JPH07197321A - Polyester-based synthetic fiber and its production - Google Patents

Abstract

PURPOSE:To obtain polyester-based synthetic fiber excellent in visual dyeing concentration in dyeing, water retention, water releasing properties, water-vapor absorption and a dry feeling in all points. CONSTITUTION:This polyester-based synthetic fiber comprises a fiber surface part which has a large number of striped traces parallel with the direction of a fiber axis in a specific plane distance on the surface of the fiber is composed of a blended polymer of a copolymer of a polyethylene terephthalate and a polyethylene glycol and a polyethylene terephthalate. A method for producing the polyester-based synthetic fiber comprises specifying the blending ratio of the copolymer having a specific polyethylene glycol content and the polyethylene terephthalate to be mixed with the copolymer.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a synthetic polyester fiber suitable for general clothing, especially for sports use, which is excellent in all of visual dyeing density at the time of dyeing, water retention, water release, hygroscopicity, and dry feeling. The manufacturing method is related.

[0002]

2. Description of the Prior Art Synthetic fibers produced by melt spinning have a drawback in that it is difficult to obtain a visual dyeing density when dyed.
For the purpose of solving this drawback, for example, polyethylene terephthalate containing fine particle silica is melt-spun, and the obtained polyester fiber is alkali-treated to elute fine particle silica, thereby forming an extremely fine and complicated uneven shape on the fiber surface. It is being formed as a whole (Japanese Patent Publication Sho 59)
-24233). However, there is a problem that it is not possible to solve water retention, water release, and hygroscopicity, which are related to comfort during sweating.

Further, in the method of extracting a part of the two-component fiber by the polymer blend, a hollow is formed inside after extraction, and a deep color is obtained even when dyed in a devitrified and non-glossy state. It is known that there is a problem that it does not exist (see Japanese Patent Publication No. 59-24233).

[0004]

Therefore, according to the present invention, it is impossible to obtain a polyester-based synthetic fiber excellent in all of the visual dyeing density, water retention, water release, hygroscopicity and dry feeling in the prior art. The problem is to solve the problem by polymer blend technology.

[0005]

It is well known that when a polyester fiber is produced by using a polymer blending technique, if polyethylene glycol is used as one component of a copolyester, the heat resistance is extremely deteriorated. Therefore, it has been attempted to reduce the polyethylene glycol content by using a metal salt of sulfoisophthalic acid in combination, and further use this blended polymer as the sheath of the composite spinning and use polyethylene terephthalate as the core to improve the operability ( (See Japanese Patent Laid-Open No. 1-314781).

As described above, when a large amount of polyethylene glycol is copolymerized as one component of the copolyester, the heat resistance is extremely deteriorated. Therefore, a technique for utilizing a blended polymer using this is studied. There were few things.

However, according to the studies by the present inventors, the use of a blended polymer of polyethylene terephthalate and a polyester polymer obtained by copolymerizing a relatively large amount of polyethylene glycol, which has been rarely studied in the prior art, leads to a conventional technique. In the present invention, a technique for obtaining a polyester-based synthetic fiber excellent in visual dyeing density, water retention, water release, hygroscopicity, and dry feeling, which are not particularly obtained, particularly in water retention and water release, was found. It has come.

In addition to the above findings, the inventors of the present invention prevent the thermal decomposition of the blended polymer by spinning the blended polymer itself by an ordinary spinning method, as compared with the case where the blended polymer is used as the sheath of the composite spinning. It was also found to be effective. Further, it is generally found that the use of the copolymer polymer deteriorates the fastness of the cloth after dyeing, especially the fastness to water, but the present invention can solve this problem.

