JP3539053B2 - Masterbatch and manufacturing method thereof - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a thermoplastic resin containing polyvinylpyrrolidone, and more particularly, to a thermoplastic resin containing polyvinylpyrrolidone, which has a good yellowness and a good spinning property when producing highly hygroscopic fibers. The present invention relates to a masterbatch and a manufacturing method thereof.

[0002]

2. Description of the Related Art Natural fibers typified by cotton and wool are preferred for their texture and good comfort such as no feeling of discomfort. The main factor in this comfortable wearing feeling is that the natural fibers have a moderate hygroscopicity. However, natural fibers lack esthetics such as suppleness, drapeability, and glossiness, and are not sufficient in smooth surface touch, abrasion resistance, strength, and the like.

On the other hand, synthetic fibers typified by polyamide fibers have strength, flexibility, drapability, glossiness,
It has excellent properties such as color developability, dyeing fastness, abrasion resistance, and softness, and is favorably used for textile products for clothing such as innerwear, sportswear, pantyhose and the like.

[0004]

However, synthetic fibers such as polyamide fibers and polyester fibers have excellent properties such as strength and dyeing fastness, but are inferior in hygroscopicity to natural fibers. For this reason, the water vapor generated by wearing is not sufficiently absorbed to be released to the outside of the clothes, and the stuffiness at the time of high temperature and high humidity in summer is unpleasant. Polyamide fibers have a higher equilibrium moisture content (moisture absorption under standard conditions) than polyester fibers, but are still insufficient from the viewpoint of comfortable wearing. For this reason, various attempts have been made to improve the moisture absorption properties of polyamide fibers.

For example, JP-A-56-24426 discloses a method for producing a hygroscopic polyamide fiber by improving the hygroscopic property of the polyamide fiber by graft polymerization. However, the hygroscopic polyamide fiber obtained by the graft polymerization has a drawback that the dyeability is significantly reduced, no deep dyeing is obtained, and the durability by washing is poor.

In Japanese Patent Publication No. 55-4852,
There is disclosed a method for producing a polyvinylpyrrolidone-containing hygroscopic polyamide fiber with good spinnability by employing a specific spinning method. However, when a polyvinylpyrrolidone is used to form a hygroscopic polyamide fiber, it is difficult to obtain a fiber having good whiteness, and there has been a problem from an aesthetic point of view for use in clothing.

Japanese Patent Application Laid-Open No. 7-150414 discloses a hygroscopic polyamide fiber containing polyvinylpyrrolidone and polyetheramide and / or polyetheresteramide in nylon. But,
Although the target moisture absorption properties can be obtained, there is a problem that many yarn breaks occur when producing ultrafine yarns or highly deformed yarns, and stable production cannot be performed.

Further, JP-A-7-150415 discloses a hygroscopic polyamide having good whiteness by using polyvinylpyrrolidone and a reducing agent. However, the yellowness before dyeing was unsatisfactory, and in addition,
There has been a problem that when yarns such as ultrafine yarns and highly deformed yarns are produced, there are many yarn breaks, and the productivity is not sufficiently satisfactory.

As described above, the present inventor has solved the above-mentioned drawbacks of the prior art, does not impair the excellent characteristics inherent in synthetic fibers, has a good yellowness, has excellent hygroscopicity, and has excellent dyeing properties. -It is an object of the present invention not only to provide good washing durability, but also to obtain a means for extremely stably and efficiently producing extra fine yarns and highly deformed yarns.

[0010]

That is, the present invention relates to a masterbatch containing a thermoplastic resin and polyvinylpyrrolidone, wherein the relative viscosity according to JIS K6810 is in the range of the following formula I.

Ηr ≦ 0.01C + 2.50 (I) (In the formula I, ηr is a relative viscosity, and C is an amount (% by weight) of polyvinylpyrrolidone in the masterbatch.)
And "A method for obtaining fibers by mixing the masterbatch and thermoplastic resin pellets and then spinning."
Consists of

[0012]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in detail.
In the present invention, “weight” means “mass”.

