[0012] One object of the invention is to provide an easily alkali soluble modified polyester
fiber which is used as a fiber having low chemical resistance in opal finishing and
is capable of being easily etching-removed by an alkali. Conventionally, an aliphatic
dicarboxylic acid and a metal sulfonate group-containing aromatic dicarboxylic acid
are copolymer components which are known to have modifying effects of dyeability of
a polyethylene terephthalate fiber. However, it is found that when specific amounts
of the aliphatic dicarboxylic acid and the metal sulfonate group-containing aromatic
dicarboxylic acid are used, the modifying effects of dyeability are maintained, and
further, it is found that an easily alkali soluble fiber, which can be easily etching-removed,
can be obtained, and thus the invention has been completed.
[0013] In addition, as described above, there has been a problem that in etching finishing
which includes etching a modified polyester fiber, sufficient etching can be achieved
only in the case when a strong alkali is used. On the contrary, when the strong alkali
is used, there has been a problem that strength of a fabric which has been subjected
to etching finishing tends to decrease. In view of this situation, another object
of the invention is to provide etching finished woven and knitted fabrics having high
etching finish properties, which can be easily etched even when a weak alkali is used,
by using a modified polyester fiber having sufficient etching finish properties, while
preventing reduction in strength of fibers in parts containing an unmodified polyester
fiber other than etchedparts . In addition, another object of the invention is to
provide a method for producing the etching finished woven and knitted fabrics.
Solution to Problem
[0014] In conventional technologies, in etching finishing of a woven or knitted fabric composed
of a modified polyester fiber and an unmodified polyester fiber, in order to prevent
the unmodified polyester fiber from being embrittled, a method which includes: printing
an alkali weight reduction accelerator without using a strong alkaline substance such
as sodium hydroxide and potassium hydroxide in an etching paste; performing heat treatment;
and promoting alkali weight reduction of printed parts at the time of the alkali weight
reduction after the printing and the heat treatment; has been considered. However,
the inventors have focused on further modification of a modified polyester fiber,
and have conducted various studies and experiments. As a result, the inventors have
found that alkali weight reduction of a certain modified polyester fiber can be performed
in a certain pH range, without using a strong alkaline substance such as sodium hydroxide
and potassium hydroxide, and without an influence of reduction in strength of an unmodified
polyester fiber and a polyurethane fiber. The inventors have found that the alkali
weight reduction only of the modified polyester fiber can be achieved.
[0015] The modified polyester fiber according to the invention is a modified polyester fiber
characterized by having a weight reduction ratio of equal to or more than 5% and equal
to or less than 15%, the weight reduction ratio being obtained by the following measuring
method:
<measuring method of weight reduction ratio of fiber>
the measuring method of the weight reduction ratio including adding 100 g of a fiber
to 2 L of an aqueous solution including 40 g/L of sodium carbonate; heating an obtained
mixture at 100°C for 30 minutes; performing drying treatment at 80°C for 60 minutes;
and after that, measuring a fiber mass A g.

[0016] It is preferable that the modified polyester fiber according to the invention is
characterized in that the modified polyester fiber is composed of a modified polyester
obtained by copolymerizing: ethylene terephthalate as a main constitutional unit;
equal to or more than 12 mol% and equal to or less than 25 mol% of an aliphatic dicarboxylic
acid having 4 to 8 carbon atoms; and equal to or more than 2 mol% and equal to or
less than 5 mol% of a metal sulfonate group-containing aromatic dicarboxylic acid.
[0017] It is preferable that the modified polyester fiber according to the invention is
characterized in that the aliphatic dicarboxylic acid is adipic acid, and the metal
sulfonate group-containing aromatic dicarboxylic acid is 5-sodium sulfoisophthalic
acid.
[0018] It is preferable that the modified polyester fiber according to the invention is
characterized by having a content of diethylene glycol of equal to or more than 0.5
mass% and equal to or less than 3.0 mass%.
[0019] It is preferable that the modified polyester fiber according to the invention has
a single fiber fineness of equal to or more than 0.6 dtex and equal to or less than
3.5 dtex, a fiber strength of equal to or more than 2.0 cN/dtex and equal to or less
than 3.5 cN/dtex, and a fiber elongation of equal to or more than 25% and equal to
or less than 45%.
[0020] It is preferable that the modified polyester fiber according to the invention is
characterized in that the modified polyester fiber contains lithium acetate and diethylene
glycol, and a content of the lithium acetate is 50 to 120 ppm in terms of lithium
atom content.
[0021] The woven or knitted fabric according to the invention contains a modified polyester
fiber and a fiber not for weight reduction, characterized in that: the modified polyester
fiber has a weight reduction ratio of equal to or more than 5% and equal to or less
than 15% and the fiber not for weight reduction has a weight reduction ratio of equal
to or more than 0% and less than 5%; a content of the modified polyester fiber in
the woven or knitted fabric is equal to or more than 5 mass% and equal to or less
than 50 mass%; a content of the fiber not for weight reduction in the woven or knitted
fabric is equal to or more than 50 mass% and equal to or less than 95 mass%; and the
weight reduction ratio is obtained by the following measuring method:
<measuring method of weight reduction ratio of fiber>
the measuring method of the weight reduction ratio including: adding 100 g of a fiber
to 2 L of an aqueous solution including 40 g/L of sodium carbonate; heating an obtained
mixture at 100°C for 30 minutes; performing drying treatment at 80°C for 60 minutes;
and after that, measuring a fiber mass A g.

[0022] The woven or knitted fabric according to the invention contains a modified polyester
fiber and a fiber not for weight reduction, characterized in that: the modified polyester
fiber has a weight reduction ratio of equal to or more than 5% and equal to or less
than 15% and the fiber not for weight reduction has a weight reduction ratio of equal
to or more than 0% and less than 5%; the woven or knitted fabric has an etching finished
part of the modified polyester fiber; a weight reduction ratio of the modified polyester
fiber in the etching finished part to the modified polyester fiber in a non-etching
finished part is equal to or more than 50 mass% and equal to or less than 100 mass%;
and the weight reduction ratio is obtained by the above-described measuring method
of the weight reduction ratio of the fiber.
[0023] It is preferable that the woven or knitted fabric according to the invention is characterized
in that a difference between said weight reduction ratio of the modified polyester
fiber and said weight reduction ratio of the non-etched fiber is equal to or more
than 5%.
[0024] It is preferable that the woven or knitted fabric according to the invention is characterized
in that a burst strength of the woven or knitted fabric in the etching finished part
is equal to or more than 250 kPa and equal to or less than 900 kPa.
[0025] It is preferable that the woven or knitted fabric according to the inventionhas a
strength retention ratio of aburst strength of the woven or knitted fabric in the
etching finished part to a burst strength of the woven or knitted fabric in the non-etching
finished part of equal to or more than 50%.
[0026] It is preferable that the woven or knitted fabric according to the invention is characterized
in that the modified polyester fiber is a modified polyester that is obtained by copolymerizing:
ethylene terephthalate as a main constitutional unit; equal to or more than 16 mol%
and equal to or less than 25 mol% of an aliphatic dicarboxylic acid having 4 to 8
carbon atoms; and equal to or more than 2 mol% and equal to or less than 5 mol% of
a metal sulfonate group-containing aromatic dicarboxylic acid.
[0027] It is preferable that the woven or knitted fabric according to the invention is characterized
in that the fiber not for weight reduction contains equal to or more than 50 mass%
and equal to or less than 95 mass% of synthetic fibers.
[0028] It is preferable that the woven or knitted fabric according to the invention is characterized
in that the synthetic fiber is at least one of a regular polyester fiber, a polyamide
fiber, an elastic fiber, a polyolefin fiber, and an acrylic fiber.
[0029] It is preferable that the woven or knitted fabric according to the invention is characterized
in that a single fiber fineness of the modified polyester fiber is equal to or more
than 0.6 dtex and equal to or less than 3.5 dtex.
[0030] It is preferable that the woven or knitted fabric according to the invention is characterized
in that the elastic fiber is composed of any one of a polyurethane fiber, a polytrimethylene
terephthalate fiber, and a polybutylene terephthalate fiber.
[0031] It is preferable that the method for producing the woven or knitted fabric according
to the invention includes: printing an etching finish agent on a cloth that contains
a modified polyester fiber having a weight reduction ratio of equal to or more than
5% and equal to or less than 15% and a fiber not for weight reduction; and performing
weight reduction processing by supplying a superheated steam to a part on which the
etching finish agent is printed; the method being characterized in that: the etching
finish agent has a pH of equal to or more than 8 and equal to or less than 13 ; the
heatingmethod includes supplying a superheated steam of equal to or higher than 150°C
and equal to or lower than 200°C; the heating time is equal to or more than 5 minutes
and equal to or less than 15 minutes; and the weight reduction ratio is obtained by
the above-described measuring method of the weight reduction ratio of the fiber.