In the present invention, the fiber surface portion is made of a blended polymer of polyethylene terephthalate and a copolymerized polymer of polyethylene terephthalate and polyethylene glycol, and the fiber surface has a large number of scratches parallel to the fiber axis direction. Provided is a polyester-based synthetic fiber in which the ridges have a plane distance X to the ridges existing adjacent to each other in the outer peripheral direction perpendicular to the fiber axis within the range defined by the following formula (1). 0.2 ≦ X ≦ 1.0 (μm) (1)

The present invention also provides a copolymer of polyethylene terephthalate and a polyethylene glycol of a weight Y defined by the following formula (2), which is copolymerized therewith, and a weight B of the copolymerized polymer. The blending ratio A / B with polyethylene terephthalate is within the range defined by the following formula (3), and at least a part of the surface portion of the fiber made of the blend polymer is within the range defined by the following formula (4) by alkali treatment. And a method for producing the above polyester-based synthetic fiber, which comprises removing by elution at a weight reduction rate V. 10 ≦ Y ≦ 30 (wt%) (2) 10/90 ≦ A / B ≦ 50/50 (3) 0.2 ≦ V ≦ 10 (% / min) (4)

In the present invention, it is necessary to finely and linearly disperse the copolymerized polymer in polyethylene terephthalate, which is the main component of the fiber before alkali treatment. This makes it possible to reduce the average distance between the scratches on the fiber surface after the alkali treatment and also to improve the spinnability and drawability. Further, in the present invention, it is necessary to preferentially elute and remove the copolymer polymer finely dispersed in a streak shape by alkali treatment. To this end, the copolymerized polymer blended with polyethylene terephthalate is
It is a copolymer of polyethylene terephthalate and polyethylene glycol, in which the proportion Y of polyethylene glycol is 10 to 30% by weight, and 15 to 25
It is preferably in the weight%.

If the ratio Y is less than 10% by weight,
The reduction rate difference between the polyethylene terephthalate and the copolymer during alkali treatment is small, the number of scratches parallel to the fiber axis direction on the fiber surface is small, and the smooth portion is large. Further, when the ratio Y is more than 30% by weight, the heat resistance of the copolymer is deteriorated, the spinnability and the drawability are deteriorated, and the dye easily detached in the dyed fiber is reduced and washed with an alkali. In doing so, the blended polymer dissolves and the fiber shape is no longer retained.

In order to improve the heat resistance of the polyester-based synthetic fiber, for example, when a metal salt of sulfoisophthalic acid is used as the base component of the copolymerization component, the dispersion of the copolymerization polymer becomes coarse and the fiber surface becomes streaky. However, it will become coarse groove-like holes, and the dry feeling, water retention and water discharge will also be reduced,
The added amount is preferably 5% by weight or less.

Further, a blend ratio A / weight of this copolymer A and weight B of polyethylene terephthalate A /
B is 10/90 to 50/50 and 20/80 to 4
0/60 is more preferable. If this ratio is less than 10/90, the number of streaks will be small, and this ratio will be 50/50.
If it is larger, the number of streaks will decrease.

The blended polymer may be used as a sheath, and a known thermoplastic polymer such as polyethylene terephthalate or nylon 66 may be used as a core for composite spinning, or the blended polymer may be spun by an ordinary spinning method. From the viewpoint of the stability of the surface structure of the fiber against the variation of the weight loss rate, it is preferable to spin the blended polymer alone using a usual spinning method. The thermal degradation of the copolymer in the blend polymer is less when the blend polymer alone is spun using conventional spinning methods.

When at least a part of the fiber surface portion made of the blend polymer is eluted and removed by alkali treatment, the weight reduction rate V needs to be 0.2 to 10% / minute, and 0.3 to 6 % / Min is preferred. This reduction speed V
Is less than 0.2% / min, the weight loss time becomes long, which is not suitable for industrial implementation. In addition, the weight reduction rate V is 10% /
If it is larger than the minute, there are few streaks. Therefore, it is preferable not to use a weight loss accelerator and to lower the alkali concentration and the alkali treatment temperature.

As described above, according to the present invention, a desired polyester synthetic fiber can be produced by subjecting the surface portion of the fiber to alkali treatment. The kind of alkali used, treatment method, treatment temperature and The time is not particularly limited, but preferably an aqueous solution of sodium hydroxide, potassium hydroxide, lithium hydroxide, sodium carbonate, potassium carbonate, tetramethylammonium hydrosulfite, a mixture thereof, or the like can be used.
Although the concentration of the aqueous solution of these alkali compounds varies depending on the kind of the alkali compound and the treatment conditions, it is usually preferably in the range of 0.01 to 40% by weight, and 0.1 to 30% by weight.
A range of weight% is more preferable. Processing temperature is usually room temperature to 1
The range of 00 ° C is preferable, and the range of 30 to 95 ° C is more preferable. Further, the treatment time is usually preferably in the range of 1 minute to 4 hours, more preferably 1 minute to 60 minutes.