The thermoplastic resin blended in the masterbatch of the present invention includes polyamide resin, polyester resin, polyolefin resin, etc. Among them, the characteristics are particularly excellent for use in clothing, and polyvinylpyrrolidone itself is a gel at high temperatures. A polyamide resin having a low spinning temperature is preferred because it has a property of easily forming.

As the polyamide resin, JIS K68
Method 10: 1% using 98% concentrated sulfuric acid as a solvent
(G / dl) It is preferable that the solution has a relative viscosity at 25 ° C. (hereinafter referred to as a relative viscosity) of 2.00 or more and 3.20 or less.
If the sulfuric acid relative viscosity is less than 2.00 or more than 3.20, the spinnability becomes very poor.

The masterbatch of the present invention requires that the relative viscosity of the masterbatch satisfy (I). ηr ≦ 0.01C + 2.50 (I) (In the formula I, ηr indicates the relative viscosity, and C indicates the amount (% by weight) of polyvinylpyrrolidone in the masterbatch.) The relative viscosity in (I) indicates the heat of the masterbatch. The resin may be dissolved in a solvent in which the plastic resin is soluble, and the relative viscosity at 25 ° C. at a concentration of 1 g / dl may be determined as specified in JIS K6810. For polyamide, 98% sulfuric acid is used as the solvent.

If the relative viscosity of the masterbatch deviates from the value obtained from the above equation, the number of yarn breakage increases and the spinnability deteriorates extremely. Further, ηr in the formula I is preferably 1.6 or more. If it is low, the difference in melt viscosity from the thermoplastic resin pellets to be blended during spinning becomes too large, and the concentration of polyvinylpyrrolidone in the yarn tends to be uneven, and the yarn breakage tends to increase.

As a method for producing the masterbatch of the present invention, a method of kneading polyvinylpyrrolidone and a thermoplastic resin is preferable, and an extruder is preferably used because strong kneading can be performed as an apparatus. The temperature at the time of kneading may be any temperature as long as it is equal to or higher than the softening temperature of the resin, and heating from outside the extruder or heat generated by shearing the resin by a screw may be used.

In order to satisfy the relative viscosity specified in the present invention, the polyvinylpyrrolidone-containing master batch of the present invention is preferably kneaded with polyvinylpyrrolidone and a thermoplastic resin at a pressure lower than the atmospheric pressure, that is, under reduced pressure. An extruder is preferably used for this purpose. As an example of the method of reducing the pressure, a method of reducing the pressure from a vent port of an extruder using a vacuum pump can be used.

When kneaded at atmospheric pressure or higher, the resulting polyvinylpyrrolidone masterbatch has a yellowness (hereinafter referred to as YI value) of 50 or more measured by a color meter, and the melt-spun yarn has a poor whiteness and is extremely unsuitable. Besides
During spinning, yarn breakage frequently occurs, and productivity is deteriorated.

The degree of decompression of the melt kneading is 88 k in absolute pressure.
Pa or less, more preferably 50 kPa or less.

In the present invention, the concentration of polyvinylpyrrolidone in the masterbatch is preferably from 10 to 50% by weight. If the content is less than 10% by weight, the chance of producing a masterbatch increases, and the energy consumption of electricity and the like tends to increase. On the other hand, if it exceeds 50% by weight, polyvinylpyrrolidone tends to gel, and the stability to melt kneading for the production of a master batch tends to be poor.

The masterbatch of the present invention may contain known additives such as a light fastener, an antistatic agent, a flame retardant, and a matting agent.

The polyvinylpyrrolidone used in the present invention may be a commercially available polyvinylpyrrolidone. However, the content of pyrrolidone as a by-product at the time of production is 0.1% based on polyvinylpyrrolidone in the master pellet. % By weight or less is preferred.

When polyvinylpyrrolidone having a pyrrolidone content exceeding 0.1% by weight is kneaded with a thermoplastic resin,
The I value becomes 50 or more, and the spinnability is remarkably deteriorated due to yarn breakage, making the material extremely unsuitable as a master batch.

