JPS616344A - Polyester knitted fabric and its production - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

DETAILED DESCRIPTION OF THE INVENTION (Field of Industrial Application) The present invention relates to a polyester woven or knitted fabric and a method for producing the same.

(Prior Art) Polyesters, particularly polyalkylene terephthalates such as polyethylene terephthalate and polybutylene terephthalate, and polyester fibers based on these have various excellent properties and have been widely used in woven and knitted fabrics. .

However, polyester lacks a dry feel and has a more complex and deep luster.

In terms of opacity and water absorption, natural 9 silk woven and knitted fabrics,
We have no choice but to give up one or two steps to cotton woven and knitted fabrics, and we are making a lot of effort to come close to them.

In the past, advances in production and processing technology for polyester woven and knitted materials have made it possible to obtain woven and knitted materials that are close to textured knitted fabrics and brocade knitted fabrics in terms of fullness, drapability, and repellency. There are significant differences in terms of dry surface touch, deep gloss, excellent opacity, and moisture absorption, which is one of the decisive differences between textured knitted fabrics, brocade knitted fabrics, and polyester woven fabrics.

Here, the dry feeling refers to the dry feeling characteristic of textured knitted fabrics or brocade knitted fabrics, and is in contrast to the slimy feel of polyester woven and knitted fabrics.

At present, quantitative measurement is difficult, and it is generally determined by the touch of the fabric manufacturer.

As described above, although it is difficult to determine the distance, it is an extremely important element in determining the properties of woven or knitted fabrics.

It also has a deep luster, not the metallic shine characteristic of synthetic fibers, but a subdued luster with fine sparkles similar to silk.

Furthermore, excellent opacity is determined by the size of the interfiber voids in the woven or knitted fabric.

One of the differences between synthetic fibers and natural fibers such as silk and cotton is that
The fineness and physical properties of each natural fiber are
It is non-uniform and has variations, but overall it is well-balanced and does not show any unevenness. However, it is presumed that the non-uniformity between each fiber affects the delicate texture and bulkiness.

Originally, efforts have been made to improve the uniformity of synthetic fibers, but on the other hand, as seen in Japanese Patent Application Laid-Open No. 54-42415, non-uniformity has been intentionally created and latent bulky filaments There are attempts to obtain in this way,
Although a non-uniform thread can be obtained, the speed difference between the two individual streams of molten polyester cannot be made too large;
Therefore, the difference in physical properties was small and the shrinkage force of the yarn was weak. Due to the weak shrinkage force of the yarn, it was not possible to obtain sufficient bulkiness, and it was not sufficient to obtain the natural bulkiness and surface touch that natural fiber woven and knitted fabrics have. (Objective of the Invention) The present invention The aim is to improve the shortcomings of conventional synthetic fibers by creating a dry surface touch and excellent opacity similar to those of silk and cotton woven and knitted fabrics.

Another object of the present invention is to provide a polyester woven or knitted fabric that has unprecedented bulkiness in addition to hygroscopicity, and a method for producing the same.

(Structure of the Invention) The present invention is characterized in that streaky voids or long micropores are distributed on the fiber surface, with the streaky direction or the long diameter direction of the slotted micropores being arranged along the fiber axis direction. A polyester filament having a cross-sectional shape that is substantially flat and has recesses on both sides sandwiching the long axis of the cross-section, and with respect to the short axis between the recesses. having an asymmetrical shape, having a hollow part in the cross section where the length between two points where a straight line parallel to the short axis intersects with the outline of the cross-sectional shape is maximum, and extending the entire cross-section along the direction of the fiber axis; A polyester woven or knitted fabric made of eccentric hollow multifilament yarns whose area changes, and in order to form streak-like voids or micropores on the surface of the polyester filaments, additives are blended into the polyester composition and melted. The spun material can be obtained by subjecting it to alkali treatment in the next step.

FIG. 1 is a diagram showing an example of an electron micrograph of the surface of a polyester filament used in the woven or knitted fabric of the present invention.

The fiber shown in FIG. 1 has linear voids on its surface that are parallel to the fiber axis.

FIG. 2 is a perspective view showing another example of the surface condition of the polyester filament used in the woven or knitted fabric of the present invention. The elongated fine pores are arranged and distributed such that the long axis direction is along the direction of the fiber axis. The size of the micropores is 0.01 to 3 μm in diameter (the largest width on the fiber surface) and 5 μm in length to the diameter.
A preferable example is one that is 0 times or less.

