JP5210856B2 - Method for producing vinyl chloride resin fiber - Google Patents

Description

The present invention relates to a manufacturing method of a vinyl chloride resin textiles having excellent thermal shrinkage hardly heat resistance.

  Conventionally, a vinyl chloride resin has been used in various applications as a typical general-purpose plastic because it is excellent in weather resistance, transparency, flame retardancy and chemical resistance and is inexpensive. The fiber is often used as a fiber for artificial hair such as hair wigs and doll hair because it is close to natural hair in strength, elongation, and feel.

  However, in order to further approximate natural hair, various fiber secondary processes are performed. As a result, there is a problem that heat shrinks more than necessary in a process such as a hair wig. As means for solving this problem, a vinyl chloride fiber composed of a vinyl chloride resin and a chlorinated vinyl chloride resin (see Patent Document 1) has been proposed. In this method, a large amount of chlorinated vinyl chloride resin is added. However, it was difficult to obtain a sufficient effect.

Furthermore, a vinyl chloride fiber (see Patent Document 2) to which two types of specific chlorinated vinyl chloride resins are added has been proposed. By this means, the amount of chlorinated vinyl chloride resin added can be increased, and thermal shrinkage at about 100 ° C. can be suppressed. However, in recent years, with the diversification and sophistication of the style of wigs for head ornaments, processing at higher temperatures has been required, and it has been difficult to cope with this means, and the processing characteristics have sometimes been inferior.
Japanese Patent Publication No. 60-18323 JP 2003-193329 A

An object of the present invention is to provide a method for producing textiles made of 100 ° C. thermal shrinkage hardly heat resistance even at a temperature higher than the superior vinyl chloride resin.

That is, the present invention has the following gist.
1. (A) mixing a vinyl chloride resin, and a resin composition containing 1 to 300 parts by weight of the crystallinity of the polylactic acid resin having a melting point of 100 to 300 ° C. with respect to 100 parts by weight of the salt of a vinyl resin Process,
(B) a step of melt spinning the resin composition from a spinning mold at a resin temperature of 150 to 200 ° C;
(C) a step of stretching the melt-spun fiber in an air atmosphere at a stretching treatment temperature of 30 to 150 ° C. in a stretching ratio of 2 to 20 times; and (d) a temperature of 80 to 200 ° C. of the stretched fiber. manufacturing method in the air atmosphere maintained, the vinyl chloride resin fibers you, comprising the step of thermal relaxation to its full length is a length of 99.8 to 50% of the pretreatment, the sequentially.
2. ^{2. The} method for producing a vinyl chloride resin fiber according to 1 above, wherein the cross-sectional area of one nozzle hole used in the melt spinning step is 3 mm ² or less.
3. 3. The method for producing a vinyl chloride resin fiber according to 1 or 2 above, wherein the single fineness of the vinyl chloride resin fiber is 1 to 200 dtex.
4). The manufacturing method of the vinyl chloride resin fiber in any one of said 1-3 whose viscosity average polymerization degree of a vinyl chloride resin is 600-2500.
5. The manufacturing method of the vinyl chloride-type resin fiber in any one of said 1-4 whose polylactic acid-type resin has a weight average molecular weight of 10,000-1 million .
6). 6. The method for producing a vinyl chloride resin fiber according to any one of 1 to 5 above, wherein the vinyl chloride resin fiber is for artificial hair .

  According to the present invention, vinyl chloride is suitable for hair decoration and artificial hair fibers because it has excellent heat resistance that does not easily shrink even at temperatures exceeding 100 ° C., has low gloss, and has little yarn breakage during melt spinning. A fiber made of a resin and a method for producing the same are provided.

The vinyl chloride resin fiber produced in the present invention is formed from a resin composition containing a vinyl chloride resin and 1 to 300 parts by mass of a polylactic acid resin with respect to 100 parts by mass of the vinyl chloride resin. Is done.

As the vinyl chloride resin used in the present invention, a resin obtained by bulk polymerization, solution polymerization, suspension polymerization, emulsion polymerization, etc. can be used. It is preferable to use what was manufactured.
The vinyl chloride resin is a homopolymer resin of vinyl chloride, which is a conventionally known homopolymer of vinyl chloride, or various conventionally known vinyl chloride copolymer resins, and is not particularly limited.