Advantageous Effects of Invention
[0032] According to the invention, in etching finishing of a woven or knitted fabric containing
a modified polyester fiber, it is possible that reduction in strength of parts other
than etched parts of the modified polyester fiber does not occur. In addition, it
is possible that reduction in strength of etched parts of the woven or knitted fabric
containing a fiber other than the modified polyester fiber does not occur. At the
same time, a good etching action can be obtained. According to the invention, it is
possible to obtain an etching finished product of which the modified polyester fiber
is etched well without causing reduction in strength.
Description of Embodiments
[0033] The modified polyester fiber according to the invention is a modified polyester fiber
characterized by having a weight reduction ratio of equal to or more than 5% and equal
to or less than 15%, the weight reduction ratio being obtained by the following measuring
method:
<measuring method of weight reduction ratio of fiber>
the measuring method of the weight reduction ratio including: adding 100 g of a fiber
to 2 L of an aqueous solution including 40 g/L of sodium carbonate; heating an obtained
mixture at 100°C for 30 minutes; performing drying treatment at 80°C for 60 minutes;
and after that, measuring a fiber mass A g.

[0034] When the modified polyester fiber according to the invention has the weight reduction
ratio of equal to or more than 5%, weight-reduction of the modified polyester fiber
is capable of being performed with an alkali easily, and deterioration in physical
properties of a fiber not for weight reduction can be suppressed. In addition, when
the weight reduction ratio is equal to or less than 15%, reduction in strength of
the modified polyester fiber according to the invention is low, and it is possible
to suppress thread breakage inaproduction process of a woven or knitted fabric.
[0035] From the above points of view, the weight reduction ratio of the fiber is more preferably
equal to or more than 7% and equal to or less than 13%, and is even more preferably
equal to or more than 8% and equal to or less than 11%.
[0036] It is preferable that the modified polyester fiber according to the invention is
composed of a modified polyester obtained by copolymerizing: ethylene terephthalate
as a main constitutional unit; equal to or more than 12 mol% and equal to or less
than 25 mol% of an aliphatic dicarboxylic acid having 4 to 8 carbon atoms; and equal
to or more than 2 mol% and equal to or less than 5 mol% of a metal sulfonate group-containing
aromatic dicarboxylic acid.
[0037] It is preferable that the modified polyester fiber according to the invention is
characterized in that the aliphatic dicarboxylic acid is adipic acid, and the metal
sulfonate group-containing aromatic dicarboxylic acid is 5-sodium sulfoisophthalic
acid.
[0038] The aliphatic dicarboxylic acid having 4 to 8 carbon atoms, which is a copolymer
component, increases alkali solubility of the polyester fiber by disturbing an amorphous
structure of the fiber. Examples of the aliphatic dicarboxylic acid having 4 to 8
carbon atoms include succinic acid, glutaric acid, adipic acid, pimelicacid, and suberic
acid, and particularly preferable examples of the aliphatic dicarboxylic acid having
4 to 8 carbon atoms include adipic acid.
[0039] An amount of the copolymerized aliphatic dicarboxylic acid having 4 to 8 carbon atoms
is equal to or more than 16 mol% and equal to or less than 25 mol%, and is preferably,
equal to or more than 18 mol% and equal to or less than 20 mol%. When the amount of
the copolymerized aliphatic dicarboxylic acid having 4 to 8 carbon atoms is within
this range, significant deterioration in dynamic and heat characteristics is suppressed,
and the amorphous structure of the fiber is disturbed, which contributes to improvement
of dyeability with a disperse dye and a cationic dye. In addition, alkali solubility
of the fiber is significantly increased. When the amount of the copolymerized aliphatic
dicarboxylic acid having 4 to 8 carbon atoms is equal to or more than 16 mol%, it
becomes easy to obtain a solubility with an alkali easily suitable for opal finishing.
When the amount of the copolymerized aliphatic dicarboxylic acid having 4 to 8 carbon
atoms is equal to or less than 25 mol%, it becomes easy to maintain physical properties,
fastness properties, and heat characteristics such as heat resistance of the fiber,
which are required to be used as a fiber.
[0040] The metal sulfonate group-containing aromatic dicarboxylic acid, which is the other
copolymer component, is a component which acts as a cationic dye-dyeing site since
a metal sulfonate group is introduced into a fiber. In addition, the metal sulfonate
group-containing aromatic dicarboxylic acid is a component which makes it possible
to dye a polyethylene terephthalate fiber with a cationic dye under normal pressure.
Further, the metal sulfonate group, together with an aromatic ring, is introduced
into the fiber, and makes it possible to improve dyeability with a disperse dye. Furthermore,
the temperature on dying can be lowered. In addition, the metal sulfonate group-containing
aromatic dicarboxylic acid also contributes to improvement of alkali solubility of
the fiber. Examples of the metal sulfonate group-containing aromatic dicarboxylic
acid include, 5-sodium sulfoisophthalic acid, potassium sulfoterephthalic acid, sodium
sulfonaphthalene dicarboxylic acid and the like. Particularly preferable examples
of the metal sulfonate group-containing aromatic dicarboxylic acid include 5-sodium
sulfoisophthalic acid.
[0041] An amount of the copolymerized metal sulfonate group-containing aromatic dicarboxylic
acid is equal to or more than 2 mol% and equal to or less than 5 mol%. When the amount
of the copolymerized metal sulfonate group-containing aromatic dicarboxylic acid is
equal to or more than 2 mol%, it becomes easy to obtain sufficient dyeability with
a cationic dye. In addition, it tends to be easy to lower a temperature on dying with
a disperse dye sufficiently. When the amount of the copolymerized metal sulfonate
group-containing aromatic dicarboxylic acid is equal to or less than 5 mol%, it tends
to be easy to decrease the thread breakage during spinning and the occurrence of fuzz.
[0042] The production of the modified polyester according to the invention can be achieved
by a known method which is the same as the production of a polyethylene terephthalate.
In other words, when terephthalic acid is used, a method which includes causing an
esterification reaction of terephthalic acid with ethylene glycol is employed. Alternatively,
when dimethyl terephthalate, which is an ester, is used, a method which includes causing
a transesterification reaction between dimethyl terephthalate and ethylene glycol,
and thereafter, performing a polycondensation reaction is employed.
[0043] The aliphatic dicarboxylic acidhaving4 to 8 carbon atoms, which is a copolymer component,
can be added at an arbitrary stage before completion of the polycondensation. For
example, the aliphatic dicarboxylic acid having 4 to 8 carbon atoms is added as a
slurry in ethylene glycol at the time of starting the esterification reaction between
terephthalic acid and ethylene glycol. Alternatively, the aliphatic dicarboxylic acid
having 4 to 8 carbon atoms is added as a dispersion or a solution of the aliphatic
dicarboxylic acid or bis-hydroxy dicarbonate in ethylene glycol to bis(β-hydroxyethyl)terephthalate
which is generated by the esterification reaction between terephthalic acid and ethylene
glycol. Meanwhile, when producing the modified polyester, a gloss reducing agent,
an antistatic agent, a flame retardant, a pigment and the like may be added at an
arbitrary stage before completion of the polycondensation.
[0044] Similarly, the metal sulfonate group-containing aromatic dicarboxylic acid, which
is a copolymer component in producing the modified polyester, can be added at an arbitrary
stage before completion of the polycondensation.
[0045] For example, the metal sulfonate group-containing aromatic dicarboxylic acid is added
as a slurry in ethylene glycol at the time of starting the esterification reaction
between terephthalic acid and ethylene glycol. Alternatively, the metal sulfonate
group-containing aromatic dicarboxylic acid is added as a dispersion or a solution
of the metal sulfonate group-containing aromatic dicarboxylic acid dimethyl ester
or diglycol ester in ethylene glycol to bis(β-hydroxyethyl)terephthalate which is
generated by the esterification reaction between terephthalic acid and ethylene glycol.
[0046] It is preferable that the modified polyester fiber according to the invention has
a content of diethylene glycol of equal to or more than 0.5 mass% and equal to or
less than 3.0 mass%.
[0047] When producing the modified polyester, especially when producing the modified polyester
by a direct esterification method, diethylene glycol, which is produced by dehydrative
dimerization of ethylene glycol, is produced as a by-product, and remains in the subsequent
polycondensation reaction system.
[0048] When the content of diethylene glycol in the modified polyester fiber according to
the invention is equal to or less than 3.0 mass%, deterioration in a fiber strength
can be suppressed. From the above points of view, the content of diethylene glycol
in the modified polyester fiber is more preferably equal to or less than 2.5 mass%,
and is further more preferably equal to or less than 2.0 mass%.