This is because if the diameter is less than 0.01 μm, a sufficient dry feel cannot be imparted to the woven or knitted fabric, and the object of the present invention cannot be fully achieved. Furthermore, if the diameter exceeds 3 μm, the fiber strength decreases and problems such as fibrils occur.

Such linear voids or elongated micropores can be formed by treating a filament obtained by blending additives with a polyester composition and melt-spinning the filament with an alkali in the drawing process.

As an additive that forms the linear voids, polyester containing an organic sulfonic acid metal salt is melt-spun through a predetermined spinneret, stretched, and then immersed in an aqueous solution of an alkali compound to be incorporated into the fiber. A method of eluting and removing at least a portion of the organic sulfonic acid metal salt is simple and preferred.

Suitable organic sulfonic acid metal salts to be added to the polyester are those represented by the following general formula % (1). When R in the general formula is a carkyl group or an alkylaryl group, it may have a linear or branched side chain. In particular, from the viewpoint of compatibility with polyester, organic sulfonic acid metal salts in which R is an alkyl group are preferred. Examples of M include alkali metals such as Na=K*L+ and alkaline earth metals such as Mg and Ca. Among these, Na and K are preferred.

Note that when using the organic sulfonic acid metal salt, it is not necessary to use a single compound, and a mixture of organic sulfonic acid metal salts having various alkyl groups or alkylaryl groups may be used.

In particular, a modified polyester obtained by copolymerizing an organic sulfonic acid compound represented by the general formula ([1)] is preferably used as an additive that forms long pores and micropores.

X-A-Y・・・・・・・・・・・・・・・(II
) SOaM' In the formula, human is a trivalent aromatic group or an aliphatic hydrocarbon group, and aromatic groups are particularly preferred.

Ml is a metal or a hydrogen atom, and particularly preferably an alkali metal or an alkaline earth metal. X is an ester-forming functional group, and specific examples thereof include OCR, COH, COR, (CHt+-0H-111I
II (However, R is a lower alkyl group or a phenyl group, & and d
is an integer of 1 or more, b is an integer of 2 or more), etc. Y represents an ester-forming functional group or a hydrogen atom that is the same as or different from X, and is preferably an ester-forming functional group.Additives that form long micropores include: In addition to the modified polyester layer mentioned above, phosphorus compounds or sulfonic acid compounds represented by the following general formula (III) or (IV) are also preferred as micropore-forming agents.

(0) m vo -p -oM yi-=--== (II) In the formula, M
The proverbs are metals, especially alkali metals, alkaline earth metals, Mn 1/2 , Co 1/2 or Znl/2 are preferred, especially Ll, Na, K.

Ca 1/'2, Mg 1/2 are particularly preferred om
is 0 to 1. (1) A monovalent organic group, specifically an alkyl group, an aryl group, an alkylaryl group, an alkyl group, or f(CH1+ohiR" (where R" is a hydrogen atom, aI!
A lorkyl group or a phenyl group, an integer of 2 or more, p an integer of 1 or more), etc. are preferable. 2 is -0H1-ov', -
0M' or -valent organic group, ■ is the same as the definition of ■ above, and V/ and V may be the same or different (
, Ml are the same as the definition of MI above, and Ml and Ml may be the same or different. In addition, the -valent organic group is the same as the definition of the organic group in V above, and
may be the same or different.

Formula (IV) is Some' where Ma and M4 are metals, and Ms is particularly an alkali metal, an alkaline earth metal, Mn 1/2, Co
l/2 or Znl/2 is preferred, especially Ll
, Na, K, Cal/2, and Mgl/2 are particularly preferred, and M4 is particularly preferably an alkali metal or alkaline earth metal, especially Ll and Na.

Particularly preferred are K, Cal/2, and Mgl/2.
, Ml and M4 may be the same or different. n is 1 or 2. W is a hydrogen atom or an ester-forming functional group, and the ester-forming functional group is -C0oR''
'(However, R″' is a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or a phenyl group) or -CO+OiCL)-←OH(
However, l is preferably an integer of 2 or more / p (p minus an integer of 1 or more).

The polyester used here has terephthalic acid as its main acid component and is selected from alkylene glycols having 2 to 6 carbon atoms, namely ethylene glycol, trimethylene glycol, tetramethylene glycol, pentamethylene glycol and hexamethylene glycol, particularly preferably ethylene glycol and hexamethylene glycol. The target is polyester whose main glycol component is at least one type of glycol selected from tetramethylene glycol. The polyester may have a portion of its acid component terephthalic acid replaced by another difunctional carboxylic acid. Further, part of the glycol component may be replaced with another glycol component.