As described above, in the present invention, the fiber surface has a large number of scratches parallel to the fiber axis direction by specifying the blend polymer composition, the blend ratio, and the alkali weight loss rate. Is a copolymerized polymer of polyethylene terephthalate and polyethylene glycol in which the fiber surface portion has a plane distance X between 0.2 to 1.0 μm to a striation existing adjacently in the outer peripheral direction perpendicular to the fiber axis. And a polyester-based synthetic fiber made of a blend polymer of polyethylene terephthalate.

The plane distance X to one striation existing adjacent to one striation in the outer peripheral direction perpendicular to the fiber axis is such that the fiber surface is magnified 2000 times with a scanning electron microscope, It can be determined by measuring the number of streaks existing per 10 μm in the perpendicular direction and calculating the average distance.

If the plane distance X to the striations existing adjacent to each other in the outer peripheral direction at right angles to the fiber axis is less than 0.2 μm, the hygroscopicity and dry feeling are deteriorated, and 1.0
If it is larger than μm, the visual stain density, water retention and water release are lowered, which is not preferable. According to the present invention, it is possible to obtain a polyester-based synthetic fiber which is excellent in all of visual dyeing density during dyeing, water retention, water release, hygroscopicity, and dry feeling, particularly water retention and water release. For example, centrifugal dehydration (18
Regarding the water retention after 00G), the water retention of the conventional polyethylene terephthalate fiber is about 1%, whereas the water retention of the fiber of the present invention is 3 to 10% (preferably 5 to 10).
%) Can be significantly increased. Regarding water discharge, the water discharge rate of conventional polyethylene terephthalate fiber after centrifugal dehydration (1800G) is about 0.1% / min, whereas the water discharge rate of the fiber of the present invention is 0.4 to 0.7.
It can be significantly increased to% / min.

The streaks are irregularities formed by eluting fine particle silica by a conventional method (see Japanese Patent Publication No. 59-24233), and streak-shaped fine pores formed by eluting polyester from polymer blend fibers. (JP-A 2-17
(See Japanese Patent No. 5965), the shape is different.

Also in the present invention, as the blend ratio A / B of the weight A of the copolymerized polymer and the weight B of polyethylene terephthalate increases from 10/90 to 50/50, the blended phase becomes coarser and parallel to the fiber axis direction. In addition to a large number of streaks, there is a tendency for streak-like micropores to be scattered.
The presence of streak-shaped fine pores is not essential in order to exert all the excellent effects of visual dyeing density, water retention, water release, hygroscopicity, and dry feeling during dyeing.
In the case of the blend spinning of the copolymerization system of the present invention, the copolymerization polymer can be dispersed in a very fine fibril state.

[0023]

EXAMPLES The present invention will be described in more detail with reference to the following examples. The definitions of terms in the following examples are as follows. Weight loss rate (%) = {(absolute dry sample weight before weight loss-absolute dry sample weight after weight loss) / absolutely dry sample weight before weight loss) x 100 Weight loss rate (% / min) = weight loss rate / time between weight marks Distance (μm) = number of streaks per 10 μm / 10 μm Moisture content (%) = (sample weight after dehydration−excessive dry sample weight / excessive dry sample weight) Equilibrium moisture content (%) = {(20 ° C., Sample weight after standing at 65% RH for one day-absolute dry sample weight) / absolute dry sample weight} x 1
00 Water discharge rate (% / min) = (Sample weight after 3500 rpm centrifugal dehydration −20 ° C., sample weight after standing at 65% relative humidity for 10 minutes) / 10 minutes K / S value (visual staining density): Macbeth CE-3
Measured with 000 type L value (color brightness): Macbeth CE-3000
Measured by mold

