JPH05230729A - Production of cation-dyeable polyester false-twisted yarn - Google Patents

Abstract

PURPOSE:To obtain a false-twisted yarn excellent in the false twist-processing property, mechanical characteristics, dyeing fastness and touch by employing cation dyeable aromatic polyester fibers containing a glass transition temperature-lowering agent and solid fine particles. CONSTITUTION:The drawn fibers of a polyester copolymerized with 5-sodium sulfoisophthalic acid as a dicarboxylic acid component having a sulfonate group in an amount of 1.0-2.6 moles based on the whole carboxylic acid component constituting the polyester, containing 1-5wt.% of a glass transition temperature- lowering agent of formula R<1>-O-X-OR<2> (X is aromatic residue; R<1>, R<2> are 6-18C alkyl or arylalkyl) and 0.1-1.0wt.% of silica particles having an average particle diameter of 15-70mum, respectively, based on the aromatic polyester, the intrinsic viscosity [eta] of the polyester and the content A wt.% of the glass transition temperature-lowering agent being satisfied with the relation of the inequality (A is 1-5), are false-twisted under a condition satisfied with an inequality 25000/D<1/2=T<=40000/D1/2 (T is false twist number/m; D is denier) at a temperature of 190-200 deg.C.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing a false twist textured yarn which is dyeable with a cationic dye. More particularly, the present invention relates to a method for producing a polyester false twist textured yarn which is dyeable with a cationic dye and is excellent in physical properties such as mechanical properties, yarn formability, processability and feel.

[0002]

2. Description of the Related Art Polyester fiber has a large strength, is chemically stable, and is excellent in dimensional stability, pleating retention, wrinkle resistance and the like and has various good properties. Twisted polyester false twisted yarn is widely used for clothing and interiors. However, as is well known, polyester fibers are inferior in dyeability and dyes other than disperse dyes are difficult to dye.

Therefore, various methods for improving the dyeability of polyester resins and fibers have been proposed. As one of them, an isophthalic acid component having a sulfonic acid metal base such as 5-sodium sulfoisophthalic acid is added to the polyester. A method for polymerizing the dye to make it dyeable with a cationic dye has been conventionally known (for example, Japanese Patent Publication No. 34-10497).

However, according to this method, the isophthalic acid component having a metal sulfonate group has a large thickening effect during the polymerization reaction, and therefore the polymerization system of the resulting polyester copolymer does not become sufficiently high. The viscosity of the polymer was remarkably increased, and the degree of polymerization thereof could not be sufficiently increased, and melt spinning of the polyester copolymer obtained thereby was difficult. In order to make the melt viscosity of the polyester copolymer obtained by copolymerizing the isophthalic acid component having a sulfonate group within the range in which the polymerization can be easily performed and melt spinning is possible, it is necessary to stop the polymerization at a stage where the polymerization degree is lower. As a result, the strength of the resulting polyester copolymer, and by extension, the yarn formed therefrom, is reduced, and its use is significantly limited.

As another method for making polyester dyeable with a cationic dye, there is known a method in which an isophthalic acid component having a phosphonium sulfonate group is copolymerized in the polyester (Japanese Patent Publication No. 47-22334). U.S. Pat. No. 3,732,183). According to this method, since the thickening effect during the polymerization reaction is small, it is possible to obtain a polyester copolymer having a high degree of polymerization and capable of melt spinning by a conventional method.

However, according to this method, the heat resistance of the isophthalic acid component having a phosphonium sulfonate group is inferior to that of the isophthalic acid component having a metal sulfonate group described above, and therefore, the polymerization reaction process of polyester or melt spinning is performed. Under high heat conditions such as processes, the degree of polymerization is reduced due to the decomposition of the isophthalic acid component having a phosphonium sulfonate group or the decomposition of the formed polymer, and the formed polyester, the fibers and molded articles made of it are yellowish brown. However, even when dyeing a yellow-brown polyester, a good color tone cannot be obtained.

Therefore, in order to improve the heat resistance of the polyester copolymerized with the isophthalic acid component having a phosphonium sulfonate group, a method of adding a heat resistance improver comprising a non-reactive quaternary onium salt is proposed. However, according to this method, although the strength of the drawn yarn itself obtained by this method is high, the strength tends to decrease when false twisting or dyeing is applied, and the strength retention ratio is high. Has the drawback of being low.