Such polyesters can be obtained by any manufacturing method. For example, to explain polyethylene terephthalate, toethylene glycol terephthalate and 'ir
A direct mx esterification reaction, a transesterification reaction between a lower alkyl ester of terephthalic acid such as dimethyl terephthalate and ethylene glycol, or a reaction site between terephthalic acid and ethylene oxide,
Easily produced by a first stage reaction in which a glycol ester of terephthalic acid and/or its low polymer is produced, followed by a second stage reaction in which the product is heated under reduced pressure and subjected to a polycondensation reaction until a desired degree of polymerization is achieved. I can see it.

Next, the polyester filament used in the present invention is characterized by its cross-sectional shape.

The cross-sectional shape will be explained with reference to the drawings.

Fig. 3 is a sectional side sectional view of the filament used in the present invention, Fig. 4 ((a) is a side view of the filament used in the invention, and Fig. 4 (b) is a front view of the side view rotated by ykg00. It is a diagram.

As shown in FIG. 3, the cross-sectional shape of the filament used in the present invention is flat, and has recesses x and x' on both sides of the long axis n. The recesses x and x' are along the long axis n
A pair of recesses x, x' sandwiching and facing each other is best exemplified.

Next, the cross-sectional shape is asymmetrical with respect to the short axis C obtained by connecting the recesses x and In some cases, a hollow portion e exists in the cross section on the side where m is maximum.

Such a filament, for example, has a hollow hole 1 as shown in FIG.
It can be obtained by spinning at a take-up speed of 2500 m7 min or more using a spinneret having a discharge hole in which a solid hole 2 and a solid hole 2 are connected by a slit 3. FIG. 5 is a plan view showing an example of the shape of the discharge hole of the spinneret for spinning the eccentric hollow multifilament yarn used in the present invention.

In the case of such a spinneret, a flow velocity difference is provided so that the flow velocity of the polymer stream discharged from the solid hole 2 is faster than that of the hollow hole 1, and the flow velocity difference is easily increased ζ
, can be done.

In this way, since the flow rate of the polymer flow passing through the hollow hole 1 is slower than the polymer flow passing through the solid hole 2, the spinning tension (draft) during spinning, especially under a high draft of 500 or more, the hollow hole The polymer stream is mainly concentrated in the discharged polymer stream. As a result, the hollow portion formed by the polymer flow discharged from the hollow hole 1 is subjected to a greater shearing force than when the hollow hole 1 is a solid hole, and has an extremely higher degree of orientation than when the hollow hole 1 is solid. It becomes.

In the present invention, the filament having the above-mentioned cross-sectional shape has a higher degree of orientation in the g part than the h part, and has irregularities in thickness as shown in FIG. 4 in the longitudinal direction of the filament. As shown in Fig. 4, the thickness unevenness in the longitudinal direction of the filaments constituting the multifilament used is such that the cross-sectional area of the h portion is wider than the cross-sectional area of the g portion in the longitudinal direction. They are joined together while changing.

Preferred embodiments of the cross-sectional shape of the filament used in the present invention include those exhibiting a substantially eyebrow shape as shown in FIG. 3(a), or those exhibiting a substantially isosceles triangular shape as shown in FIG. 3(o). is preferred. In particular, a filament having a cross-sectional shape of approximately 5 isosceles triangles is preferable because it can exhibit a unique luster.

The hollowness ratio of the part g in such a flat hollow filament is 2 to 30%, particularly preferably 10 to 15%, and the cross-sectional area S' including the hollow part e of the part g and the cross-sectional area sh of the part h are The ratio (Sg/ah) is 1.2 to 3, especially 1
．． It is preferable that it is 5-2.

However, the hollowness ratio and cross-sectional area of 8g and sh were determined from a microscopic photograph of the cross-section of the filament.

Next, polyester woven or knitted fabrics woven using such eccentric hollow multifilament yarns are processed through the usual scouring and dyeing finishing processes, but in this case, the woven or knitted fabrics are subjected to a relaxing treatment to swell and become electrically conductive. The step of obtaining the fiber and the alkali weight reduction process to obtain streaky voids or elongated micropores on the fiber surface are essential.

Relaxation-treated Nyorei woven and knitted fabrics have larger inter-fiber voids than normal 7Y yarn woven and knitted fabrics due to the difference in shrinkage between the hollow cross section and the solid cross-section. In addition, streak-like voids or long micropores are generated on the surface of all the constituent fibers, and the effect of providing a dry feeling, which is the object of the present invention, is remarkable.

