KR930000244B1 - Polyester fiber - Google Patents

Abstract

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Description

Polyester fiber

1 and 2 are X-ray photographs showing incineration X-ray scattering images of quadruple stretched yarn obtained in Comparative Example 2 and Example 6, respectively.

TECHNICAL FIELD The present invention relates to a melt viscosity reducing agent for polyester resins and a polyester fiber having high strength and easy spinning.

Conventionally, polyester resins are widely used as synthetic fibers, but in order to increase the strength of synthetic fibers, the polymerization degree of the polymer may be increased. However, when the polymerization degree of the polymer is increased, the melt viscosity naturally increases, resulting in poor workability and lower productivity. In order to lower the melt viscosity, it is also possible to increase the melting temperature, but since the decomposition of the resin is promoted, the object of lowering the polymer polymerization degree and obtaining a fiber having a high degree of polymerization cannot be achieved.

Polyester filaments having a high degree of polymerization are used in the field of industrial high strength, and there is a demand to further increase the strength, and therefore, it is necessary to lower the melt viscosity of the resin. In staple yarns, lowering the melt viscosity of the polymer contributes to increasing productivity in connection with the improvement of the extrusion capacity from the nozzle or the reduction of power.

Even in the field of high-speed spinning, which has recently been put into practical use, it is effective to lower the melt viscosity of resins in order to increase the discharge amount.

In order to solve these problems, the addition of a lubricant is considered. For example, adding ethylene bis stearate, stearic acid, stear alcohol, etc. to the resin lowers the melt viscosity but at the same time reduces the polymerization degree of the resin. .

On the other hand, polyester fibers have a bad feel and a gritty feeling. In order to solve this problem, fine denierization, alkali weight reduction processing, and softening agent processing are performed.

These prior arts are described in [Dyeing Industry] 38, 288-299 for fine denier, and J. Soc.Dyers Colorsts (IEHaden) 78, 9 for alkaline weight reduction. Cotton, 1962, The Textile Mfr. (BCMDorset), page 293 (July 1963), describes the processing of softeners in US Pat. No. 33,77249.

The problem to be solved by the present invention is to find a melt viscosity reducing agent that can lower the melt viscosity without essentially lowering the polymerization degree of the polyester resin, and using the same, easy spinning and excellent polyester fiber To get.

Compounds (1), (2), and (3) used in the present invention are disclosed in Japanese Patent Application Laid-Open Nos. 58-93752, 57-2824, and 62-18463.

The present invention is a method for producing a polyester fiber in which the compound (b) represented by the general formula (1), (2) or (3) is added to the polyester (a) having ethylene terephthalate as the main repeating unit for melt spinning. to be.

(Wherein A ₁ and A ₂ are an alkyl group or an arylalkyl group having 6 to 18 carbon atoms, n is 0 or 1, and X is Any one of -S-, -SO _2- , or -O-. In addition, R ₁ and R ₂ represent H or an alkyl group having 4 or less carbon atoms.)

(Wherein R ₃ and R ₄ are each an alkyl group having 6 to 18 carbon atoms, l and m are integers in which l + m is 1 or more and 3 or less, and n and X are as described above.)

(Wherein R ₅ and R ₆ represent a straight chain alkyl group having 12 to 22 carbon atoms.)

In the present invention, preferably, the compound represented by the general formula (1) or (2) is added, followed by melt spinning, followed by preheat stretching at 60 to 100 ° C and heat treatment at 150 to 250 ° C under tension.

It is preferable that the raw polyester resin has an intrinsic viscosity of 0.8 or more at 25 ° C. in phenol / tetrachloroethane (60/40).

It is preferable that draw ratio becomes four times or more.

Moreover, this invention provides the polyester fiber obtained by the said manufacturing method, and it is preferable that the strength of the polyester fiber obtained is 7 g / d or more.

In other words, the present invention is a general formula (1)

(Wherein A ₁ and A 2 are an alkyl group or an arylalkyl group having 6 to 18 carbon atoms, n is 0 or 1, and X is Any one of -S-, -SO _2- , or -O-. In addition, R ₁ and R ₂ represent H or an alkyl group having 4 or less carbon atoms.)