[0049] Preferable examples of the method for suppressing the by-production of diethylene
glycol include a method which includes adding a weak acid salt or a hydroxide of an
alkali metal or an alkali earth metal to the reaction system during the esterification
reaction. In particular, sodium hydroxide, sodium acetate, lithium acetate and the
like are effective for suppressing the by-production of diethylene glycol, and are
preferably used when the content of dicarboxylic acids, which are copolymer components,
is equal to or more than 10 mol%. In the invention, lithium acetate is more preferably
used.
[0050] It is preferable that the modified polyester fiber according to the invention contains
lithium acetate and a content of the lithium acetate is 50 to 120 ppm in terms of
lithium atom content.
[0051] The content of lithium acetate is preferably 50 to 150 ppm to a polymer composition
in terms of lithium atom content, is more preferably 100 to 150 ppm, and is even more
preferably 120 to 150 ppm. When such an amount of lithium acetate is added and contained,
the modified polyester having a content of ethylene glycol of equal to or more than
0.5 mass% and equal to or less than 3.0 mass% can be obtained.
[0052] It is preferable that the modified polyester fiber according to the invention has
a single fiber fineness of equal to or more than 0.6 dtex and equal to or less than
3.5 dtex, a fiber strength of equal to or more than 2 cN/dtex and equal to or less
than 3.5 cN/dtex, and a fiber elongation of equal to or more than 25% and equal to
or less than 45%.
[0053] It is preferable that the modified polyester fiber according to the invention has
a single fiber fineness of equal to or more than 0.6 dtex, because a fiber strength
can be maintained and the manufacturability of a woven or knitted fabric is good.
It is preferable that the modified polyester fiber according to the invention has
a single fiber fineness of equal to or less than 3.5 dtex, because the weight reduction
processability is good. From the above points of view, the single fiber fineness is
more preferably equal to or more than 1 dtex and equal to or less than 3 dtex, and
is further more preferably equal to or more than 1.3 dtex and equal to or less than
2.5 dtex.
[0054] It is preferable that the modified polyester fiber according to the invention has
a fiber strength of equal to or more than 2 cN/dtex and equal to or less than 3.5
cN/dtex, because there is no problem in the manufacturability of a woven or knitted
fabric . It is more preferable that the modified polyester fiber according to the
invention has a fiber strength of equal to or more than 2.3 cN/dtex and equal to or
less than 3 cN/dtex. In addition, it is preferable that the modified polyester fiber
according to the invention has an elongation of equal to or more than 25% and equal
to or less than 45%, because the manufacturability of a woven or knitted fabric is
good. It is more preferable that the modified polyester fiber according to the invention
has an elongation of equal to or more than 30% and equal to or less than 40%.
[0055] The modified polyester according to the invention is produced through, for example,
the following production steps:
the step of supplying a slurry of terephthalic acid and ethylene glycol into an esterification
reaction vessel in which bis(β-hydroxyethyl)terephthalate and an oligomer thereof
are present, and causing an esterification reaction at a temperature around 250°C
for 3 to 8 hours to give a reaction product having an esterification rate of equal
to or more than 95%; the step of transferring the esterification reaction product
to a polymerization vessel, adding each of an aliphatic dicarboxylic acid and a metal
sulfonate group-containing aromatic dicarboxylic acid, which are copolymer components,
lithium acetate, magnesium acetate, triethyl phosphate, and germanium dioxide as a
solution or a dispersion in ethylene glycol, and thereafter, adding antimony trioxide,
which is a polymerization catalyst, as a dispersion in ethylene glycol, raising the
temperature, and performing a polycondensation reaction at a temperature around 270°C
under reduced pressure until a polycondensate reaches a predetermined limiting viscosity;
and after that,
the step of removing the polycondensate to give a strand and making the strand as
a chip.
[0056] The modified polyester fiber according to the invention can be obtained by a known
melt spinning method similar to a method for producing a polyethylene terephthalate
fiber. As a method for making a yarn which includes spinning by extruding a modified
polyester chip from a spinning hole of a spinning nozzle and subsequent drawing, a
known method may be also employed. For example, for the production of the modified
polyester fiber, a condition of: a spinning temperature of 240 to 300°C; a spinning
speed of 1,000 to 2,000 m/min; a drawing temperature of 60 to 90°C; a drawing speed
of 400 to 1,000 m/min; a drawing ratio of 1.8 to 3.5 times; a drawing ratio of 0.65
to 0.80 times the maximum drawing ratio; and a heat set temperature of 110 to 160°C;
is used. Here, the maximum drawing ratio refers to a ratio obtained when drawing is
performed until an undrawn yarn is cut at a drawing temperature of 80°C, a heat set
temperature of 145°C, and a drawing speed of 600 m/min.
[0057] In a yarn manufacturing process, a method which includes winding an undrawn yarn
after spinning once and then drawing, a method which includes drawing without winding
an undrawn yarn after spinning, a method which includes winding a yarn as a half undrawn
yarn by high speed spinning at a spinning speed of equal to or more than 2,000 m/min,
a method which includes high speed spinning and drawing without winding, or a similar
method may be employed.
[0058] The modified polyester fiber according to the invention is suitably used for opal
finishing in which a part of component fibers of a woven or knitted fabric is etching
removed. Accordingly, a single fiber fineness of the modified polyester fiber, or
when the form of the fiber is a filament yarn, a single yarn fineness, is preferably
equal to or more than 0.6 dtex and equal to or less than 3.5 dtex because etching
removal of the fiber is easy. The cross sectional shape of the modified polyester
fiber may be any shapes including a circular shape, a flat shape, a triangle shape,
a Y-shape, a multilobed shape and the like. In addition, the form of the modified
polyester fiber may be any of a short fiber, and a filament. When the form of the
fiber is a filament, the filament yarn may be subjected to crimping processing or
false twist processing.
[0059] The modified polyester fiber according to the invention has easy dyeability, that
is, capability of being dyed with a disperse dye under normal pressure, as well as
dyeability, that is, capability of being dyed with a cationic dye under normal pressure.
At the same time, the modified polyester fiber according to the invention has solubility
with an alkali easily, that is, capability of being etching removed easily. Accordingly,
when a mixed woven or knitted fabric, which is obtained by combined weaving or knitting
of the modified polyester fiber according to the invention with another fiber having
high chemical resistance, is subj ected to opal finishing, opal finished products
having various colors and color tones can be obtained by adding a disperse dye or
a cationic dye to an etching paste or a paste containing an etching finish accelerator
for printing. Especially preferable examples of the fiber having high chemical resistance
which is used in combination include a polyethylene terephthalate fiber. Accordingly,
the modified polyester fiber according to the invention is capable of producing an
opal finished product of a mixed woven or knitted fabric consisting only of polyester
fibers, by being combined with a polyethylene terephthalate fiber. In addition, the
modified polyester fiber according to the invention may be used in combination with
another fiber having low chemical resistance or another fiber having different chemical
resistance, for example, wool, silk, cotton, rayon, an acetate fiber, a polyamide
fiber or the like, other than a fiber having high chemical resistance, according to
the need. The modified polyester fiber according to the invention is capable of producing
an opal finished product having various colors, color tones, and textures, by adding
a dye suitable for the fiber to be combined to an etching paste.
[0060] In addition, the modified polyester fiber according to the invention makes it possible
to obtain an opal finished product having stretchability due to its solubility with
an alkali easily. The opal finished product having stretchability can be obtained
by combining the modified polyester fiber with a polyethylene terephthalate fiber
and a polyurethane fiber and performing opal finishing under a mild alkali treatment
condition such that a highly stretchable part in which only the modified polyester
fiber is etching removed is formed without embrittling the polyurethane fiber. The
polyurethane fiber which is used may be any of a polyether-based polyurethane fiber,
and a polyester-based polyurethane fiber.
[0061] For opal finishing performed on a mixed woven or knitted fabric obtained by combined
weaving or knitting of the modified polyester fiber according to the invention with
a polyethylene terephthalate fiber, and optionally, a polyurethane fiber, for example,
a method which includes the steps of printing an etching paste which contains sodium
hydroxide as an etching agent, drying, etching treating by wet heating or dry heating,
and soaping and washing with water; a method which includes the steps of printing
a paste containing an etching finish accelerator, drying and heat treating, soaping
and washing with water, and alkali weight reduction treating (etching treating) with
sodium hydroxide; and the like may be employed. However, conditions of the methods
vary depending on a woven or knitted fabric texture, a mixing ratio of fibers, an
etching pattern, a use or the like. In the case of opal finishing of a mixed woven
or knitted fabric composed of the modified polyester fiber according to the invention,
a polyethylene terephthalate fiber, and optionally, a polyurethane fiber, the alkali
weight reduction treatment (etching treatment) in the latter method may be performed
by alkali weight reduction processing which is generally applied to a woven or knitted
fabric of a polyester fiber, and the latter method is more preferably employed. When
opal finishing is performed, a dye may be appropriately added to an etching paste
or a paste containing an etching finish accelerator such that etching and coloring
of a non-etched fiber are performed simultaneously. In addition, dying maybe combinedly
performed before or after opal finishing. As a result, an opal finished product which
has various colors, a low single fiber fineness, as well as a high-grade sense can
be obtained.