Potassium hydroxide and sodium hydroxide are used as alkaline substances for alkaline reduction.

Examples include sodium carbonate, but in addition to this, it is advantageous to use quaternary ammonium salts such as 2uryldimethylbenzylammonium chloride and cetyldimethylbenzylammonium chloride as an alkali treatment accelerator.

(Function of the invention) The polyester woven or knitted fabric of the present invention is characterized in that the eccentric hollow multifilament yarns constituting the woven or knitted fabric have linear voids arranged in a striped manner in the fiber axis direction on the surface thereof, or A woven or knitted fabric having a dry feel, which is one of the objects of the present invention, can be obtained by using a woven fabric having an array of holes. Furthermore, the above-mentioned cross-sectional shape, the relative positional relationship between the hollow parts as shown in Fig. By arranging them on the fiber surface, they impart unprecedented opacity to woven or knitted fabrics.

Furthermore, the woven or knitted fabric of the present invention has a nonuniform structure in which the filaments constituting it are made of eccentric hollow multifilament yarns and the area of the entire cross section changes along the direction of the fiber axis. It has the subtle bulkiness that woven and knitted fabrics have. In particular, when the eccentric hollow multifilament yarn is produced using a spinneret as shown in FIG. Since the difference in shrinkage can be increased, the bulkiness is further increased.

Furthermore, since such cross-sectional area changes and shrinkage differences exist along the fiber axis direction of a single filament, these changes can be expressed in the scouring and relaxing process, resulting in natural fibers that cannot be obtained with conventional synthetic fibers. It is a product that has succeeded in imparting a sense of bulk.

In addition, the woven or knitted fabric of the present invention has hygroscopicity or water retention due to the interfiber voids created by the aggregated form of fibers that impart novel bulkiness, and the above-mentioned striped voids or elongated micropores. improves.

In particular, when long micropores are arranged on the surface, the hygroscopicity and water retention are greatly improved.

Example 1 Polyethylene terephthalate to which 0.6% by weight of a mixture of sodium alkylsulfonate having an average carbon number of 14 was added as an additive was spun at a speed of 4.500 m/min using a spinneret having the spinning holes shown in FIG. After melt spinning, Figure 3 @
) An eccentric hollow polyester multifilament yarn of 75 denier/36 filaments was obtained. This fabric was woven under the conditions shown in Table 1, and the fabric was scoured and relaxed at a temperature of 80°C and subjected to alkali treatment with a weight loss rate of 18%. The obtained woven fabric was composed of filaments having streak-like voids on the surface, and the texture of the woven fabric was excellent.

The results of the texture evaluation are shown in Table 1.

Comparative Example 1 As a comparative example, polyethylene terephthalate to which no alkyl sulfonic acid sorter was added was spun in the same manner as in Example 1 to obtain an eccentric hollow polyester multifilament yarn of 75 denier/36 filaments. This was woven in the same manner as in Example 1, scoured and relaxed, and treated with alkali. Table 1 shows the evaluation of the texture of the obtained fabric.

Example 2 A mixture of sodium alkylsulfonate having an average carbon number of 14 as an additive + i 0.6% by weight of polyethylene terephthalate) ii Spinning speed 3.000 m/min using a spinneret having the spinning holes shown in Figure 5 Spun at a stretching ratio of 1
．． 4. Stretch and heat set at a heat setting temperature of 180°C.
Figure <()K 75 denier/36 with the cross-sectional shape shown
An eccentric hollow polyester multifilament yarn of filament was obtained. This was woven under the conditions shown in Table 1, and subjected to scouring relaxation and alkali treatment in the same manner as in Example 1. The obtained woven fabric was composed of filaments having streak-like voids on the surface, and the texture of the woven fabric was excellent. The results of the texture evaluation are shown in Table 1.

Comparative Example 2 The polymer used in Example 2 was
Using a spinneret with spinning holes as described in the publication, the take-up speed was 3. Spinning at ooom/min, stretching ratio 1
．． 4. Heat setting The multifilament yarn was drawn and heat set at a temperature of 180'O to obtain a 75 denier 736 filament multifilament yarn having a double-shaped solid irregular cross section. This filament yarn was woven under the same conditions as in Example 2 to obtain a scouring lux.

Alkali treatment was performed in the same manner. The texture evaluation is also shown in Table 1.