Or, general formula (2)

(Wherein R ₃ and R ₄ are each an alkyl group having 6 to 18 carbon atoms, l and m are integers having 1 + m or more and 3 or less, n and X are the same as above) It is providing the polyester fiber obtained by melt-spinning the polyester resin composition which adds and mixes the said melt viscosity reducing agent for polyester resins with the melt viscosity reducing agent for resins, and a raw material polyester resin.

In the compound of formula (1) according to the present invention, the carbon number of A ₁ and A ₂ can be arbitrarily selected within the above range. A1, A ₂ of the carbon atoms is less than 6 when the molecular weight is too low, air bubbles caused by the melting temperature and the boiling if insufficient effect deteriorates in compatibility with a resin or the addition exceeding 18. Specifically, A ₁ and A ₂ are linear alkyl groups such as n-hexyl group, n-octyl group, n-dodecyl group, n-octadecyl group, branched alkyl groups such as 2-hexyldecyl group and methyl branched octadecyl group, Or an arylalkyl group, such as a benzyl group and 2-phenylmethyl group.

Compound represented by the general formula (1) according to the present invention It is obtained easily by making the C6-C18 halogenated alkyl and / or halogenated arylalkyl react with the aromatic glycol represented by following alkali catalysts, such as NaOH and KOH.

The specific example of the compound represented by General formula (1) which concerns on this invention is as follows.

(Hereinafter abbreviated as compound (1) of the present invention)

(Hereinafter abbreviated as compound (2) of the present invention)

(Hereinafter abbreviated as compound (3) of the present invention)

(Hereinafter abbreviated as compound (4) of the present invention)

(Hereinafter abbreviated as compound (5) of the present invention)

(Hereinafter abbreviated as compound (6) of the present invention)

(Hereinafter abbreviated as compound (7) of the present invention)

Moreover, in the compound of Formula (2) which concerns on this invention, R <_3> , R <_4> is a linear or side chain alkyl group, The carbon number can be arbitrarily selected in the said range.

If the carbon number of R ₃ and R ₄ is less than 6, the molecular weight is too low, the melting temperature may boil and bubbles may be generated. If the carbon number of R ₃ and R ₄ is exceeded, the compatibility with the resin is deteriorated, so the effect is insufficient. R <_3> , R <_4> is a hexyl group, an octyl group, a dodecyl group, an octadecyl group, etc. specifically ,.

The compound represented by General formula (2) which concerns on this invention can be obtained easily by a well-known method. For example, it is obtained by reacting biphenyl, diphenyl ether, diphenyl sulfide and the like with an alkyl olefin having 6 to 18 carbon atoms in the presence of a catalyst such as aluminum chloride or boron trifluoride ethyl ether.

The specific example of the compound represented by General formula (2) which concerns on this invention is as follows.

(Hereinafter abbreviated as compound (8) of the present invention)

(Hereinafter abbreviated as compound (9) of the present invention)

(Hereinafter abbreviated as compound of the present invention)

(Hereinafter abbreviated as compound of the present invention)

(Hereinafter abbreviated as compound of the present invention)

(Hereinafter abbreviated as compound of the present invention)

That is, the present invention is represented by general formula (3)

(In formula, R <_5> , R <_6> represents a C12-C22 linear alkyl group.) The said melt viscosity reducing agent for polyester resins and the raw material polyester resin are made into the melt viscosity reducing agent for polyester resins which consist of compounds represented by It is to provide a polyester fiber obtained by melt spinning a polyester resin composition formed by addition mixing.

In the compound of formula (3) according to the present invention, the carbon number of R ₅ and R ₆ can be arbitrarily selected within the above range. If the carbon number of R ₅ and R ₆ is less than 12, the molecular weight is too low, the melting temperature may boil and bubbles may be formed. If the carbon number of R ₅ and R ₆ is exceeded, the compatibility with the resin may be deteriorated. .

The compound represented by the general formula (3) according to the present invention is easily obtained by reacting 1 mol of pyromellitic anhydride with 2 mol of an amine having 12 to 22 carbon atoms to form a dicarboxylic acid diamide compound, followed by dehydration and condensation.