Example 1 25% by weight of polyethylene glycol having a molecular weight of 6000,
1% by weight of methyl sulfoisophthalate, 51% by weight of dimethyl terephthalate, and 23% by weight of ethylene glycol were added with an ester exchange catalyst and a polymerization catalyst and polymerized by a conventional method.
A copolymerized polymer was obtained. Weight of this copolymer A
And chip blending so that the blending ratio A / B with the weight B of polyethylene terephthalate to be mixed therewith becomes 2/8, and spinning is performed using a normal screw extruder,
After stretching, 70d / 24f fibers were obtained. The fiber was knitted into 28 gauge nits and treated in a 30 g / L NaOH aqueous solution at 90 ° C. for 30 minutes. The weight loss rate was 22%, and the weight loss rate was 0.7% / min.

When the knitted fabric after the weight reduction was observed with a scanning electron microscope, the plane distance X to one streak adjacent to one striation on the fiber surface in the outer peripheral direction perpendicular to the fiber axis was 0. It was 0.5 μm. Immerse this knitted fabric in water at 20 ° C,
Moisture content after holding one end and suspending for 5 minutes is 328
%Met. The water content after centrifugal dehydration at 3500 (1800 G) rotations per minute was 5.4%. The equilibrium moisture content was 0.8% when left in a high temperature room at 20 ° C and 65% relative humidity for one day. The water discharge rate at this time is 0.47
It was as high as% / min. The texture of this knitted fabric was excellent in dry feeling. A photograph showing the shape (surface state) of the obtained fiber is shown in FIG.

Next, this knitted fabric is dyed with Kayalon P
o. Using Blue 3R-SF, 20% owf, pH =
5. Dyeing was carried out at a bath ratio of 1:50 at 130 ° C. for 60 minutes. When the knitted fabric after dyeing was subjected to color measurement using Macbeth CE-3000 type, the K / S value showing the visual dyeing density was 25.
The value was as large as 8, and the L value indicating the brightness was as small as 14.1.

Subsequent to dyeing, reduction washing was carried out at 80 ° C. for 10 minutes at a bath ratio of 1: 100 in an aqueous solution containing 2 g / L of NaOH and 2 g / L of hydrosulfite. The knitted fabric has sufficient strength without damage to the knitted fabric during reduction washing which often occurs when a copolymer having a high alkali weight loss rate is used. The K / S fabric has 24.7 and the L value is 14. There was almost no change at 2.

Example 2 The same procedure as in Example 1 was carried out except that the fiber was treated in a 100 g / L NaOH aqueous solution at a temperature of 90 ° C. for 10 minutes. The weight loss rate was 39%, and the weight loss rate was 3.9% / min. When the knitted fabric after the weight reduction was observed by a scanning electron microscope, the plane distance X to one striation on the fiber surface adjacent to the striation existing in the outer peripheral direction perpendicular to the fiber axis was 0.7 μm. there were. Further, the water content after immersing this knitted fabric in water at 20 ° C., gripping one end of the knitted fabric and leaving it suspended for 5 minutes was 377%.
It was 5.1% when the water content was measured by stretching and dehydrating at 3500 rpm. Equilibrium moisture content is 0.8% when left in a high temperature room at 20 ° C and 65% relative humidity for one day.
Met. The drying rate at this time was as high as 0.42% / min. The texture of this knitted fabric was excellent in dry feeling.

Example 3 25% by weight of polyethylene glycol having a molecular weight of 6000,
A copolymerization polymer was obtained by adding an ester exchange catalyst and a polymerization catalyst to 1% by weight of methyl sulfoisophthalate, 51% by weight of dimethyl terephthalate, and 23% by weight of ethylene glycol, and polymerizing by an ordinary method. Chip blending was performed so that the blending ratio A / B of the weight A of this copolymer and the weight B of polyethylene terephthalate to be mixed with this was 4/6, spinning was performed using a normal screw extruder, and after stretching, Fibers of 70d / 24f were obtained. 2 this fiber
30-g / L NaO at 90 ℃
Treated in aqueous H solution for 10 minutes. The weight loss rate was 39%, and the weight loss rate was 3.9% / min.