[0062] Examples of the opal finished product of the mixed woven or knitted fabric obtained
by using the modified polyester fiber according to the invention include an embroidery
lace, an outerwear as well as an innerwear such as lingerie, a foundation, a swimsuit,
an underwear for sports, a bodysuit, a leotard, tights for sports and a girdle.
[0063] The woven or knitted fabric according to the invention is a woven or knitted fabric
containing a modified polyester fiber and a fiber not for weight reduction, characterized
in that: the modified polyester fiber has a weight reduction ratio of equal to or
more than 5% and equal to or less than 15% and the fiber not for weight reduction
has a weight reduction ratio of equal to or more than 0% and less than 5%; a content
of the modified polyester fiber in the woven or knitted fabric is equal to or more
than 5 mass% and equal to or less than 50 mass%; a content of the fiber not for weight
reduction in the woven or knitted fabric is equal to or more than 50 mass% and equal
to or less than 95 mass%; and the weight reduction ratio is obtained by the following
measuring method:
<measuring method of weight reduction ratio of fiber>
the measuring method of the weight reduction ratio including: adding 100 g of a fiber
to 2 L of an aqueous solution including 40 g/L of sodium carbonate; heating an obtained
mixture at 100°C for 30 minutes; performing drying treatment at 80°C for 60 minutes;
and after that, measuring a fiber mass A g.

[0064] The woven or knitted fabric according to the invention contains the fiber not for
weight reduction having the weight reduction ratio of equal to or more than 0% and
less than 5%, and therefore, when the modified polyester fiber according to the invention
is subjected to weight reduction with an alkali, the fiber not for weight reduction
remains and etching finishing can be performed.
[0065] From the above point of view, the weight reduction ratio of the fiber not for weight
reduction is more preferably equal to or less than 4%, and is further more preferably
equal to or less than 3%.
[0066] In addition, when the content of the modified polyester fiber in the woven or knitted
fabric is equal to or more than 5 mass%, an effect of etching finishing tends to be
easily exhibited. Further, when the content of the modified polyester fiber in the
woven or knitted fabric is equal to or less than 50 mass%, the non-etched fiber remains
sufficiently, and therefore, strength of the woven or knitted fabric can be maintained
sufficiently.
[0067] From the above points of view, the content of the modified polyester fiber in the
woven or knitted fabric is more preferably equal to or more than 10 mass% and equal
to or less than 40 mass%, and is even more preferably equal to or more than 15 mass%
and equal to or less than 30 mass%.
[0068] The woven or knitted fabric according to the invention is a woven or knitted fabric
containing a modified polyester fiber and a fiber not for weight reduction, characterized
in that: the modified polyester fiber has a weight reduction ratio of equal to or
more than 5% and equal to or less than 15% and the fiber not for weight reduction
has a weight reduction ratio of equal to or more than 0% and less than 5%; the woven
or knitted fabric has an etching finished part of the modified polyester fiber; a
weight reduction ratio of the modified polyester fiber in the etching finished part
to the modified polyester fiber in a non-etching finished part is equal to or more
than 50 mass% and equal to or less than 100 mass%; and the weight reduction ratio
is obtained by the following measuring method:
<measuring method of weight reduction ratio of fiber>
the measuring method of the weight reduction ratio including: adding 100 g of a fiber
to 2 L of an aqueous solution including40 g/Lof sodium carbonate; heating an obtained
mixture at 100°C for 30 minutes; performing drying treatment at 80°C for 60 minutes;
and after that, measuring a fiber mass A g.

[0069] The woven or knitted fabric according to the invention having the etching finished
part has a weight reduction ratio of the modified polyester fiber in the etching finished
part to the modified polyester fiber in the non-etching finished part of equal to
or more than 50 mass% and equal to or less than 100 mass%.
[0070] When the weight reduction ratio is 50%, an effect of weight reduction processing
on a woven fabric is sufficient. When the weight reduction ratio is 100%, there is
no modified polyester fiber in the etching finished part, and such a state is preferable.
However, from the point of view of a designing effect on the woven or knitted fabric,
it is preferable to make at least a part of the modified polyester remain in the etching
finished part.
[0071] It is preferable that the woven or knitted fabric according to the invention has
a burst strength of the woven or knitted fabric in the etching finished part of equal
to or more than 250 kPa and equal to or less than 900 kPa.
[0072] When the burst strength is equal to or more than 250 kPa, the strength has no problem
for the woven or knitted fabric to be used as a product. In addition, when the burst
strength is 900 kPa, the strength is sufficient for the woven or knitted fabric to
be used.
[0073] From the above points of view, the burst strength is preferably equal to or more
than 400 kPa, and is more preferably equal to or more than 600 kPa.
[0074] It is preferable that the woven or knitted fabric according to the invention has
a strength retention ratio of a burst strength of the woven or knitted fabric in the
etching finished part to a burst strength of the woven or knitted fabric in the non-etching
finished part of equal to or more than 50%.
[0075] When the strength retention ratio of the burst strength of the woven or knitted fabric
in the etching finished part to the burst strength of the woven or knitted fabric
in the non-etching finished part is equal to or more than 50%, the break of the woven
or knitted fabric due to the excess stress concentration to the etching finished part
is suppressed.
[0076] From the above points of view, the strength retention ratio is more preferably equal
to or more than 70%, and is further more preferably equal to or more than 85%.
[0077] It is preferable that the woven or knitted fabric according to the invention is characterized
in that the modified polyester fiber is a modified polyester fiber that is obtained
by copolymerizing: ethylene terephthalate as a main constitutional unit; equal to
or more than 16 mol% and equal to or less than 25 mol% of an aliphatic dicarboxylic
acid having 4 to 8 carbon atoms; and equal to or more than 2 mol% and equal to or
less than 5 mol% of a metal sulfonate group-containing aromatic dicarboxylic acid.
[0078] When the modified polyester fiber has an amount of the copolymerized aliphatic dicarboxylic
acid having 4 to 8 carbon atoms of equal to or more than 16 mol%, weight reduction
tends to be easily performed even in a range of pH equal to or more than 9 and equal
to or less than 13. When the amount of the copolymerized aliphatic dicarboxylic acid
having 4 to 8 carbon atoms is equal to or less than 25 mol%, thread breakage of said
fiber during spinning canbe suppressed, and productivity becomes good.
[0079] From the above points of view, it is more preferable that the amount of the copolymerized
aliphatic dicarboxylic acid having 4 to 8 carbon atoms is equal to or less than 20
mol%.
[0080] It is preferable that the woven or knitted fabric according to the invention is characterized
in that the fiber not for weight reduction contains equal to or more than 50 mass%
and equal to or less than 95 mass% of synthetic fibers.
[0081] When the content of the synthetic fiber in the woven or knitted fabric is equal to
or more than 50 mass%, deterioration in the burst strength of the etching finished
part can be suppressed. In addition, when the content of the synthetic fiber is equal
to or less than 95 mass%, an etched fiber can be contained, and therefore, it becomes
possible to exhibit effects of etching finishing easily. From the above points of
view, the content of the synthetic fiber is more preferably equal to or more than
60 mass% and equal to or less than 80 mass%.
[0082] It is preferable that the woven or knitted fabric according to the invention is characterized
in that the synthetic fiber is at least one of a regular polyester fiber, a polyamide
fiber, an elastic fiber, a polyolefin fiber, and an acrylic fiber.
[0083] Among the above, from the point of view of strength, the synthetic fiber is preferably
a regular polyester fiber, and from the point of view of exhibiting stretchability,
the synthetic fiber is preferably an elastic fiber.
[0084] It is preferable that the woven or knitted fabric according to the invention is characterized
in that a single fiber fineness of the modified polyester fiber is equal to or more
than 0.6 dtex and equal to or less than 3.5 dtex.
[0085] When the single fiber fineness is equal to or more than 0.6 dtex, strength of the
woven or knitted fabric can be increased, and when the single fiber fineness is equal
to or less than 3.5 dtex, etching finish properties become good, and the texture of
the woven or knitted fabric tends to be easily made to be soft.