  A conventionally known copolymer resin can be used as the vinyl chloride copolymer resin. For example, vinyl chloride and vinyl ester copolymer resins such as vinyl chloride-vinyl acetate copolymer resin, vinyl chloride-vinyl propionate copolymer resin; vinyl chloride-butyl acrylate copolymer resin, vinyl chloride-2-ethylhexyl acrylate copolymer resin, etc. Typical examples include vinyl chloride and acrylate copolymer resins; vinyl chloride-ethylene copolymer resins, vinyl chloride-propylene copolymer resins and other vinyl chloride and olefin copolymer resins; vinyl chloride-acrylonitrile copolymer resins, etc. Is done. It is particularly preferable to use a homopolymer resin, a vinyl chloride-ethylene copolymer resin, a vinyl chloride-vinyl acetate copolymer resin or the like that is a homopolymer of vinyl chloride.

  In the vinyl chloride copolymer resin, the content of the comonomer is not particularly limited, and can be determined according to required quality such as moldability and yarn characteristics. The content of the comonomer is preferably 2 to 30% by mass, particularly preferably 2 to 20% by mass.

  600-2500 are preferable and, as for the viscosity average polymerization degree of the vinyl chloride-type resin used for this invention, 600-1800 are more preferable. When the viscosity average polymerization degree of the vinyl chloride resin is less than 600, the melt viscosity is lowered, so that the obtained fiber may be easily heat-shrinked. On the other hand, when the viscosity average degree of polymerization exceeds 2500, the melt viscosity becomes high, so that the nozzle pressure becomes high and it may be difficult to produce safely. The viscosity average degree of polymerization is a value calculated by JIS-K6720-2 by dissolving 200 mg of resin in 50 ml of nitrobenzene, measuring the specific viscosity of this polymer solution in a constant temperature bath at 30 ° C. using an Ubbelohde viscometer. It is.

The polylactic acid resin in the present invention has a melting point of 100 to 300 ° C., particularly preferably 120 to 250 ° C., most preferably 130 to 200 ° C. , and preferably has crystallinity. When the melting point of the polylactic acid resin is less than 100 ° C., the heat resistance of the obtained fiber may be inferior. On the other hand, when the melting point exceeds 300 ° C., mixing with the vinyl chloride resin may be difficult.
The melting point of the polylactic acid- based resin is a temperature at which the peak of the heat of fusion is obtained when a sample is heated at a heating rate of 10 ° C./min in nitrogen using a differential scanning calorimeter (DSC). This is a value calculated according to JISK-7121.

Preferred polylactic acid resin in the present invention, one common optical purity is low, the crystallinity of the polylactic acid resin is reduced to, in particular known that the melting point is lowered. For this reason, those containing 70% or more, preferably 80% or more, particularly preferably 90% or more of L-form are used.
The molecular weight of the polylactic acid-based resin used in the present invention is preferably 10,000 to 1,000,000, more preferably 20,000 to 750,000, particularly preferably as a weight average molecular weight in terms of standard polystyrene measured by gel permeation chromatography. 30,000 to 500,000. If the weight average molecular weight is small, the effect of improving the heat resistance of the resulting fiber is poor, and if it is large, mixing with the vinyl chloride resin may be difficult.

As a resin composition which forms the fiber of the present invention, 1 to 300 parts by mass, preferably 2 to 200 parts by mass, and particularly 2 to 200 parts by mass of polylactic acid resin with respect to 100 parts by mass of vinyl chloride resin and vinyl chloride resin. Preferably 5 to 150 parts by mass, and most preferably 10 to 100 parts by mass. When the polylactic acid resin is less than 1 part by mass, the heat resistance of the resulting fiber is poor. On the other hand, if the polylactic acid resin exceeds 300 parts by mass, the flame retardancy of the resulting fiber is poor.

In addition to the vinyl chloride resin and the polylactic acid resin, conventionally known additives used for the vinyl chloride resin depending on the purpose are mixed in the resin composition for fiber formation of the present invention. These additives are not particularly limited, but known additives are blended depending on the purpose. For example, lubricants, heat stabilizers, processing aids, reinforcing agents, UV absorbers, antioxidants, antistatic agents, fillers, flame retardants, pigments, initial color improvers, conductivity imparting agents, surface treatment agents, light There are stabilizers and fragrances.

Next, a method for producing the vinyl chloride resin fiber of the present invention will be described.
A resin composition containing a vinyl chloride resin, a polylactic acid resin, and, if necessary, an additive used in the production of the fiber of the present invention is a conventionally known mixer such as a Henschel mixer, a super mixer, It can be used as a powder compound formed by mixing using a ribbon blender or the like, or a pellet compound formed by melt-mixing this.

  The powder compound can be produced under conventionally known normal conditions. The pellet compound can be produced in the same manner as ordinary vinyl chloride pellets. For example, pellet compound using a kneader such as a single screw extruder, a different direction twin screw extruder, a conical twin screw extruder, a same direction twin screw extruder, a kneader, a planetary gear extruder, or a roll kneader. It can be.