Further, as another conventional example of polyester fiber or yarn made dyeable with a cationic dye, a false twisting process comprising an ethylene terephthalate copolymer obtained by copolymerizing both 5-sodium sulfoisophthalic acid and isophthalic acid is used. Threads are known (Japanese Examined Patent Publication No. 55-26205, Japanese Unexamined Patent Publication No. 56-26034, etc.). However, in this false twisting yarn, when the false twisting process is performed under the conditions of the high false twisting number and the high false twisting set temperature which are usually required in the false twisting process of the cationic dye dyeable polyester yarn, A large number of so-called "caterpillar-like" fluffs are generated, and the commercial value thereof is significantly reduced. Moreover, the false twisting process reduces the strength of the yarn, making it unusable for practical use. Moreover, the woven or knitted fabric obtained from this false twisting process has a "paper-like" elasticity and an inferior feel without tightness. It has the drawback that

Further, a drawn yarn of ethylene terephthalate copolymerized polyester obtained by copolymerizing sodium sulfoisophthalic acid in an amount of 0.8 to 1.8 mol% is false twisted with a specific false twist number to give a cationic dye dyeable dye. Although it has been proposed to produce a false twisted textured yarn (Japanese Patent Laid-Open No. 59-71488), the results of additional tests by the present inventors show that the strength of the false twisted textured yarn after dyeing with a cationic dye is usually It fell to 3.5 g / d or less, which was also a problem in practical use.

[0010]

SUMMARY OF THE INVENTION Therefore, an object of the present invention is a polyester false twisting process which is dyeable with a cationic dye and is excellent in mechanical properties, yarn formability, processability, unwinding property, dyeing fastness, feeling and the like. It is to provide a method of manufacturing a yarn.

[0011]

As a technique for obtaining a polyester fiber dyeable with a cationic dye having a high strength, the inventors of the present invention have achieved a high strength of the fiber by stretching at a higher ratio than conventional ones. As a result of proceeding, we found the following facts. That is, in an attempt to obtain a high-strength fiber, if the degree of polymerization of the polyester is increased within a melt-spinnable range, the stretchability of the obtained fiber is lowered and a high-strength fiber cannot be easily obtained. When it is lowered, the drawability is improved and the draw ratio can be increased, but the strength of the fiber cannot be increased due to the low degree of polymerization.

Surprisingly, however, a specific amount of both the glass transition point depressant and the solid fine particles are contained in the cationic dye-dyeable aromatic polyester fiber having a sulfonate group, and the intrinsic viscosity [η When the above range is set within a specific range, it is possible to obtain a drawn yarn of high strength and good quality, because of the synergistic effect thereof, it is possible to carry out uniform drawing at a high draw ratio and without causing fluff or drawing unevenness. It was found that when the drawn yarn is false twisted, a high strength and high quality cationic dye dyeable false twisted yarn which has never been obtained can be obtained.

That is, the present invention relates to a method for producing a cationic dye-dyed polyester false twisted yarn by false twisting a drawn yarn made of an aromatic polyester fiber having a sulfonate group. As the drawn yarn, (a) the aromatic polyester having a sulfonate group constituting the fiber has 1.0 to 2.6 moles of a dicarboxylic acid component having a sulfonate group with respect to all carboxylic acid components constituting the polyester. % Of the glass transition point depressant and 0.1 to 0.5% of solid fine particles based on the weight of the aromatic polyester having a sulfonate group. 1.0% by weight; and (c) the intrinsic viscosity [η] of the aromatic polyester having a sulfonate group constituting the fiber and the content of the glass transition point depressant ( ) And (wt%) satisfy the relationship:;

[0014]

## EQU00004 ## 0.01.times.A + 0.54.ltoreq. [. Eta.]. Ltoreq.0.01.times.A + 0.68 (where 1.ltoreq.A.ltoreq.5) drawn yarn is used, and (2) The false twisting process of the drawn yarn is performed by the following relational expression;

[0015]

[Equation 5] [Where T is the false twist number (times / m), and D is the fineness of the drawn yarn.
(Denoting denier)] at a temperature of 190 to 2
It is a method for producing a polyester false twisted yarn dyeable with a cationic dye, which is carried out in a range of 20 ° C.

In the present invention, the cationic dye-dyeable polyester constituting the fiber of the drawn yarn is an aromatic polyester having a sulfonate group, and the sulfonate group is added to all carboxylic acid components constituting the polyester. It is necessary that the dicarboxylic acid component contained therein is copolymerized at a ratio of 1.0 to 2.6 mol%.