[0086] From the above points of view, it is more preferable that the single fiber fineness
is equal to or more than 0.9 dtex and equal to or less than 2.5 dtex.
[0087] It is preferable that the woven or knitted fabric according to the invention is characterized
in that the elastic fiber is anyone of apolyurethane fiber, a polytrimethylene terephthalate
fiber, and a polybutylene terephthalate fiber, as described above.
[0088] It is preferable that the woven or knitted fabric according to the invention is composed
of the modified polyester fiber, the regular polyester fiber and the polyurethane
fiber. When the woven or knitted fabric has the above-described constitution, the
woven or knitted fabric which has stretchability, high strength, and a soft texture
can be obtained.
[0089] The method for producing the woven or knitted fabric according to the invention is
a method for producing a woven or knitted fabric, the method including: printing an
etching finish agent on a cloth that contains a modified polyester fiber, which is
weight reduced under a condition of pH of equal to or more than 8 and equal to or
less than 13, and a fiber not for weight reduction; and performing weight reduction
processing by supplying a superheated steam to a part on which the etching finish
agent is printed; the method being characterized in that: the etching finish agent
has a pH of equal to or more than 8 and equal to or less than 13 ; the heating method
includes supplying a superheated steam of equal to or higher than 150°C and equal
to or lower than 200°C; and the heating time is equal to or more than 5 minutes and
equal to or less than 15 minutes.
[0090] The heating method includes supplying a superheated steam of equal to or higher
than 150°C and equal to or lower than 200°C onto a part on which an etching finish
agent is printed. When the temperature of the superheated steam is equal to or higher
than 150°C, etching finish properties becomes good, and when the temperature of the
superheated steam is equal to or lower than 200°C, it becomes possible to prevent
the texture of the polyester fiber from becoming hard.
[0091] It is preferable that the heating time is equal to or more than 5 minutes and equal
to or less than 15 minutes.
[0092] When the heating time is equal to or more than 5 minutes, etching finish properties
become good, and when the heating time is equal to or less than 15 minutes, reduction
in strength of the non-etching finished part can be suppressed.
[0093] An etching finish agent is characterized by containing a pasting agent and a component
having an etching action in a specific range of pH (pH of equal to or more than 8
and equal to or less than 13) except for guanidine carbonate. It is preferable that
the component having the etching action is one or two types selected from sodium carbonate
and potassium carbonate, and it is more preferable that the component having the etching
action is one type which is sodium carbonate. An amount of sodium carbonate or potassium
carbonate used may be adjusted depending on the mass of the modified polyester fiber
to be etched. In general, it is preferable that the amount of sodium carbonate or
potassium carbonate used may be in a range of equal to or more than 5 mass% and equal
to or less than 15 mass% to the amount of the etching finish agent. The etching finish
agent may contain an etching finish accelerator, according to the need. The etching
finish accelerator is not particularly limited, and a commercially available etching
finishaccelerator may be used. For example, it is preferable that the etching finish
accelerator is a Mei printer OP-2 manufactured by Meisei Chemical Works, Ltd.
[0094] Examples of the pasting agent contained in the etching finish agent which may be
used include a natural pasting agent, a processed pasting agent, a semisynthetic pasting
agent, and a synthetic pasting agent. Examples of the pasting agent include a locust
bean gum based pasting agent, a starch based pasting agent, a dextrin based pasting
agent, a crystal gum based pasting agent, a tragacanth gum based pasting agent, a
cellulose based pasting agent, carboxymethyl cellulose, polyvinyl alcohol, sodium
polyacrylate and the like. The pasting agent may be used alone or two or more types
of them may be used. A ratio of the pasting agent is not particularly limited as long
as a viscosity suitable for printing the etching finish agent and performing heat
treatment can be maintained. For example, it is preferable that the pasting agent
is contained in a ratio equal to or more than 1 mass% and equal to or less than 10
mass% to the etching finish agent.
[0095] The etching finish agent may further contain other compounds such as a dye.
[0096] A method for etching finishing which includes using the above-described etching finish
agent is described hereinbelow.
[0097] The above-described etching finish agent is preferably applied to a woven or knitted
fabric containing a modified polyester fiber.
[0098] A fiber which is used in combination with the modified polyester fiber is not particularly
limited as long as the fiber has a weight reduction resistant property different from
the modified polyester fiber. Examples of the fiber which may be used in combination
with the modified polyester fiber include an unmodified polyester fiber (which is
composed of an unmodified polyethylene terephthalate, and is also referred to as a
regular polyester fiber), a polyamide fiber, a polytrimethylene terephthalate fiber,
a polybutylene terephthalate fiber, a polypropylene fiber, a polyethylene fiber, a
polyurethane fiber and the like. The modified polyester fiber and the above-described
fiber are combined by an arbitrary method such as mixed spinning, mixed fiber producing,
intertwisting and the like to give a woven or knitted fabric composed of a yarn, a
staple yarn and the like. Then, the woven or knitted fabric is subjected to etching
finishing. As the above-described woven or knitted fabric, a fabric which is dyed
may be used, according to the need. Dying is performed by a known arbitrary method
on all parts or one part of the fabric by plain dyeing or printing.
[0099] Etching finishing may be performed by using the above-described etching finish agent,
according to a known method which generally includes printing, heat treating, and
washing. In the step of printing, an etching finish agent is printed on a woven or
knitted fabric containing a modified polyester fiber in a shape in accordance with
a desired pattern. For printing the etching finish agent, a printing method, a spraying
method and the like may be used. The printing method is not particularly limited,
and a frame mold printing method, a flat screen printing method, a rotary screen printing
method, a roller printing method and the like may be used. An adhesion amount of the
etching finish agent onto the woven or knitted fabric may be determined arbitrarily
depending on the printing method, the woven or knitted structure of the fabric, and
the desired pattern.
[0100] For example, when the flat screen printing method is employed, a viscosity of the
etching finish agent, a hardness of a rubber squeegee, a pressure of a rubber squeegee
whenprinting of the etching finish agent is performed, and a printing speed of a squeegee
are determined, depending on the woven or knitted structure to which printing is performed,
a mesh of a flame mold which prints a desired pattern and the like. Then, the etching
finish agent is applied on the fabric in a desired pattern uniformly. In order to
confirm that the etching finish agent is uniformly adhered to the fabric, confirmation
of whether there is a blur in a printed part, confirmation of whether there is a difference
in a pattern between the right and left of the rubber squeegee, confirmation of whether
the etching finish agent is permeated uniformly into the back surface of the printed
part and the like visually are performed. In addition, a coloring paste which does
not contain an etching finish agent maybe printed onto a part other than the adhered
part of the etching finish agent, in a shape in accordance with a desired pattern.
A method for printing the coloring paste is not particularly limited, and the same
printing method as that of the etching finish agent may be employed. After printing
the etching finish agent and the coloring paste to the woven or knitted fabric, the
woven or knitted fabric is appropriately dried, and thereafter, heat treating is performed.
[0101] Examples of the heat treating method include a baking method, a steam method, a HT
steam method and the like. The HT steam method is more preferably employed.
[0102] After the heat treating step, removal of the modified polyester fiber which is embrittled
on the printed parts, removal of a dye unfixed to the fiber, which is a dye used in
combination with the etching finish agent, and washing of a pasting agent used for
a coloring paste which is used for parts other than the adhesion part of the etching
finish agent, the dye unfixed to the fiber and the like are performed. A washing method
is not particularly limited, and washing is performed by a known method. Examples
of the washing method include washing with 2 g/L of a surfactant, alkali washing with
2 g/L of a surfactant and 2 g/L of soda ash, acidic washing with 2 g/L of a surfactant
and 2 g/L of acetic acid (90%), alkali reduction washing with 2 g/L of a surfactant,
2 g/L of soda ash, and 2 g/L of hydrosulfite or thiourea dioxide, and acidic reduction
washing with 2 g/L of a surfactant, 2 g/L of acetic acid (90%) and 4 g/L of rongalite.
A washing temperature is preferably equal to or higher than 60°C and equal to or lower
than 100°C, and a washing time is preferably equal to or more than 5 minutes and equal
to or less than 30 minutes. After that, washing with water, dehydrating and drying
are performed.
[0103] Examples of the surfactant used for washing include a nonionic surfactant, an anionic
surfactant, a cationic surfactant, and an amphoteric surfactant. The surfactant may
be used alone or two or more types of them may be used in combination.