When the knitted fabric after the weight reduction was observed with a scanning electron microscope, the plane distance X to one streak adjacent to one striation on the fiber surface in the outer peripheral direction perpendicular to the fiber axis was 0. It was 0.8 μm. In addition to this, streak holes with a length of 1 to 15 μm were also mixed. The knitted fabric was dipped in water at 20 ° C., one end of the knitted fabric was held, and the knitted fabric was suspended for 5 minutes.
It was 06%. It was 9.0% when the water content was measured by stretching and dehydration at 3500 rpm. 20 ℃,
The equilibrium water content was 1.7% when left for one day in a high temperature room with relative humidity of 65%. The water discharge rate at this time is 0.6
It was as large as 7% / min. The texture of this knitted fabric was excellent in dry feeling.

Next, this knitted fabric was dyed with Kayalon P
o. Using Blue 3R-SF, 20% owf, pH =
5. Dyeing was carried out at a bath ratio of 1:50 at 130 ° C. for 60 minutes. When the color of the knitted fabric after dyeing was measured using a Macbeth CE-3000 model, the K / S value showing the visual dyeing density was 29.
9 was large, and the L value indicating brightness was small, 13.9.

Subsequent to the dyeing, reduction washing was carried out at a bath ratio of 1: 100 at a temperature of 80 ° C. for 10 minutes in an aqueous solution containing 2 g / L of NaOH and 2 g / L of hydrosulfite. The knitted fabric has sufficient strength without damage to the knitted fabric during reductive washing that often occurs when a copolymer having a high alkali weight loss rate is used, and has a K / S value of 26.9 and an L value of 14. At 9 there was almost no change.

EXAMPLE 4 1 fiber was placed in a 50 g / L NaOH aqueous solution at a temperature of 90.degree.
The same treatment as in Example 3 was performed except that the treatment was performed for 0 minutes. The weight loss rate was 60%, and the weight loss rate was 6.0% / min. When the knitted fabric after the weight reduction was observed with a scanning electron microscope, the plane distance X to one striation on the fiber surface adjacent to the striation adjacent to the outer peripheral direction perpendicular to the fiber axis was 0.9 μm. there were. The water content after immersing this knitted fabric in water at 20 ° C., holding one end of the knitted fabric and suspending it for 5 minutes was 520%.
The water content was measured by stretching and dehydration at 3500 rpm and the water content was 8.5%. Equilibrium moisture content is 1.6% when left in a high temperature room at 20 ° C and 65% relative humidity for one day.
Met. The water discharge rate at this time was as high as 0.64% / min, and the texture of this knitted fabric was excellent in dry feeling.

Comparative Example 1 Fibers of 70d / 24f were obtained from polyethylene terephthalate homopolymer in the same manner as in Example. This fiber was formed into a single knitted piece, dipped in water at 20 ° C., one end thereof was gripped, and the water content after hanging for 5 minutes was 222%. 3 per minute
When the water content was measured after stretching and dehydration at 500 rpm,
It was 1.2%. The equilibrium moisture content was 0.4% when left in a high temperature room at 20 ° C and 65% relative humidity for one day. The water discharge rate at this time was 0.06% / min. The texture of this knitted fabric gave a slimy feel.

Next, this knitted fabric is dyed with Kayalon P
o. Using Blue 3R-SF, 20% owf, pH =
5. Dyeing was performed at a bath ratio of 1:50 at a temperature of 130 ° C. for 60 minutes.
When the color of the dyed knitted fabric was measured using a Macbeth CE-3000 model, the K / S value showing the visual dyeing density was 2
The value was as small as 0.8, and the L value indicating the brightness was as large as 17.8.

Comparative Example 2 A treatment was carried out in the same manner as in Example 3 except that the fiber was treated for 5 minutes in a boiling 100 g / L NaOH aqueous solution. The weight loss rate was 71%, and the weight loss rate was 14.2% / min. When the knitted fabric after the weight reduction was observed with a scanning electron microscope, a plane distance X to one striation on the fiber surface adjacent to the striation existing in the outer peripheral direction perpendicular to the fiber axis was 1.2 μm. there were.
Further, the water content after immersing this knitted fabric in water at 20 ° C., gripping one end of the knitted fabric and leaving it suspended for 5 minutes was 500%. When the water content was measured by stretching and dehydrating at 3500 rpm,
The water content was 5.4%. Also, 20 ° C, relative humidity 65
% Equilibrium moisture content when left in a high temperature room of 1% for one day.
2%, water discharge rate at this time is 0.35% / min, L value is 1
Although it was 5.8, the feel of this knitted fabric was inferior in dry feeling, and the K / S value was also reduced to 23.2.