The "aromatic polyester having a sulfonate group" in the present invention is an aromatic polyester obtained from an acid component mainly composed of terephthalic acid and at least one glycol component, and in the polyester. A polyester in which a dicarboxylic acid component having a sulfonate group is copolymerized. As the glycol component, it is preferable to use at least one kind of ethylene glycol, trimethylene glycol and tetramethylene glycol, and it is particularly preferable that the aromatic polyester mainly comprises ethylene terephthalate units and / or butylene terephthalate units.

However, the aromatic polyester in the present invention may optionally contain a terephthalic acid component, a dicarboxylic acid having a sulfonate group, and a copolymerization component other than the above-mentioned glycol, in which case Usually, it is desirable that the ratio of the other copolymerization component is about 5 mol% or less.

Examples of the dicarboxylic acid component having a sulfonate group to be copolymerized in the aromatic polyester include dicarboxylic acid having a sulfonate group such as 5-sodium sulfoisophthalic acid, 5-potassium sulfoisophthalic acid and 5-lithium sulfoisophthalic acid. Acid components; 5-tetraalkylphosphonium sulfoisophthalic acid such as 5-tetrabutylphosphonium sulfoisophthalic acid and 5-ethyltributylphosphonium sulfoisophthalic acid can be mentioned, and of these, 5-sodium sulfoisophthalic acid is preferable. As for the dicarboxylic acid component having a sulfonate group, only one kind may be copolymerized in the aromatic polyester, or two or more kinds may be copolymerized.

As described above, in the present invention, the dicarboxylic acid component having a sulfonate group is 1.0 to 1.0 with respect to the total carboxylic acid component constituting the aromatic polyester.
It must be copolymerized at a ratio of 2.6 mol%. The ratio of the dicarboxylic acid component having a sulfonate group is 1.0
If it is less than mol%, it is impossible to obtain a cationic dye-dyeable polyester having a clear and good color tone when dyed with a cationic dye. On the other hand, when the copolymerization ratio of the dicarboxylic acid component having a sulfonate group exceeds 2.6 mol%, the viscosity of the polyester is remarkably increased and spinning becomes difficult, and moreover, the dyeing seat of the cationic dye is increased to the fiber. The amount of dyed cationic dye becomes excessive, and the vividness of the color tone is rather lost. From the standpoint of the sharpness and spinnability of the dyed product, the copolymerization ratio of the dicarboxylic acid component having a sulfonate group is preferably in the range of 1.5 to 2.0 mol%.

The above aromatic polyester can be synthesized by any method. For example, in the case of a polyester mainly composed of ethylene terephthalate units, terephthalic acid and ethylene glycol are directly esterified using a dicarboxylic acid component having a sulfonate group, or a lower alkyl ester of terephthalic acid and ethylene are used. A glycol ester of terephthalic acid or a low polymer thereof is produced by transesterification with glycol or by reacting terephthalic acid with ethylene oxide, which is heated under reduced pressure to a desired degree of polymerization. It can be produced by an ordinary synthetic method of carrying out a polycondensation reaction until a certain amount. The dicarboxylic acid component having a sulfonate group may be added at any time as long as it can be introduced as a copolymerization component in the polyester, for example, it may be added to the polyester synthesis raw material or after transesterification and before polymerization. May be added.

In the present invention, it is necessary that the aromatic polyester having a sulfonate group constituting the drawn yarn contains a glass transition point depressant (hereinafter glass transition point is referred to as "Tg") and solid fine particles. is there. In the present invention, a Tg depressant and solid fine particles are contained in a fiber made of an aromatic polyester having a sulfonate group,
A high-quality drawn yarn having unprecedented high strength and free from fluff and uneven drawing can be obtained.

The mechanism by which a high-strength drawn yarn is obtained in the present invention is not clear, but it is presumed as follows. That is, the Tg depressant acts to improve the mobility of the polyester molecular chain, and the drawability of the fiber is remarkably improved, and as a result, it is possible to draw at a high ratio and the strength of the fiber is increased. .. However, high-magnification drawing causes fluffing of drawing yarns and uneven drawing, and it is difficult to obtain a sufficiently high-quality drawn yarn in industry only by the action of the Tg depressant. However, when the solid fine particles are contained in the fiber together with the Tg depressant, unexpectedly, drawn fluff and drawing unevenness are not generated, and it is possible to obtain a drawn yarn of good quality and unprecedented high strength. Conceivable.