[0025] The polyvinylpyrrolidone may be produced under any production conditions, but a K value of 20 or more and 60 or less is preferable as an index of the molecular weight.

The K value is a value determined from the relative viscosity of the aqueous solution, and can be calculated from the Fikenscher equation according to the following equation.

(Equation 1) Z: relative viscosity of the aqueous solution having a concentration C k: K value × 10 ⁻³ C: aqueous solution concentration (W / V%)

When the K value is small, that is, when the molecular weight is small, the entanglement with the thermoplastic resin during kneading is weak.
Polyvinylpyrrolidone elutes during the cooling of the gut after kneading. On the other hand, if the K value is large, the viscosity increases, and it becomes difficult to discharge after melt-kneading.

The resulting polyvinylpyrrolidone-containing masterbatch is pellet-blended with thermoplastic resin pellets and melt-spun into fibers by a conventional method. As the thermoplastic resin, those described for the master batch are exemplified, and polyamide is particularly preferably used.

[0029]

The present invention will be described in more detail with reference to the following examples. Various characteristic values measured in the following examples were measured according to the following measurement methods. <Relative viscosity of sulfuric acid> The relative viscosity of sulfuric acid is based on JIS K6810.
1 g of the sample was dissolved in 100 ml of 98% sulfuric acid, and the relative viscosity at 25 ° C. was measured. <Yellowness> The yellowness was measured by filling a master pellet into a cylindrical resin container using a color computer SM-3 manufactured by Suga Test Instruments Co., Ltd., and measuring the YI indicating the yellowness. The lower the YI, the higher the whiteness, and the better the whiteness when made into yarn. <Yarn-forming property> Nylon 6 pellets and polyvinylpyrrolidone master pellets are blended by a rotary vacuum dryer so that the polyvinylpyrrolidone concentration becomes 7% by weight, dried by a usual method, and then melted at 270 ° C. The liquid is discharged from the Y-hole of the hole, and the spinning speed is 1300 m / min.
A multifilament having a degree of deformation of 2.6, 30 denier, and 13 filaments was obtained by a direct spin drawing method at a draw ratio of 2.3 times and a winding speed of 3000 m / min.

Table 1 shows the results of each embodiment and comparative examples.

[Example 1] Polyvinylpyrrolidone having a K value of 30 (rubiscol K30 special grade manufactured by BASF: hereinafter referred to as K30sp) was extruded (φ3).
0, 2 and 2 axes), kneaded with nylon 6 having a relative viscosity of sulfuric acid of 2.16 at a barrel temperature of 230 ° C., extruded in a gut shape, cooled and pelletized to obtain a polyvinylpyrrolidone concentration of 10, 20, Master pellets of 30 and 40% by weight were prepared (Experiments Nos. 1-4, 12, and 13). At this time, the pressure was reduced to 60 kPa or less from a vent port by a vacuum pump. The pyrrolidone content in the pellets was 0.02% based on polyvinyl pyrrolidone.

The relationship between the relative viscosity of sulfuric acid and the concentration of polyvinylpyrrolidone in the obtained master pellets satisfied the formula I, and both the yellowness and the spinnability were good.

[0033]

[Table 1]

Example 2 A master pellet having a polyvinylpyrrolidone concentration of 30% by weight was prepared in the same manner as in Example 1 except that the relative viscosity of sulfuric acid of nylon 6 was changed to 2.61 (Experiment No. 5).

The relationship between the relative viscosity of sulfuric acid and the concentration of polyvinylpyrrolidone in the obtained master pellets satisfied the formula I, and both the yellowness and the spinnability were good.

Example 3 A master pellet having a polyvinylpyrrolidone concentration of 30% by weight or 40% by weight was prepared in the same manner as in Example 1 except that the relative viscosity of sulfuric acid of nylon 6 was changed to 2.80 (Experiment No. 6). , 7).