It is also preferable that the raw material polyester resin which concerns on this invention makes polyethylene terephthalate the main repeating unit, and it is preferable that the intrinsic viscosity of 25 degreeC is 0.8 or more in phenol / tetrachloroethane (60/40, weight ratio). If the intrinsic viscosity of the raw material polyester resin is less than 0.8, the melt viscosity of the polyester resin is not so large as to significantly inhibit productivity, and the high strength to be targeted may not be expressed.

Polyester copolymerized with sulfonated sodium isophthalate or the like can also be used, which is a cationic salt.

Even if the melt viscosity reducing agent of the present invention is added and mixed uniformly to the polyester resin and fades to a high temperature during melt spinning, there is little fuming or coloring and excellent heat resistance.

The polyester fiber of the high strength can be obtained from the polyester resin composition which added the melt viscosity reducing agent for polyester resins of this invention.

Furthermore, from the polyester resin composition to which the melt viscosity reducing agent represented by General formula (3) was added, polyester fiber with a good touch can be obtained irrespective of spinning conditions.

In producing high strength fibers, the premise is to use high molecular weight polymer tips. In the case of spinning, this polymer tip is usually melted at 280 to 300 ° C. However, due to the entanglement of the polymer chains, the polymer tip has a higher melt viscosity than a high molecular weight polymer, and is easy to cause an increase in discharge pressure and poor sharpness. However, the presence of the melt viscosity reducing agent of the present invention lowers the spinning pressure and the mounting force and facilitates spinning.

The yarn discharged from the nozzle is once cooled and solidified. When polyester resin is used for injection molding, promotion of crystallization at the time of cooling is preferable for the purpose of improving moldability, but crystallization at the time of melt spinning of polyethylene terephthalate resin or the like is not preferable. The lowering agent does not bring about the crystallization of the resin in the cooling process from the spinning nozzle. The cooled and drawn uncalcined fibers are orientationally crystallized in the next drawing and heat treatment process to form a high strength fiber.

In order to achieve the desired performance, the melt viscosity reducing agent of the present invention needs to be added in an amount of 0.1 to 10 parts, preferably 0.5 to 5 parts, based on 100 parts of the raw polyester resin. . In 0.1 parts or less, the effect is hardly expected, and in 10 parts or more, a bad influence on resin physical property appears.

The method of adding the melt viscosity reducing agent of the present invention to the raw polyester resin may be added at a suitable step at the time of resin production or production, or may be added to the resin pellets or molten resin during spinning.

The high strength polyester fiber of the present invention is obtained by uniformly mixing the raw polyester resin and the melt viscosity reducing agent of the present invention, releasing it in a molten state, stretching and cooling after cooling, and performing heat treatment. After cooling, the discharged yarn may be preheated and then continuously heat treated under tension after winding as undrawn yarn, or drawn into a take-out roller without winding the discharged yarn, and then drawn and heat-treated on a heating roller.

Stretching and heat processing can be performed without change with normal polyester fiber. The preferable preheating temperature at the time of stretching is 60-100 degreeC, and the preferable temperature of heat processing is 150-250 degreeC. It is preferable that the draw ratio for obtaining a high strength fiber is four times or more.

It is preferable that the polyester resin which concerns on this invention makes polyethylene terephthalate the main repeating unit, and another component, for example, polyethyleneglycol, POE (2) bisphenol A, sodium sulfonate isophthalate, 1, 4- butanediol, etc. Some copolymerization is also good.

The cationic salt salt polyester fiber which concerns on this invention is a polyester fiber which used as a raw material the thing which the sulfonated sulfonate is partially copolymerized as a structural component of a polyester resin.

EXAMPLE

Although an Example demonstrates this invention concretely below, this invention is not limited to these Examples.

Example 1

After adding the compound shown in Table 1 to polyethylene terephthalate resin, the strand obtained by melt-mixing by the extruder was cut after water cooling, and it was set as the sample. The melt flow index of this resin composition was measured by the amount of melt resin extruded from an orifice having a diameter of 2.095 mm and a length of 8 mm at a temperature of 275 ° C. and a load of 2160 g for 10 minutes. The larger the melt flow index, the lower the melt viscosity. The sample after meltflow index measurement was melt | dissolved in the phenol / tetrachloroethane (60/40, weight ratio) solution, and intrinsic viscosity [(eta)] was measured at 25 degreeC. It can be said that the thing of [eta] without an additive does not fall in resin polymerization degree essentially. The results are shown in Table 1.