Here, the Tg lowering agent in the present invention means
It means an agent having a property of lowering the Tg of the polyester by 2 ° C. or more when 2% by weight of the Tg lowering agent is added to the aromatic polyester having a sulfonate group, as compared with the case where the Tg lowering agent is not added. .. The Tg of the aromatic polyester at that time can be easily measured by DSC or the like. In the present invention, as the Tg lowering agent, any agent can be used as long as it can lower the Tg of the aromatic polyester having a sulfonate group by 2 ° C. or more when 2% by weight thereof is added. , The following general formula (I);

[0025]

Embedded image R ¹ O—X—OR ² (I) (wherein X represents an aromatic residue, and R ¹ and R ² represent an alkyl group having 6 to 18 carbon atoms or an arylalkyl group). Preference is given to using at least one of the compounds mentioned.

In the compound represented by the above general formula (I), preferable examples of the aromatic residue X include divalent groups represented by the following formulas (II) to (IX). it can.

[0027]

[Chemical 3]

[0028]

[Chemical 4]

[0029]

[Chemical 5]

[0030]

[Chemical 6]

[0031]

[Chemical 7]

[0032]

[Chemical 8]

[0033]

[Chemical 9]

[0034]

[Chemical 10]

And a Tg suitable for use in the present invention.
Specific examples of the depressant include, for example, the following general formula (X) to
The compound represented by (XII) can be mentioned.

[0036]

[Chemical 11]

[0037]

[Chemical 12]

[0038]

[Chemical 13]

The content of the Tg depressant is in the range of 1 to 5% by weight based on the weight of the aromatic polyester constituting the drawn yarn. When the content of the Tg lowering agent is less than 1% by weight, the Tg lowering effect is not sufficiently exhibited and it becomes impossible to stretch at a high magnification. On the other hand, if the content of the Tg depressant exceeds 5% by weight, the polyester is colored and the dyeing fastness is deteriorated, which is not preferable. Tg depressant content is 2
It is preferably about 4% by weight.

As the solid fine particles, inorganic fine particles having an average particle size of about 15 to 70 mμ are preferable. If the average particle size of the solid fine particles is less than 15 mμ, drawn fluff and uneven drawing are likely to occur, while if the average particle size exceeds 70 mμ, the fibers are easily fibrillated, which is not preferable. The surface of the solid fine particles may be modified by aluminum coating, introduction of an alkyl group, or the like. The refractive index of the solid fine particles is not particularly limited, but if it is desired to maintain the brilliant transparency of the aromatic polyester, it is preferable to use solid fine particles having a refractive index of 1.65 or less, which is smaller than the refractive index of the aromatic polyester. .. For example, while maintaining the transparent transparency of the target aromatic polyester, the refractive index is 1.65.
The following solid fine particles and solid fine particles having a refractive index of more than 1.65 can be used together. Examples of solid fine particles preferably used in the present invention include silica having a refractive index of 1.65 or less, alumina, kaolin, calcium carbonate and the like, and among them, the average particle diameter is 15 to 70.
mμ silica is especially preferred.

The content of the solid fine particles is 0.1 to 1.0 based on the weight of the aromatic polyester constituting the drawn yarn.
The range is wt%. When the content of the solid fine particles is less than 0.1% by weight, good stretchability due to the synergistic effect with the Tg depressant is not exhibited and high-stretching cannot be performed. On the other hand, when the content of the solid fine particles exceeds 1.0% by weight, the strength of the fiber is reduced, which is not preferable. The content of solid fine particles is preferably 0.3 to 0.5% by weight.

The timing and method of adding the Tg depressant and solid fine particles to the aromatic polyester are not particularly limited. For example, the Tg depressant and solid particulates may be added at the same time, sequentially or at completely different times. Further, for example, the Tg depressant and solid fine particles may be added before, during, or after the polymerization of polyester at an appropriate time, or added as a masterbatch in polyester chips, or during melt spinning. You may add.

In the present invention, the purpose is to obtain a false twisted yarn having a strength of 3.5 g / d or more even after dyeing at 120 ° C. In order to obtain such a high strength false twisted yarn. Requires the strength of the drawn yarn before false twisting to be 4.0 g / d or more and the elongation to be 26% or more. For that purpose, the intrinsic viscosity [η] of the aromatic polyester having a sulfonate group is required. And the content (A) (% by weight) of the Tg depressant must satisfy the following relational expression.