The relationship between the relative viscosity of sulfuric acid and the concentration of polyvinylpyrrolidone in the obtained master pellets satisfied the formula I, and both the yellowness and the spinnability were good.

Comparative Example 1 A master pellet having a polyvinylpyrrolidone concentration of 20% by weight was prepared in the same manner as in Example 1 without depressurization (Experiment No. 8).

The obtained master pellets did not satisfy the formula I, and neither the yellowness nor the spinning property was at a satisfactory level.

Comparative Example 2 A master pellet having a polyvinylpyrrolidone concentration of 30% by weight was prepared in the same manner as in Example 2 without depressurizing (Experiment No. 9).

The obtained master pellets did not satisfy the formula I, and the yellowness and the spinnability were not at satisfactory levels.

[Comparative Example 3] Polyvinylpyrrolidone was changed to polyvinylpyrrolidone having a K value of 30 (normal grade of Luviscol K30 manufactured by BASF: hereinafter referred to as K30).
Using an extruder (φ30, double, biaxial), kneaded with nylon 6 having a sulfuric acid relative viscosity of 2.16 at a barrel temperature of 230 ° C., extruded in a gut shape, cooled, and pelletized to obtain a polyvinyl pyrrolidone concentration of 10%. , 20, 4
The master pellet was 0% by weight. At this time, the pressure was reduced to 60 kPa or less by a vacuum pump from the vent port (Experiment N
o. 10-12). The pyrrolidone content in polyvinylpyrrolidone was 0.15%.

The relative viscosity of sulfuric acid of the obtained master pellet was larger than the range obtained by calculation, and the yellowness and the spinning property were not at satisfactory levels.

Comparative Example 4 A master pellet having a polyvinylpyrrolidone concentration of 20% by weight was obtained in the same manner as in Comparative Example 3 without depressurizing (Experiment No. 13).

The relative viscosity of sulfuric acid of the obtained master pellet was larger than the range determined by calculation, and neither the yellowness nor the spinning property was at a satisfactory level.

Table 1 summarizes the yellowness and the spinnability of the master pellets obtained in Examples and Comparative Examples. In the table, polyvinylpyrrolidone is indicated as PVP.

[0047]

By using a masterbatch having the characteristics of the present invention, fibers can be produced with excellent whiteness (no yellowness) and excellent yarnmaking properties.

Continuation of front page (56) References JP-A-9-188917 (JP, A) JP-A-7-150414 (JP, A) JP-A-7-150415 (JP, A) JP-A-8-113688 (JP) JP-A-50-148625 (JP, A) JP-A-50-148626 (JP, A) (58) Fields investigated (Int. Cl. ⁷ , DB name) C08L 39/06 C08L 77/00 D01F 6/90

Claims (7)

(57) [Claims] 1. A master batch containing a thermoplastic resin and polyvinylpyrrolidone, wherein the master batch is JIS K68.
A masterbatch whose relative viscosity according to 10 is in the range of formula I below. ηr ≦ 0.01C + 2.50 (I) (In the formula I, ηr indicates relative viscosity, and C indicates the amount (% by weight) of polyvinylpyrrolidone in the masterbatch.) 2. The master batch according to claim 1, wherein the thermoplastic resin is a polyamide. 3. The masterbatch according to claim 1, wherein the amount of pyrrolidone present as an impurity is 0.1% by weight or less based on polyvinylpyrrolidone. 4. The method for producing a master batch according to claim 1, wherein the polyvinylpyrrolidone and the thermoplastic resin are kneaded under a pressure lower than the atmospheric pressure. 5. The method for producing a master batch according to claim 4, wherein the kneading is performed by using an extruder at a temperature equal to or higher than the softening point of the thermoplastic resin. 6. A method for producing a fiber, comprising mixing the masterbatch according to claim 1 and thermoplastic resin pellets and then spinning. 7. A method for producing polyamide fibers, comprising mixing the masterbatch according to claim 2 and polyamide pellets and then spinning.