  In the present invention, the resin composition is made into a fibrous undrawn yarn by a conventionally known spinning method. The spinning method is not particularly limited, but the melt spinning method is preferable. A conventionally known extruder can be used for melt spinning. For example, a single-screw extruder, a different-direction twin-screw extruder, a conical twin-screw extruder, etc. can be used. It is preferred to use a conical twin screw extruder.

In the present invention, melt spinning can be performed using a conventionally known nozzle. For example, a nozzle having a cross-sectional area of one nozzle hole of preferably 3 mm ² or less, more preferably 1 mm ² or less, particularly preferably 0.5 mm ² or less is attached to the tip of a die (spinning die) to perform melt spinning. It is preferred to do so. When the cross-sectional area of one nozzle hole exceeds 3 mm ² , it is necessary to apply an excessive tension in order to obtain an undrawn yarn having a fineness or a drawn yarn, and the yarn may break. The shape of the cross-sectional area of the nozzle hole is preferably a circular hollow shape, a glasses shape, a Y shape, or a C shape.

In the present invention, a multi-type nozzle hole formed by arranging a plurality of nozzle holes having a sectional area of 3 mm ² or less in a die on a die (the number of nozzle holes is preferably 50 to 500, the number of nozzle arrays Is preferably 1 to 5 rows), and it is preferable to produce an undrawn yarn having a single fineness of preferably 300 dtex or less by allowing the strands to flow out.
Specifically, an undrawn yarn is obtained by melt spinning a pellet compound of the resin composition at a resin temperature of preferably 150 to 200 ° C., more preferably 155 to 195 ° C., using, for example, a short screw extruder. be able to.

  The undrawn yarn obtained by melt spinning can be subjected to drawing treatment and heat treatment by a known method, so that a fiber (drawn yarn) having a fineness of preferably 600 dtex or less can be obtained. As the stretching treatment conditions, the stretching treatment temperature is preferably 30 to 150 ° C. In an air atmosphere maintained at a temperature of 30 to 150 ° C., the stretching ratio is preferably 2 to 20 times. In particular, the stretching treatment temperature is preferably 80 to 140 ° C., and the stretching ratio is preferably 2 to 10 times in an air atmosphere.

Furthermore, in an air atmosphere in which the drawn fiber is preferably kept at a temperature of 80 to 200 ° C., the total length of the fiber is preferably 99.8 to 50% before treatment, more preferably 99.8 to 70%. By performing the thermal relaxation treatment until it becomes, the thermal contraction rate can be reduced. The thermal relaxation treatment can be performed in conjunction with the stretching treatment or can be performed separately.
In the present invention, it is possible to freely combine and apply conventionally known techniques related to melt spinning, for example, techniques related to various nozzle cross-sectional shapes, techniques related to a heating cylinder, and techniques related to heat treatment. .

The unstretched yarn is subjected to a stretching treatment and a heat treatment, and the single fineness thereof is preferably 1 to 200 dtex, more preferably 5 to 150 dtex, and particularly preferably 10 to 100 dtex. Here, even if the fiber is thin or thick, it will deviate from the natural product, and the natural feeling is impaired.
The decitex is a value obtained by measuring the weight of 20 fibers having a length of 100 cm and multiplying the average weight per fiber by 10,000.
Although not particularly limited in the present invention, the above-mentioned fibers do not necessarily have a uniform fineness, and in some cases, a plurality of fibers having different single finenesses are mixed (blended) during or after spinning. It is also possible to do.

  Hereinafter, the present invention will be described in more detail based on examples, but the present invention should not be construed as being limited thereto.

Example 1
(A) 100 parts by mass of vinyl chloride resin (TH-1000 manufactured by Taiyo PVC Co., Ltd., viscosity average polymerization degree 1000) and 50 parts by mass of polylactic acid resin (Terramac TE-4000 manufactured by Unitika Ltd., melting point 170 ° C.), hydrotalcite 100 parts of a composite heat stabilizer (CP-410A, manufactured by Nissan Chemical Industries, Ltd.) and 0.75 parts by weight of an ester lubricant (EW-100, manufactured by Riken Vitamin Co., Ltd.) were mixed using a Henschel mixer. (B) The resin composition is obtained by using a spinning die having a round nozzle, a nozzle hole cross-sectional area of 0.05 mm ² , and a nozzle hole number of 180, A 40 mm single-screw extruder controlled at 175 to 185 ° C. was melt-spun at a mold temperature of 190 ° C. and an extrusion rate of 15 kg / hour to produce an undrawn yarn having an average fineness of 150 dtex. (C) a step of stretching the melt-spun fiber to 300% in an air atmosphere of 105 ° C., and (d) a total length of the fiber before treatment in an air atmosphere of 140 ° C. The step of heat-relaxing until it contracts to 75% of the length of the fiber was sequentially passed through to obtain a fiber having a single fineness of 65 dtex.