[0044]

## EQU7 ## 0.01 × A + 0.54 ≦ [η] ≦ 0.01 × A + 0.68 (where 1 ≦ A ≦ 5) In the above, the intrinsic viscosity [η] of the aromatic polyester
Is the value when the aromatic polyester is dissolved in a mixed solvent of phenol / tetrachloroethane (weight ratio 1: 1) and measured at 30 ° C., and the strength and elongation of the drawn yarn and the dyed yarn are It is a value when measured according to JIS L 1013.

When the intrinsic viscosity [η] of the aromatic polyester having a sulfonate group is larger than 0.01 × A + 0.68, the thickening effect of the aromatic polyester becomes too large and spinning becomes difficult. Intrinsic viscosity [η] of aromatic polyester having acid base is 0.01 × A + 0.5
If it is less than 4, a sufficiently high strength fiber cannot be obtained because the degree of polymerization is small.

The stretched aromatic polyester yarn used in the present invention is produced by producing a polyester fiber by a general melt spinning method from an aromatic polyester having a sulfonate group containing a Tg depressant and solid fine particles, and producing the polyester fiber from a conventional melt spinning method. It can be produced by stretching by the method. For example, an aromatic polyester having a sulfonate group containing a Tg depressant and solid fine particles may be added at about 280 to 310 ° C.
After producing polyester fiber by melt spinning at the temperature of
After pre-heating the obtained spun raw yarn with a heating roller to a temperature (generally 70 to 95 ° C.) higher than the Tg of the aromatic polyester,
The speed of the winding roller is set to a predetermined draw ratio (usually about 3.0 to
It is adjusted to 5.0), wound up and stretched, and then heated to a temperature above the crystallization temperature of the aromatic polyester (usually 1
A drawn yarn for false twisting can be obtained by heat treatment at 50 to 180 ° C. The drawn yarn thus obtained has a high strength and does not cause fluff or draw unevenness, and is extremely suitable as a base yarn for false twisting. However, in some cases, this high-strength and high-quality drawn yarn capable of dyeing with a cationic dye can also be used for other applications other than false twisting.

The thickness of the aromatic polyester fiber before drawing and the thickness of the drawn yarn are not particularly limited, but when the fineness of each single fiber constituting the drawn yarn is set to 1.0 denier or less, the drawn yarn is drawn. When a false twisted yarn obtained by false twisting is used as a fabric, a fabric that is soft and has a good feel can be obtained. In addition, in the present invention, in addition to the Tg depressant and the solid fine particles, the aromatic polyester may contain other additives which are usually used in aromatic polyester fibers, if necessary. Further, in the present invention, as the spinning base yarn for the drawn yarn, it is also possible to use a composite fiber composed of the above-mentioned aromatic polyester having a sulfonate group and another polymer, a mixed-spun fiber and the like.

In the present invention, the drawn aromatic polyester yarn obtained as described above has a false twist number (T) (twice / time).
m) so that the following relational expression is satisfied, the temperature 19
False twisting is performed at 0 to 220 ° C.

[0049]

[Equation 8] (In the formula, T and D are the same as above.)

If the false twist number (T) is smaller than the lower limit of the above relational expression, the woven or knitted fabric obtained by weaving the false twisted yarn obtained by false twisting has a flat texture, while the false twist is obtained. When the number (T) is larger than the upper limit value of the above relational expression, fluff is generated during false twisting, the strength of the false twisted yarn is reduced, and it cannot be put to practical use. Further, when the false twisting process is performed at a temperature of less than 190 ° C., the crimpability of the obtained false twisted yarn becomes low, while when the false twisting process is performed at a temperature higher than 220 ° C.,
The decrease in the strength of the yarn, the fusion between the fibers, the occurrence of fluff, the occurrence of uneven dyeing, etc. become remarkable, and it becomes unusable for practical use.

Further, in the present invention, the drawn specific aromatic polyester yarn described above is false twisted under the specified conditions described above so as to be 3.
An unprecedented high-strength false twisted yarn that can be a dyed yarn having a strength of 5 g / d or more is obtained. The false twisted yarn obtained by the method of the present invention can be subjected to knitting or weaving or other processing by a conventional method to give a cloth or the like which can be used for various purposes.

[0052]

EXAMPLES The present invention will be specifically described below with reference to examples, but the present invention is not limited thereto. In the following examples, the intrinsic viscosity [η] of the aromatic polyester is phenol / tetrachloroethane (weight ratio 1:
It is a value when it is dissolved in the mixed solvent of 1) and measured at 30 ° C., and the strengths of the drawn yarn and the dyed yarn are JIS L.
It is a value when measured by 1013. Further, the dyeing of the knitted fabric obtained from the false twist textured yarn was performed under the following conditions.