TABLE 1

The compounds of the present invention make it possible to lower the melt viscosity essentially without lowering the ultimate viscosity and to facilitate polyester spinning of high melt viscosity.

Example 2

To 100 parts by weight of the polyethylene terephthalate resin having an intrinsic viscosity of 1.2, 5 parts by weight of the compound ① of the present invention was added as a melt viscosity reducing agent and dry blended. The blend was put into an extruder type melt spinning machine, and the discharge part temperature was set to 290 ° C and discharged at a rate of 3 g / min from a spinning nozzle having a diameter of 0.5 mm. The discharge yarn was wound at 100 m / min at a position of 2.5 m directly under the nozzle. The film was stretched five times to 80 ° C. in a wound unstretched oil oil bath (bath) and heat-treated at 170 ° C. for 30 minutes under formal conditions.

The pressure of the nozzle part at the time of discharge | release was 65 kg / cm <2>, the intrinsic viscosity of the undrawn yarn was 0.98, and the strength of the drawn yarn was 9.5 g / d.

Comparative Example 1

The same experiment as in Example 2 was conducted without adding compound (1) of the present invention.

As a result, the pressure of the nozzle part at the time of discharge | release was 100 kgf / cm <2>, the intrinsic viscosity of the undrawn yarn was 0.97, and the strength of the drawn yarn was 9.7 g / d.

Example 3

The same experiment as in Example 2 was conducted using the compound of the present invention ② as a melt viscosity reducing agent.

As a result, the pressure of the nozzle part at the time of discharge | release was 60 kgf / cm <2>, the intrinsic viscosity of the undrawn yarn was 0.98, and the strength of the drawn yarn was 9.4 g / d.

Example 4

The same experiment as in Example 2 was conducted using the compound 8 of the present invention as a melt viscosity reducing agent.

As a result, the pressure of the nozzle portion at the time of discharge was 65 kgf / cm 2, the intrinsic viscosity of the undrawn yarn was 0.98, and the strength of the drawn yarn was 9.5 g / d.

As shown in Examples 2 to 4, by adding a compound that serves as a melt viscosity reducing agent for the polyester resin of the present invention, the spinning nozzle pressure can be significantly reduced, and a high molecular weight polyester fiber is produced. Was easy.

Example 5

After adding the compound shown in Table 2 to polyethylene terephthalate resin, it melt-mixed with the extruder, the obtained strand was cut after water cooling, and it was set as the sample. The melt flow index of this resin composition was measured by the amount of melt resin extruded from an orifice having a diameter of 2.095 mm and a length of 8 mm at a temperature of 275 ° C. and a load of 2160 g for 10 minutes. The larger the melt flow index, the lower the melt viscosity. The sample after melt flow index measurement was melt | dissolved in the phenol / tetrachloroethane (60/40, weight ratio) solution, and the intrinsic viscosity [eta] was measured at 25 degreeC. It can be said that what [eta] does not have an additive, there is essentially no fall of resin polymerization degree. The results are shown in Table 2.

TABLE 2

The compound of the present invention was essentially effective in lowering the melt viscosity without lowering the intrinsic viscosity, and was effective in lowering the release pressure of the resin and improving the release rate.

Example 6

To 100 parts by weight of polyester resin of intrinsic viscosity 1.0

After addition of the distearic pyromellitic acid imide represented by the following, it was melt-mixed with the extruder, the obtained strand was cut after water cooling, and it tipped. The ultimate viscosity of this tip was 0.85. This tip was put into an extruder type melt spinning machine, and the discharge part was discharged at a rate of 2 g / min from a spinning nozzle having a diameter of 5 mm at a temperature of 290 ° C. The discharge yarn was wound at 1000 m / min at a position of 2.5 m directly under the nozzle. The wound undrawn yarn was stretched by changing the stretching ratio to 80 ° C. in an oil bath, and heat-treated at 170 ° C. for 30 minutes under formal conditions.