[0104] Examples of the nonionic surfactant include: an ether type nonionic surfactant such
as a higher alcohol alkylene oxide adduct, an alkylphenol alkylene oxide adduct, a
styrenated alkylphenol alkylene oxide adduct, a styrenated phenol alkylene oxide adduct,
a higher alkylamine alkylene oxide adduct; an ether ester type nonionic surfactant
such as a fatty acid alkylene oxide adduct, a polyalcohol fatty acid ester alkylene
oxide adduct, a fatty acid amide alkylene oxide adduct, and an alkylene oxide adduct
of anoil and fat; apolyalkylene glycol type nonionic surfactant such as a polypropylene
glycol ethylene oxide adduct; an ester type nonionic surfactant such as a fatty acid
ester of glycerol, a fatty acid ester of pentaerythritol, a fatty acid ester of sorbitol,
a fatty acid ester of sorbitan, and a fatty acid ester of sucrose; other nonionic
surfactants such as an alkyl ether of a polyalcohol, and a fatty acid amide of alkanolamines.
Examples of the alkylene oxide include ethylene oxide, propylene oxide, and butylene
oxide. A form of an adduct of the alkylene oxide may be a random adduct of two or
more types or may be a block adduct.
[0105] Examples of the anionic surfactant include: an anionic surfactant of a carboxylate
such as a fatty acid soap; a sulfuric acid ester salt such as a sulfuric acid ester
salt of a higher alcohol, a sulfuric acid ester salt of a higher alcohol alkylene
oxide adduct, a sulfuric acid ester salt of a polyoxyalkylene ether, a sulfuric acid
ester salt of a phenol alkylene oxide adduct, a sulfuric acid ester salt of an alkylphenol
alkylene oxide adduct, a sulfuric acid ester salt of a styrenated alkylphenol alkylene
oxide adduct, a sulfuric acid ester salt of a styrenated phenol alkylene oxide adduct,
a sulfuric acid ester salt of a polyalcohol alkylene oxide adduct, a sulfated oil,
a sulfated fatty acid ester, a sulfated fatty acid, and a sulfated olefin; an anionic
surfactant of a salt of a sulfonic acid ester such as a formalin condensate such as
an alkylbenzene sulfonate, an alkylnaphthalene sulfonate, and a naphthalene sulfonic
acid, and a sulfonate such as an α-olefin sulfonate, a paraffin sulfonate, and a salt
of sulfosuccinate diester; a salt of a phosphoric acid ester such as sodium methyl
oleoyl taurate, a salt of a phosphoric acid ester of a higher alcohol, a salt of a
phosphoric acid ester of a polyoxyalkylene ether, a salt of a phosphoric acid ester
of a phenol alkylene oxide adduct, a salt of a phosphoric acid ester of an alkylphenol
alkylene oxide adduct, a salt of a phosphoric acid ester of a styrenated alkylphenol
alkylene oxide adduct, a salt of a phosphoric acid ester of a styrenated phenol alkylene
oxide adduct, and a salt of a phosphoric acid ester of a polyalcohol alkylene oxide
adduct; and other anionic surfactants such as N-methyltaurine oleate, and N-methyltaurine
stearate. Examples of the alkylene oxide include ethylene oxide, propylene oxide,
and butylene oxide. A form of an adduct of the alkylene oxide may be a random adduct
of two or more types or may be a block adduct. Examples of the salt include: an alkali
metal salt such as a lithium salt, a sodium salt, and a potassium salt; an ammonium
salt, and an amine salt such as a salt of a primary amine such as a methylamine salt,
an ethylamine salt, a propylamine salt, a butylamine salt, and an allylamine salt;
a salt of a secondary amine such as a dimethylamine salt, a diethylamine salt, a dipropylamine
salt, a dibutylamine salt, and a diallylamine salt; a salt of a tertiary amine such
as a trimethylamine salt, a triethylamine salt, a tripropylamine salt, and a tributylamine
salt; and a salt of an alkanolamine such as a monoethanolamine salt, a diethanolamine
salt, and a triethanolamine salt.
[0106] Examples of the cationic surfactant include a quarternary ammonium salt of an alkyl
ether, a quarternary ammonium salt of an alkylamide, a quarternary ammonium salt of
a dialkyl ester, a quarternary ammonium salt of a dialkyl imidazoline, an alkylamide
amine, an alkyl ether amine, an alkylamide guanidine, and an arginine derivative.
[0107] Examples of the amphoteric surfactant include an alkylbetaine type surfactant, an
amidopropylbetaine type surfactant, an imidazolinium betaine type surfactant and the
like.
[0108] By the above-described processing method, an etching finished product from which
the modified polyester fiber in the part where the etching finish agent is printed
is removed can be obtained. The obtained etching finished product is subjected to,
according to the need, a known treatment such as dyeing and final finishing.
Examples
[0109] The invention is more specifically described hereinbelow by referring to Examples.
However, the invention is not limited to these Examples. Meanwhile, methods for measuring
and evaluating various characteristic values in Examples are as follows.
(Limiting viscosity [η])
[0110] A temperature of a modified polyester was adjusted to 20°C in a mixed solvent of
phenol/tetrachloroethane = 1/1, and a limiting viscosity was measured by the Ubbelohde
method.
(Content of diethylene glycol (hereinafter, abbreviated as DEG))
[0111] An obtained modified polyester was subj ected to alkaline hydrolysis, and thereafter,
each number of moles of ethylene glycol and DEG was quantified by using a Gas Chromatograph
GC-9A manufactured by Shimadzu Corporation, and a content of DEG was obtained as a
ratio (%) of the number of moles of DEG to the total number of moles of ethylene glycol
and DEG.
(Glass transition temperature Tg)
[0112] A glass transition temperature Tg (°C) of a modified polyester was measured by using
a Differential Scanning Calorimeter DSC 220 manufactured by Seiko Instruments Inc.,
at a temperature raising rate of 10°C/min.
(Strength and elongation)
[0113] A strength (cN/dtex) and an elongation (%) were measured according to JIS L1013 by
using a tension tester Tensilon UTM-4-100 type manufactured by ORIENTEC CORPORATION.
(Alkali weight reduction ratio)
[0114] A weight reduction ratio of a fiber on which alkali weight reduction was performed
was calculated as a weight reduction ratio (%) from a mass of the fiber before treatment
and that of the fiber after treatment according to the following formula:

[0115] It is preferable that alkali weight reduction is performed by making a fiber to take
the form of a knitted fabric from the point of view of handleability.
(Burst strength)
[0116] A burst strength was measured according to the Mullen method of JIS L 1018.
(Burst strength retention ratio)
[0117] 
(Example 1)
[0118] To an esterification reaction vessel in which bis(β-hydroxyethyl)terephthalate and
oligomers thereof were present, a slurry of terephthalic acid (hereinafter abbreviated
as TPA) and ethylene glycol (hereinafter abbreviated as EG) at a molar ratio of 1/1.6
was supplied continuously, and an esterification reaction was performed under a condition
of a temperature of 250°C, a pressure of 0.1 Pa, and a residence time of 8 hours.
Then, 15.4 kg of the obtained esterification reaction product was transferred to a
polycondensation reaction vessel, and 4.6 kg of an EG dispersion in which a concentration
of adipic acid (hereinafter abbreviated as ADA) was adjusted to 50 mass% was added
thereto. In addition, in order to suppress the by-production of DEG, lithium acetate
was added such that a concentration of lithium acetate was 120 ppm in terms of lithium
atom content. After that, the mixture was stirred and mixed at a temperature of 230°C
for 5 minutes, and thereafter, as stabilizers, 120 ppm of magnesium acetate in terms
of magnesium atom content, 140 ppm of triethyl phosphate in terms of phosphorus atom
content and 30 ppm of germanium dioxide in terms of germanium atom content were added,
and 2.6 kg of an EG solution of 5-sodium sulfoisophthalic acid (hereinafter abbreviated
as SIP) in which a concentration of the EG ester of SIP was adjusted to 35 mass% was
added, and then the mixture was stirred and mixed at a temperature of 230°C. Then,
as a polycondensation catalyst, 400 ppm of antimony trioxide was added, and thereafter,
the pressure was gradually reduced such that the reduced pressure after 60 minutes
was equal to or less than 1.2 hPa. The mixture was stirred and mixed, and thereafter,
the temperature was raised to a temperature of 270°C, and a polycondensation reaction
was performed until a polycondensate reached a predetermined limiting viscosity [η].
As a result, a modified polyester having an amount of the copolymerized ADA of 18
mol%, and an amount of the copolymerized SIP of 2.5 mol% was obtained, and the modified
polyester was made to be a chip. Polymer physical properties of the modified polyester
were shown in Table 1.