[0053]Knitted fabric dyeing conditions  Cationic dyeing bath composition: Cathilon Brill Red 4GH 2% owf (manufactured by Hodogaya Chemical Co., Ltd.) Sodium sulfate 3 g / liter Acetic acid 1% owf Sodium acetate 0.5% owf ETA 0.1 g / liter Bath ratio: 1:50 Dyeing color temperature Degree: 120 ℃ Dyeing time: 40 minutes

Example 1 5 as dicarboxylic acid component
-Sodium dimethyl sulfoisophthalate (hereinafter "SI
P ") was used and dimethyl terephthalate containing 2.5 mol% and ethylene glycol were used to carry out polymerization according to a conventional method by a transesterification method to produce a polyester having an intrinsic viscosity [η] = 0.63. .. At that time, 3% by weight of the Tg depressant represented by the general formula (X) and 0.3% by weight of silica having an average particle diameter of 30 mμ and a refractive index of 1.55 were added in the latter stage of the polymerization after transesterification. Using the obtained polyester chips, the base temperature is 305
Melt spinning was performed at a temperature of 1000 ° C. and a take-up speed of 1000 m / min by a conventional method to produce polyester fibers of 252 denier / 72 filaments.

The spun raw yarn obtained above is preheated by a heating roller at a temperature of 80 ° C., drawn at a draw ratio of 3.3 times, wound by a winding roller, and then heat treated at a temperature of 145 ° C. A drawn yarn of 75 denier / 72 filaments for false twisting was produced. When the strength of this drawn yarn was measured by the method described above, it was as shown in Table 1 below. Using the spindle false twisting machine, the drawn yarn obtained above had a false twist number (T) of 3380 times / m and a tension on the spindle side of about 2
Adjust the overfeed rate to be 0g, and
False twisting was performed at a false twisting temperature of 0 ° C. A knitted fabric is produced by a tubular knitting machine using the obtained false twist textured yarn, and ordinary scouring,
After pre-setting, dyeing was carried out under the above dyeing conditions.
Then, the dyed knitted fabric was unwound, and the strength of the yarn was measured by the method described above. The results are shown in Table 1 below.

Comparative Example 1 Spinning, drawing, false twisting, knitting and dyeing were carried out in the same manner as in Example 1 except that the Tg depressant was not added. The results are shown in Table 1.

Comparative Example 2 Intrinsic viscosity [η] = 0.73
In the same manner as in Example 1 except that the above polyester was used, spinning, drawing, false twisting, knitting and dyeing were performed. The results are shown in Table 1.

Comparative Example 3 Spinning, drawing, false twisting, knitting and dyeing were carried out in the same manner as in Comparative Example 2 except that the Tg depressant was not added. The results are shown in Table 1.

Example 2 Using dimethyl terephthalate containing 1.7 mol% of SIP and ethylene glycol, polymerization was carried out according to a conventional method by a transesterification method to obtain an intrinsic viscosity [η] = 0.67. Of polyester was produced. At that time, 2% by weight of a Tg depressant represented by the general formula (X) and 0.3% by weight of silica having an average particle diameter of 30 mμ and a refractive index of 1.55 were added in the latter stage of polymerization after transesterification. Using the obtained polyester chips,
Melt spinning was performed at a spinneret temperature of 305 ° C. and a take-up speed of 1000 m / min by a conventional method to produce 252 denier / 72 filament polyester fibers.

The spun raw yarn obtained above is preheated by a heating roller at a temperature of 80 ° C., drawn at a draw ratio of 3.3 times, wound by a winding roller, and then heat treated at a temperature of 145 ° C. A drawn yarn of 75 denier / 72 filaments for false twisting was produced. When the strength of this drawn yarn was measured by the method described above, it was as shown in Table 1 below. The drawn yarn obtained above was false twisted, knitted and dyed in the same manner as in Example 1. The results are shown in Table 1.

Comparative Example 4 Spinning, drawing, false twisting, knitting and dyeing were performed in the same manner as in Example 2 except that the Tg depressant was not added. The results are shown in Table 1.

Comparative Example 5 Spinning, drawing, false twisting, knitting and dyeing were carried out in the same manner as in Example 2 except that the Tg depressant and silica were not added. The results are shown in Table 1.