Example 3 197 parts of dimethyl terephthalate, 1 part of ethylene glycol
24 parts, 3-carbomethoxy; Sodium benzenesulfonate
-4 parts of Na-5-carboxylate (13 mol% based on dimethyl terephthalate), calcium acetate monohydrate n, t i
Part s is placed in a glass flask equipped with a rectification column, and a transesterification reaction is carried out according to a conventional method. After the theoretical amount of methanol has been distilled off, the reaction product is placed in a polycondensation flask equipped with a rectification column,
112 parts of trimethyl phosphate O as a stabilizer and 0.079 parts of antimony trioxide as a polycondensation catalyst were added and reacted at a temperature of 280°C for 20 minutes under normal pressure and 15 minutes under reduced pressure of 30 Mg, and then under high vacuum. The reaction was carried out for 80 minutes.

The final internal pressure was 0.38ffiHg f, and the obtained modified polymer had an intrinsic viscosity of 0.600. Softening point is 258°0
Met. After the reaction was completed, the modified polymer was formed into chips according to a conventional method and dried.

Next, this dried chip was melted, heated to 300°, and discharged from the discharge hole shown in FIG. 5 at a discharge rate of 37.5 y/f+.

Then, the polymer stream discharged from the solid hole 2 collides with one side of the polymer stream discharged from the hollow hole 1 just below the spinneret surface, bounces and joins, and then the joined polymer stream 3 Q
After spraying at a linear velocity of cs/yx and cooling and solidifying, apply oil with an oiling roller and then take off at a speed of 4500α/
A multifilament of 75 do/36 flj'@ was obtained by winding with ll11.

The filaments are used as warps and wefts and are woven into a plain weave with a warp density of 35/- and a weft density of 30/α, and then the gray fabric is scoured and relaxed in a conventional manner and preset. It was finished with a weight loss rate of 20% in an alkaline bath.

As a comparative example, chips similar to those in the example were melt-spun through a conventional spinneret, wound at a speed of 15 (j Om/sii+), and the undrawn yarn was drawn 3.0 times in accordance with a conventional method to produce 80 (j Om/sii+). 75de/36fl at a stretching speed of 1m/saki
A drawn yarn of /a was obtained.

The drawn yarn was woven and finished into a fabric having the same density as in the example.

The performance of the obtained fabrics is summarized in Table 2.

Table 2 The opacity and dryness of the examples were higher than that of the comparative examples.

Both swelling and water absorption were good.

Here, the opacity is as follows.

×100 (%) Regarding the opacity value, if the reflectance when backed with a black backing plate and a white backing plate is the same, then the opacity is 1.
On the other hand, if the reflectance when backed with a black backing plate is 0, the opacity is 0%.9, indicating that the material is completely transparent. .

[Brief explanation of the drawing]

FIG. 1 is a diagram showing an example of an electron micrograph of the surface of the polyester filament used in the woven or knitted fabric of the present invention. FIG. 2 is a perspective view showing another example of the surface of the polyester filament used in the present invention. FIG. 3 is a sectional view showing an example of the cross section of the polyester filament used in the present invention, FIG. 4 (A) is a side view of the polyester filament used in the present invention, FIG. FIG. 5 is a plan view showing an example of the shape of the discharge hole of the spinneret for spinning the eccentric hollow multifilament yarn used in the present invention. C...Short axis between the recesses e...Hollow part m...Maximum flame length between two points intersecting the outline n...Long axis x, x'/Concavity

Claims (1)

[Claims] 1. Linear voids or long micropores are distributed on the fiber surface, with the linear direction or the long diameter direction of the micropores being arranged along the fiber axis direction. A polyester filament, the polyester filament has a substantially flat cross-sectional shape, has recesses on both sides of the long axis of the cross-section, and has an asymmetrical shape with respect to the short axis between the recesses. and has a hollow part in the cross section where the length between two points where a straight line parallel to the short axis intersects with the outline of the cross-sectional shape is maximum, and the area of the entire cross section changes along the direction of the fiber axis. A polyester woven or knitted fabric made of eccentric hollow multifilament yarn. 2. The polyester filament obtained by blending additives into a polyester composition and melt-spinning the polyester filament has a substantially flat cross-sectional shape, and has concave portions on both sides of the long axis of the cross-section; It has an asymmetrical shape with respect to the short axis existing between the recesses, and has a hollow part in the side cross section where the length between two points where a straight line parallel to the short axis intersects with the outline of the cross-sectional shape is maximum. In addition, a polyester fabric characterized in that it is woven and knitted using eccentric hollow multifilament yarn whose entire cross-sectional area changes along the fiber axis direction, and the woven and knitted fabric is subjected to finishing processing including scouring relaxation treatment and alkali treatment. Method of manufacturing knitted fabrics.