[0119] The obtained chip of the modified polyester was subjected to spinning by using a
spinning nozzle with a circular shape of a hole and the number of holes of 24 at a
spinning temperature of 255°C, and a spinning speed of 1,800 m/min. The undrawn yarn
was subjected to drawing at a drawing temperature of 65°C, a drawing ratio of 2.28
times, and a ratio of a drawing ratio to the maximum drawing ratio (an MDR ratio)
of 0.72 times. Then, heat setting was performed at 150°C to give a modified polyester
fiber having 84 dtex/24 f (a single yarn fineness of 3.5 dtex) .
[0120] A weft knitted fabric of the modified polyester fiber was produced, and 10 g of the
knitted fabric was subjected to soaking treatment in 1 L of an aqueous solution of
sodium hydroxide at a concentration of 10 g/L, at a temperature of 98°C for 20 minutes.
Thereafter, the knitted fabric was subjected to washing with water, dehydrating, and
drying. A weight reduction ratio was measured according to the following formula:

[0121] Physical properties of the obtained modified polyester filament yarn were shown in
Table 1.
(Example 2)
[0122] By using the modified polyester chip obtained in Example 1, spinning and drawing
were performed in the same manner as Example 1 except that an amount of a polymer
discharged during spinning was changed to 2/5 of that in Example 1 to give a modified
polyester filament yarn having 33 dtex/24 f (a single yarn fineness of 1.38 dtex).
Physical properties of the obtained modified polyester filament yarn were shown in
Table 1.
(Example 3)
[0123] A modified polyester in which 16 mol% of ADA and 2.25 mol% of SIP were copolymerized
was obtained and was made to be a chip in the same manner as Example 1, except that
15.9 kg of the esterification reaction product obtained in Example 1 was transferred
to the polycondensation reaction vessel, and an addition amount of the EG dispersion
of ADA was changed to 4.1 kg and an addition amount of the EG solution of SIP was
changed to 2.4 kg. Polymer physical properties of the modified polyester are shown
in Table 1. By using the obtained modified polyester chip, spinning and drawing were
performed in the same manner as Example 1 except that a spinning speed during spinning
was changed to 1,200 m/min. As a result, a modified polyester filament yarn having
84 dtex/24 f (a single yarn fineness of 3.5 dtex) was obtained. Physical properties
of the obtained modified polyester filament yarn were shown in Table 1.
(Comparative Example 1)
[0124] A modified polyester in which 14 mol% of ADA and 2. 0 mol% of SIP were copolymerized
was obtained and was made to be a chip in the same manner as Example 1, except that
16.4 kg of the esterification reaction product obtained in Example 1 was transferred
to the polycondensation reaction vessel, and an addition amount of the EG dispersion
of ADA was changed to 3.6 kg and an addition amount of the EG solution of SIP was
changed to 2.1 kg. Polymer physical properties of the modified polyester were shown
in Table 1. By using the obtained modified polyester chip, spinning and drawing were
performed under a spinning condition and a drawing condition shown in Table 1. As
a result, a modified polyester filament yarn having 84 dtex/24 f (a single yarn fineness
of 3.5 dtex) was obtained. Physical properties of the obtained modified polyester
filament yarn were shown in Table 1.
(Comparative Example 2)
[0125] A modified polyester in which 10 mol% of ADA and 2.0 mol% of SIP were copolymerized
was obtained and was made to be a chip in the same manner as Example 1, except that
16.9 kg of the esterification reaction product obtained in Example 1 was transferred
to the polycondensation reaction vessel, and an addition amount of the EG dispersion
of ADA was changed to 2.6 kg and an addition amount of the EG solution of SIP was
changed to 2.1 kg. Polymer physical properties of the modified polyester were shown
in Table 1. By using the obtained modified polyester chip, spinning and drawing were
performed under a spinning condition and a drawing condition shown in Table 1. As
a result, a modified polyester filament yarn having 84 dtex/24 f (a single yarn fineness
of 3.5 dtex) was obtained. Physical properties of the obtained modified polyester
filament yarn were shown in Table 1.
(Comparative Example 3)
[0126] A modified polyester in which 5 mol% of ADA and 2.25 mol% of SIP were copolymerized
was obtained and was made to be a chip in the same manner as Example 1, except that
17.6 kg of the esterification reaction product obtained in Example 1 was transferred
to the polycondensation reaction vessel, and an addition amount of the EG dispersion
of ADA was changed to 1.3 kg and an addition amount of the EG solution of SIP was
changed to 2.3 kg. Polymer physical properties of the modified polyester were shown
in Table 1. By using the obtained modified polyester chip, spinning and drawing were
performed under a spinning condition and a drawing condition shown in Table 1. As
a result, a modified polyester filament yarn having 84 dtex/24 f (a single yarn fineness
of 3.5 dtex) was obtained.
[0127] Said fiber has copolymer components of a polyester fiber which is cation dyeable
under normal pressure, which is generally used in the market.
[0128] Physical properties of the obtained modified polyester filament yarn were shown in
Table 1.
[Table 1]
|
Copolymer components |
Polymer physical properties |
Spinning condition |
Drawing condition |
Filament physical properties |
ADA |
SIP |
DEG |
Tg |
[η] |
Temperature |
Speed |
Temperature |
Drawing ratio |
MDR ratio |
Single fiber fineness |
Strength |
Elongation |
Weight reduction ratio |
mol% |
mol% |
% |
°C |
°C |
(m/min) |
°C |
Times |
Times |
dtex |
cN/dtex |
% |
% |
Example 1 |
18 |
2.5 |
1.24 |
46 |
0.558 |
255 |
1800 |
65 |
2.28 |
0.72 |
3.5 |
2.43 |
34.6 |
22.5 |
Example 2 |
18 |
2.5 |
1.38 |
47 |
0.565 |
255 |
1800 |
65 |
2.19 |
0.72 |
1.38 |
2.32 |
31.2 |
27.6 |
Example 3 |
16 |
2.25 |
1.30 |
48 |
0.562 |
255 |
1200 |
65 |
2.79 |
0.75 |
3.5 |
2.45 |
43.4 |
12.5 |
Comparative Example 1 |
14 |
2.0 |
1.33 |
50 |
0.613 |
255 |
1200 |
75 |
1.89 |
0.76 |
3.5 |
1.56 |
32.9 |
11.7 |
Comparative Example 2 |
10 |
2.0 |
1.34 |
56 |
0.543 |
270 |
1200 |
71 |
2.34 |
0.7 |
3.5 |
2.02 |
29.0 |
7.1 |
Comparative Example 3 |
5 |
2.25 |
2.40 |
70 |
0.544 |
283 |
1800 |
82 |
2.55 |
0.71 |
3.5 |
2.99 |
32.0 |
6.3 |
*ADA: adipic acid SIP: 5-sodium sulfoisophthalic acid DEG: diethylene glycol |
(Example 4)
[0129] 48 filaments of a modified polyester fiber having a fineness of 84 dtex which was
composed of a modified polyester resin obtained by copolymerizing ethylene terephthalate
as a main constitutional unit, 16 mol% of ADA and 2.5 mol% of SIP were knitted to
give a weft knitted fabric having a Jersey stitch structure.
[0130] Alkali weight reduction processing was performed on 100 g of the weft knitted fabric
by using a Mini Color dyeing machine (manufactured by Texam Technical Research Institute,
Co. Ltd. , a multicolor rotation pot dyeing test machine), at a concentration of sodium
carbonate of 40 g/L, in a mass ratio of the weft knitted fabric to the sodium carbonate
aqueous solution of 1 : 20, at a temperature of the aqueous solution of 100°C × 30
minutes. Then, washing with water, dehydrating, and drying treatment at 80°C for 60
minutes were performed to give a processed knitted fabric.
[0131] In addition, alkali weight reduction processing was also performed by using an aqueous
solution of each of potassium carbonate, and sodium hydroxide instead of sodium carbonate
in the same manner to give a knitted fabric.
[0132] The pH of each of the aqueous solutions, and the weight reduction ratio of each of
the modified polyester fibers are shown in Table 2.
[0133] Weight reduction ratio (%) = { (mass of weft knitted fabric before alkali weight
reduction processing - mass of processed knitted fabric after alkali weight reduction
processing) /mass of weft knitted fabric before alkali weight reductionprocessing}
× 100.
(Comparative Example 4)
[0134] A processed knitted fabric was obtained in the same manner as Example 4 except that,
as yarns used for the weft knitted fabric, 48 filaments of a cation dyeable polyester
fiber having a fineness of 84 dtex composed of a polyester resin obtained by copolymerizing
ethylene terephthalate as a main constitutional unit, 5 mol% of ADA and 2.3 mol% of
SIP were used.
[0135] The weight reduction ratio is shown in Table 2.