Comparative Example 3 16% by weight of polyethylene glycol having a molecular weight of 6000,
A transesterification catalyst and a polymerization catalyst were added to 10% by weight of sodium sulfoisophthalate, 51% by weight of dimethyl terephthalate and 23% by weight of ethylene glycol, and the mixture was polymerized by an ordinary method to obtain a copolymer. The weight A of this copolymer and the weight B of polyethylene terephthalate to be mixed with the copolymer A were chip-blended so that the blend ratio A / B was 2/8, spun using an ordinary screw extruder, and stretched. Fibers of 70d / 24f were obtained. The spinnability and drawability of this fiber were poor. The fiber was knitted into 28 gauge nits and treated in a 30 g / L NaOH aqueous solution at a temperature of 90 ° C. for 5 minutes. Weight loss rate is 55%, weight loss rate is 1
It was 1% / min.

When the knitted fabric after the weight reduction obtained above was observed with a scanning electron microscope, the fiber surface had a structure in which elliptical holes were scattered. This knitted fabric was immersed in water at 20 ° C., one end thereof was held, and the knitted fabric was suspended for 5 minutes and left to stand, and the water content was 239%. The water content after centrifugal dehydration at 3500 rpm was 5.5%, and the equilibrium water content was 0.9% when left in a high temperature room at 20 ° C. and 65% relative humidity for one day. . The water discharge rate at this time was 0.32% / min. However, the feel of this knitted fabric was less dry.

Next, the knitted fabric obtained above is dyed with Kayalon.
Po. With Blue 3R-SF, 20% owf,
Dyeing was carried out at a temperature of 130 ° C. for 60 minutes at pH = 5 and a bath ratio of 1:50. When the knitted fabric after dyeing was dyed using Macbeth CE-3000 type, the K / S value showing the visual dyeing density was as large as 25.9 and the L value showing the brightness was as small as 14.0. It was

Subsequent to the dyeing, reduction washing was carried out at a bath ratio of 1: 100 at a temperature of 80 ° C. for 10 minutes in an aqueous solution containing 2 g / L of NaOH and 2 g / L of hydrosulfite. The damage to the knitted fabric was so great that it could not be put to practical use.

[0041]

As described above, according to the present invention, it is possible to obtain a polyester-based synthetic fiber which is excellent in all of visual dyeing density, water retention, water release, hygroscopicity, and dry feeling during dyeing.

[Brief description of drawings]

FIG. 1 is an electron micrograph (× 2,000) showing an example of the shape (surface state) of the polyester-based synthetic fiber of the present invention.

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Claims (2)

[Claims] 1. A copolymerized polymer of polyethylene terephthalate and polyethylene glycol having a fiber surface portion,
Composed of polyethylene terephthalate and bunred polymer, the fiber surface has a large number of scratches parallel to the fiber axis, and the scratches are adjacent to each other in the outer peripheral direction perpendicular to the fiber axis. The polyester synthetic fiber is characterized in that the plane distance X to is within the range defined by the following formula (1). 0.2 ≦ X ≦ 1.0 (μm) (1) 2. A blend of polyethylene terephthalate and polyethylene glycol having a weight Y defined by the following formula (2), which is copolymerized therewith, with a copolymer having a weight A and polyethylene terephthalate having a weight B mixed therewith. At least a part of the surface portion of the fiber made of the blend polymer having a ratio A / B within the range defined by the following formula (3) is treated with an alkali at a weight reduction rate V within the range defined by the following formula (4). The method for producing a polyester-based synthetic fiber according to claim 1, wherein the polyester-based synthetic fiber is eluted and removed. 10 ≦ Y ≦ 30 (wt%) (2) 10/90 ≦ A / B ≦ 50/50 (3) 0.2 ≦ V ≦ 10 (% / min) (4)