Example 3 Using dimethyl terephthalate containing 1.2 mol% of SIP and ethylene glycol, polymerization was carried out according to a usual method by a transesterification method to obtain an intrinsic viscosity [η] = 0.65. Of polyester was produced. At that time, 2% by weight of a Tg depressant represented by the general formula (X) and 0.3% by weight of silica having an average particle diameter of 30 mμ and a refractive index of 1.55 were added in the latter stage of polymerization after transesterification. Using the obtained polyester chips,
Melt spinning was performed at a spinneret temperature of 300 ° C. and a take-up speed of 1000 m / min by a conventional method to produce polyester fibers of 252 denier / 72 filaments.

The spun raw yarn obtained above is preheated by a heating roller at a temperature of 80 ° C., drawn at a draw ratio of 3.3 times, wound by a winding roller, and then heat treated at a temperature of 145 ° C. A drawn yarn of 75 denier / 72 filaments for false twisting was produced. When the strength of this drawn yarn was measured by the method described above, it was as shown in Table 1 below. The drawn yarn obtained above was false twisted, knitted and dyed in the same manner as in Example 1. The results are shown in Table 1.

Comparative Example 6 Spinning, drawing, false twisting, knitting and dyeing were carried out in the same manner as in Example 3 except that the Tg depressant was not added. The results are shown in Table 1.

Comparative Example 7 Using dimethyl terephthalate containing 1.5 mol% of SIP and ethylene glycol, polymerization was carried out according to a conventional method by a transesterification method to obtain an intrinsic viscosity [η] = 0.55. Of polyester was produced. Using the obtained polyester chips,
Melt spinning was performed at a spinneret temperature of 300 ° C. and a take-up speed of 1200 m / min by a conventional method to produce polyester fibers of 570 denier / 48 filaments.

The spun raw yarn obtained above was preheated by a heating roller at a temperature of 80 ° C., stretched at a draw ratio of 3.8 times, wound by a winding roller, and then heat treated at a temperature of 145 ° C. A drawn yarn of 150 denier / 48 filament for false twisting was produced. When the strength of this drawn yarn was measured by the method described above, it was as shown in Table 1 below. Using the spindle false twisting machine, the drawn yarn obtained above was false twisted (T) = 2590 times / m at an overfeed rate of 0%.
False twisting was performed at a false twisting temperature of 200 ° C. Using the obtained false-twisted yarn, the knitted fabric was prepared, scoured, preset and dyed in the same manner as in Example 1, and the dyed knitted fabric was unwound and the strength of the yarn was measured by the method described above. It was measured.
The results are shown in Table 1 below.

Comparative Example 8 Dimethyl terephthalate 10
0 parts, ethylene glycol 66 parts, manganese acetate tetrahydrate 0.03 parts (0.024 parts to dimethyl terephthalate)
Mol%), and 1.7 with respect to dimethyl terephthalate.
Mol% 3,5-dicarbomethoxybenzenesulfonic acid tetra-n-butylphosphonium salt (hereinafter referred to as “DBT”) was charged into a transesterification can and heated from 140 ° C. to 220 ° C. in a nitrogen gas atmosphere for 4 hours. The mixture was heated to cause a transesterification reaction. Subsequently, the obtained product was added with 0.03 part of a 56% aqueous solution of orthophosphoric acid (0.03 mol% based on dimethyl terephthalate) and 0.04 part of antimony trioxide.
Part (0.027 mol% relative to dimethyl terephthalate)
Was added and transferred to a polymerization vessel. Then 76 hours
The pressure was reduced from 0 mmHg to 1 mmHg, and simultaneously the temperature was raised from 230 ° C. to 280 ° C. over 1 hour to polymerize until the intrinsic viscosity of the product [η] = 0.64.

The obtained polyester was dried and then melt-spun by a conventional method at a spinneret temperature of 310 ° C. and a take-up speed of 1200 m / min to produce a polyester fiber of 252 denier / 72 filaments. The spun raw yarn obtained above is preheated by a heating roller at a temperature of 85 ° C., drawn at a draw ratio of 3.3 times, wound by a winding roller, and then heat treated at a temperature of 145 ° C. for false twisting. A 75 denier / 72 filament draw yarn was produced. When the strength of this drawn yarn was measured by the method described above, it was as shown in Table 1 below. The drawn yarn obtained above was false twisted using a spindle false twisting machine at a false twisting temperature (T) of 2380 times / m and an overfeed rate of 0% at a false twisting temperature of 210 ° C.
Using the obtained false-twisted yarn, the knitted fabric was prepared, scoured, preset and dyed in the same manner as in Example 1, and the dyed knitted fabric was unwound and the strength of the yarn was measured by the method described above. It was measured. The results are shown in Table 1 below.