(Comparative Example 5)
[0136] As yarns used for the weft knitted fabric, yarns composed of a polyethylene terephthalate
fiber (an unmodified polyethylene terephthalate) were used. Hereinafter, the polyethylene
terephthalate fiber is also referred to as "a regular polyester fiber". A processed
knitted fabric was obtained in the same manner as Example 4 except that the yarns
composed of the regular polyester fiber were constituted by those manufactured by
TEIJIN LIMITED., and 36 filaments each having a fineness of 84 dtex were used.
[0137] The weight reduction ratio is shown in Table 2.
[Table 2]
|
Fiber |
Copolymer components |
Weight reduction ratio (%) |
ADA |
SIP |
Sodium carbonate 40 g/L |
Potassium carbonate 40 g/L |
Sodium hydroxide 10g/L |
mol% |
mol% |
pH of aqueous solution = 11.8 |
pH of aqueous solution = 11.8 |
pH of aqueous solution = 13.8 |
Example 4 |
Modified polyester |
16 |
2.5 |
9% |
8% |
39% |
Comparative Example 4 |
Cation dyeable polyester |
5 |
2.3 |
3% |
2% |
20% |
Comparative Example 5 |
Regular polyester |
0 |
0 |
0% |
0% |
1% |
[0138] As shown in Table 2, when alkali weight reduction was performed by using sodium carbonate,
the result was that the modified polyester fiber of Example 4 had a higher weight
reduction ratio than the generally used cation dyeable polyester fiber of Comparative
Example 4, and the regular polyester fiber of Comparative Example 5 was not capable
of being alkali weight reduced by using sodium carbonate. In addition, when alkali
weight reduction was performed by using potassium carbonate, the result was that the
modified polyester fiber of Example 4 had a higher weight reduction ratio than the
generally used cation dyeable polyester fiber of Comparative Example 4, and the weight
reduction ratio of the generally used cation dyeable polyester fiber of Comparative
Example 4 was as low as 2% when being weight reduced by using potassium carbonate,
as shown in Table 2. When alkali weight reduction was performed by using sodium hydroxide,
the modified polyester fiber of Example 4 exhibited a higher weight reduction ratio
than the generally used cation dyeable polyester fiber of Comparative Example 4, and
the regular polyester fiber of Comparative Example 5.
(Example 5)
[0139] Etching finishing which dissolves a modified polyester fiber was performed by using
a warp knitted fabric obtained by using the modified polyester fiber used in Example
4 and the regular polyester fiber used in Comparative Example 5 (the modified polyester
fiber = 16.7%, and the regular polyester fiber = 83.4%) and using an etching finish
agent having the following composition. The composition of the etching finish agent
was shown in Table 3.
- Sorbitose C-5 (10% aqueous solution) (manufactured by AVEBE Co., Ltd.) 50 mass%
- Sodium carbonate (manufactured by Tokuyama Corporation, trade name: soda ash) 10 mass%
- Water 40 mass%
[0140] A square pattern was printed on the knitted fabric to be treated with the above-described
etching finish agent, and drying at 110°C × 2 minutes was performed. Then, a superheated
steam treatment was performed by using a HT steamer at 180°C × 8 minutes. After that,
washing was performed at 80°C × 20 minutes by using a soaping bath containing 2 g/L
of Laccol ISF (manufactured by Meisei Chemical Works, Ltd., a nonionic surfactant),
and thereafter, washing with water, dehydrating, and drying were performed to give
a processed warp knitted fabric which was etching finished.
[0141] Evaluation: Etching finish properties were evaluated visually. As evaluation criteria,
as shown in Table 3, with regard to etching finish properties, when a fiber on which
etching is performed in printed parts cannot be visually confirmed, the etching finish
property was marked by ⊙, when etching can be performed though a little residue can
be confirmed visually, and the knitted fabric can be determined as capable of being
used as a commercial product, the etching finish property was marked by ○, and when
etching cannot be performed and a residue can be visually confirmed, and the knitted
fabric can be determined as incapable of being used as a commercial product, the etching
finish property was marked by ×. In addition, the burst strength in the etching finished
part was measured according to the Mullen method of JIS L 1018. The results are shown
in Table 3. The burst strength of the processed knitted fabric in the non-etching
finished part was 755 kPa.
(Example 6)
[0142] An etching finished knitted fabric was obtained in the same manner as Example 5 except
that the composition of a paste liquid was changed to that shown in Table 3, that
is, an etching finish accelerator (manufacturedbyMeisei Chemical Works, Ltd. a Mei
printer OP-2) was used. The evaluation of the etching finish properties is shown in
Table 3.
[0143] By using the etching finish accelerator, etching finish properties which were similar
to etching finish properties exhibited when a strong alkali was used were obtained.
On the other hand, deterioration in the burst strength was little.
(Comparative Examples 6 and 7)
[0144] Etching finishing was performed in the same manner as Example 5 except that each
composition of the etching finish agents and each of conditions were changed to those
shown in Table 3. Then, the obtained etching finished knitted fabric was evaluated.
The results are shown in Table 3.
[0145] Since a strong alkali was used, etching finish properties were good, but deterioration
in the burst strength was large.
[Table 3]
Composition of paste liquid |
Example 5 |
Example 6 |
Comparative Example 6 |
Comparative Example 7 |
Sorbitose C-5 (10% aqueous solution) |
50 |
50 |
50 |
50 |
Sodium carbonate |
10 |
10 |
|
|
Guanidine carbonate |
|
|
10 |
|
Sodium hydroxide |
|
|
|
10 |
Etching finish accelerator (Mei printer OP-2) |
|
20 |
|
|
Water |
40 |
20 |
40 |
40 |
pH of finish agent |
12.0 |
12.2 |
11.8 |
14.5 |
Etching finish properties |
○ |
⊙ |
⊙ |
⊙ |
Burst strength (kPa) |
755 |
628 |
39 |
265 |
Strength ratio (%) |
94.0 |
78.0 |
4.9 |
33.0 |
[0146] As shown in Table 3, in Example 5 in which only sodium carbonate was contained, etching
finishing was capable of being performed, and reduction in strength in the etched
part was also low. On the other hand, in Comparative Example 6 in which guanidine
carbonate was used as well as Comparative Example 7 in which sodium hydroxide was
used, etching finish properties of the etched parts were good, but extreme reduction
in strength in the etched parts was observed.
[0147] The finish agent which used guanidine carbonate had a pH of 11.8, but it is known
that guanidine carbonate becomes a strong alkali when being heated. Accordingly, deterioration
in the burst strength became large.
[0148] In addition, in Example 6 in which a Mei printer OP-2, which is an etching finish
accelerator, and sodium carbonate were contained, good etching finish properties were
able to be obtained, and reduction in strength in the etched parts was also little.
(Example 7)
[0149] Etching finishing was performed in the same manner as Example 6 except that a knitted
fabric (50% modified polyester fiber/500 regular polyester fiber) obtained by using
the modified polyester fiber that is the same as Example 4 and the regular polyester
fiber (manufactured by TEIJIN LIMITED., 84 dtex) that is the same as Comparative Example
5 was used as a knitted fabric to be treated. Then, an etching finished knitted fabric
was obtained. The evaluation of the etching finish properties is shown in Table 4.
With regard to the evaluation of etching finish properties, no fiber was capable of
being confirmed visually in printed parts to which etching was performed, and therefore,
the evaluation result was ⊙.
(Comparative Examples 8 to 11)
[0150] An etching finished fabric was obtained in the same manner as Example 5 except that
the modified polyester fiber used in Example 5 was changed to each of polyester fibers
shown in Table 4. The evaluation of the etching finish properties is shown in Table
4.
[Table 4]
|
Fiber for etching |
Etching finish properties |
Example 7 |
Modified polyester fiber |
⊙ |
Comparative Example 8 |
Polyester fiber cation dyeable under normal pressure (manufactured by KB SEIREN, LTD.) |
× |
Comparative Example 9 |
Polyester fiber cation dyeable under normal pressure (manufactured by MITSUBISHI RAYON
CO., LTD.: AHY) |
× |
Comparative Example 10 |
Polyester fiber cation dyeable under high pressure (manufactured by Huvis Corp) |
× |
Comparative Example 11 |
Polyester fiber cation dyeable under high pressure (manufactured by Nan Ya Plastics
Corporation) |
× |
Industrial Applicability
[0151] According to the invention, it is possible to obtain an etching finished cloth with
good etching finish properties of a modified polyester fiber by using the certain
modified polyester fiber as a modif iedpolyester fiber, without performing alkali
weight reduction on a woven or knitted fabric composed of the modifiedpolyester fiber
and an unmodified polyester fiber and without causing embrittlement of the unmodified
polyester fiber, while removing only the modified polyester fiber in printed parts.
Since no strong alkaline substance which has high toxicity to human is used, it becomes
possible to perform etching finishing with high safety in operation.