The pressure value of the nozzle part at the time of discharge | release was 50 kgf / cm <2>, and the intrinsic viscosity of undrawn yarn was 0.70.

Table 3 shows the elongation, trimming frequency and actual strength during stretching when the stretching ratio is changed.

TABLE 3

* ○: Thread is not cut at all.

(Triangle | delta): Some threads are cut | disconnected.

Washing the unstretched yarn and the drawn yarn with carbon tetrachloride sufficiently was very soft to the touch, and there was no rough feeling inherent in polyester.

Comparative Example 2

The same operation as in Example 6 was performed without adding anything to 100 parts by weight of the polyester resin having an intrinsic viscosity of 1.0.

As a result, the ultimate viscosity of the tip cargo after melting was 0.85, the pressure of the nozzle portion at the time of discharge was 75 kgf / cm 2, and the ultimate viscosity of the undrawn yarn was 0.67.

Table 4 shows the trimming frequency and actual strength when the draw ratio is changed.

TABLE 4

* ○: Thread is not cut at all.

(Triangle | delta): Some threads are cut | disconnected.

X: The thread is almost cut.

There was an unpleasant feeling that the undrawn and drawn yarns were sufficiently washed with carbon tetrachloride.

From Example 6 and Comparative Example 2, the distearate pyromellitic acid diimide, which is a melt viscosity reducing agent for polyester resins of the present invention, has an effect of lowering the discharge pressure during spinning, and has a durable feel that does not change even when washed with carbon tetrachloride. It can be seen that there is an improvement in performance. Moreover, also in the stretching behavior, it was effective in reducing the elongation at the time of stretching to increase the stretching ratio, and it was found that the addition of the compound of the present invention did not deteriorate the actual strength.

Thus, it is estimated that the characteristic of the compound which concerns on this invention is based on showing the special orientation distribution in the system of this compound.

1 and 2 are X-ray photographs showing incineration X-ray scattering images of quadruple stretched yarn obtained in Comparative Example 2 and Example 6, respectively.

From Fig. 2, the yarn containing distearic pyromellitic acid diimide had a diffraction image oriented outside the polyester's original long period diffraction image. This peak, which corresponds to the plane spacing 47A, corresponds to the long period diffraction of the distearic pyromellitic acid diimide alone, and it became clear that the present compound was oriented and crystallized in the polyester fiber.

Example 7

In Example 6, the same experiment as in Example 6 was carried out using the compound shown in Table 5 instead of distearic pyromellitate diimide, and the nozzle pressure at the time of release, the intrinsic viscosity of the undrawn yarn, and the feel of the undrawn yarn were examined. . The results are shown in Table 5.

TABLE 5

Claims (7)

A method for producing a polyester fiber, comprising adding a compound represented by the formula (1), (2) or (3) to a polyester (a) containing ethylene terephthalate as a main repeating unit. (Wherein A ₁ and A ₂ are an alkyl group or an arylalkyl group having 6 to 18 carbon atoms, n is 0 or 1, and X is Any one of -S-, -SO _2- , or -O-. Here, R 1 and R 2 represent H or an alkyl group having 4 or less carbon atoms.) (Wherein R ₃ and R ₄ are each an alkyl group having 6 to 18 carbon atoms, l and m are integers in which l + m is 1 or more and 3 or less, and n and X are the same as above). (Wherein R ₅ and R ₆ represent a straight chain alkyl group having 12 to 22 carbon atoms.) The method according to claim 1, characterized in that it is added to the compound represented by the general formula (1) or (2) and melt-spun and then preheated and stretched to 60 to 100 ° C, and then heat treated under tension at 150 to 250 ° C. The manufacturing method of the polyester fiber. The method for producing a polyester fiber according to claim 1, wherein the raw polyester resin has an intrinsic viscosity of 0.8 or more at 25 ° C. in phenol / tetrachloroethane (60/40). The method for producing a polyester fiber according to claim 2, wherein the draw ratio is four times or more. It is obtained by the manufacturing method of Claim 1, The polyester fiber characterized by the above-mentioned. The polyester fiber of Claim 5 whose strength of the obtained polyester fiber is 7 g / d or more. It is a cationic salt obtained by the manufacturing method of Claim 1, The polyester fiber characterized by the above-mentioned.