[0070]

[Table 1]

From the results of Example 1, Example 2 and Example 3 in Table 1 above, the addition amounts of the Tg depressant and silica are within the scope of the present invention, and the intrinsic viscosity of the aromatic polyester having a sulfonate group is shown. In the present invention in which [η] satisfies the above relational expression and the false twisting of the drawn yarn is performed under the condition represented by the above relational expression, the strength of the drawn yarn is 4.
The strength of the yarn obtained by false-twisting the drawn yarn is as high as 2 g / d or more and is 3.5 g / d or more even after dyeing with a cationic dye, and an extremely high-strength drawn yarn and false-twisted yarn are obtained. You can see that. On the other hand, Comparative Example 1 and Comparative Example 3
From the results of Comparative Example 6, when an aromatic polyester containing no Tg depressant was used, the obtained drawn yarn was as low as less than 4 g / d, even if other requirements were the same as those of the present invention, and It can be seen that the strength of the false twisted yarn obtained therefrom is as low as 3.1 g / d or less after dyeing with a cationic dye.

From the results of Comparative Example 2, when an aromatic polyester having a high intrinsic viscosity [η] of 0.73 which does not satisfy the above relational expression is used, it contains a Tg depressant and silica and It can be seen that even if the requirement of 1 is the same as that of the present invention, the strength of the obtained drawn yarn and false twisted yarn is low and single yarn breakage occurs. Further, comparing the results of Example 2 with Comparative Example 4, it is found that the strength of the obtained drawn yarn and false twisted yarn is reduced when silica is not added to the aromatic polyester.

The same can be seen from the comparison between Example 3 using an aromatic polyester containing both a Tg depressant and silica and Comparative Examples 6 and 7 lacking either one. Recognize. Furthermore, in Comparative Example 8, the strength of the drawn yarn was a high value of 4.5 g / d, but after dyeing the false twisted yarn obtained therefrom, the strength of the yarn was 3.2 g.
It has fallen to / d.

[0074]

INDUSTRIAL APPLICABILITY According to the present invention, a specific amount of glass transition point depressant and solid fine particles are contained in a fiber composed of a cationic dye-dyeable aromatic polyester having a specific ratio of sulfonate group and a specific intrinsic viscosity. By containing both of these in a specific amount, it is possible to obtain a high-strength and high-quality drawn yarn, which enables uniform drawing at a high draw ratio and without causing drawing fluff or drawing unevenness. By false-twisting the drawn yarn, a polyester false-twisted yarn with unprecedented cationic dyeability and excellent mechanical properties such as strength, processability, unwindability, dyeing fastness, and feel is obtained. Obtainable.

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Claims (2)

[Claims] 1. A method for producing a cationic dye-dyed polyester false twisted yarn by false twisting a drawn yarn made of an aromatic polyester fiber having a sulfonate group, wherein (1) the drawn yarn is: (A) The aromatic polyester having a sulfonate group constituting the fiber has a proportion of the dicarboxylic acid component having a sulfonate group of 1.0 to 2.6 mol% with respect to all carboxylic acid components constituting the polyester. (B) 1-5% by weight of glass transition point depressant and 0.1-1.0% by weight of solid fine particles, based on the weight of the aromatic polyester having a sulfonate group. %, And (c) the intrinsic viscosity [η] of the aromatic polyester having a sulfonate group constituting the fiber and the content (A) (% by weight) of the glass transition point depressant are as follows. Satisfying the relational expression; [Equation 1] 0.01 × A + 0.54 ≦ [η] ≦ 0.01 × A + 0.68 (where 1 ≦ A ≦ 5) drawn yarn is used, Then, (2) the false twisting process of the drawn yarn is performed by the following relational expression; [Where T is the false twist number (times / m), and D is the fineness of the drawn yarn.
(Denoting denier)] at a temperature of 190 to 2
A process for producing a polyester false-twisted yarn dyeable with a cationic dye, which is carried out in a range of 20 ° C. 2. A dicarboxylic acid component having a sulfonate group is based on 5-sodium sulfoisophthalic acid, solid fine particles are silica particles having an average particle diameter of 15 to 70 μm, and a glass transition point depressant is represented by the following general formula: (I); R ¹ O—X—OR ² (I) (wherein, X is an aromatic residue, and R ¹ and R ² are an alkyl group having 6 to 18 carbon atoms or an arylalkyl group. It represents at least one compound represented by the formula 1).
Manufacturing method.