(Examples 2 to 10)
Fibers were obtained in the same manner as in Example 1 using the blending amounts of vinyl chloride resin and polyester resin shown in Table 1.

(Example 11)
A fiber was obtained in the same manner as in Example 1 except that the vinyl chloride resin was changed to a vinyl chloride resin having a low polymerization degree (TH-700, Taiyo PVC Co., Ltd., viscosity average polymerization degree 700).

(Example 12)
A fiber was obtained in the same manner as in Example 1 except that the vinyl chloride resin was changed to a vinyl chloride resin having a high degree of polymerization (TH-2000 manufactured by Taiyo PVC Co., Ltd., viscosity average polymerization degree 2000).

(Example 13)
The fiber was treated in the same manner as in Example 1 except that the vinyl chloride resin was changed to vinyl chloride-ethylene copolymer resin (E-1050 manufactured by Taiyo PVC Co., vinyl chloride content 98 mass%, viscosity average polymerization degree 1050). Obtained.

(Example 14)
A fiber is obtained in the same manner as in Example 1 except that the vinyl chloride resin is changed to a vinyl chloride-vinyl acetate copolymer resin (TV-800 manufactured by Taiyo PVC Co., Ltd., vinyl chloride content 93 mass%, viscosity average polymerization degree 780). Got.

(Comparative Example 1)
A fiber was obtained in the same manner as in Example 1 except that the polylactic acid resin was not included.

(Comparative Examples 2 and 3)
Fibers were obtained in the same procedure as in Example 1 using a chlorinated vinyl chloride resin (HA-24K manufactured by Sekisui Chemical Co., Ltd.) in place of the polylactic acid-based resin in the amount shown in Table 2.

The results of Examples 1 to 14 and Comparative Examples 1 to 3 are shown in Table 1 and Table 2, respectively.

  In Table 1, “spinnability” represents moldability when melt spinning the resin composition. In the spinnability test, when 120 fibers were simultaneously extruded from a spinning mold, the number of occurrences of yarn breakage of the fibers (measured by the phenomenon that several filaments were interrupted during melt extrusion) The time is 30 minutes, and the number of measurements is 3.)

  In Table 1, “heat shrinkage (%)” represents the heat shrinkage rate generated when the specimen is heat-treated. Specifically, twelve fiber specimens adjusted to a length of 100 mm were left in a gear oven at 130 ° C. for 15 minutes, and the ratio of the lengths of the specimens before and after being left ((length before leaving) -Length after standing) / Length before standing) × 100. Further, the numerical value is an average value of 10 out of 12 values excluding the maximum value and the minimum value.

In Table 1, “gloss” was evaluated by bundling 24,000 fibers and visually judging in a room exposed to direct sunlight and under a fluorescent lamp. The evaluation criteria are as follows.
Excellent: Smoothness and low gloss Good: Low smoothness but low gloss Possible: Unevenness and low gloss or smooth and slightly glossy Defect: Large unevenness or Strong gloss

  As is apparent from Tables 1 and 2, according to the present invention, it is understood that fibers having excellent heat shrinkability, low gloss, and few yarn breakage during melt spinning can be easily obtained.

The fiber obtained using the resin composition of the present invention is suitable for, for example, clothing textile products such as underwear and socks, life-related textile products such as rugs, curtains and towels, especially for hair decoration and artificial hair fibers. Can be used.

The entire contents of the specification, claims, and abstract of Japanese Patent Application No. 2006-051859 filed on February 28, 2006 are incorporated herein as the disclosure of the specification of the present invention. Is.

Claims (6)

(A). 1 to a vinyl chloride resin, and has a melting point of 100 to 300 ° C. with respect to 100 parts by weight of said salt of vinyl resin, and a crystalline polylactic acid resin having 70% or more L-form Mixing the resin composition containing 300 parts by mass;
(B) a step of melt spinning the resin composition from a spinning mold at a resin temperature of 150 to 200 ° C;
(C) a step of stretching the melt-spun fiber in an air atmosphere at a stretching treatment temperature of 30 to 150 ° C. in a stretching ratio of 2 to 20 times; and (d) a temperature of 80 to 200 ° C. of the stretched fiber. manufacturing method in the air atmosphere maintained, the vinyl chloride resin fibers you, comprising the step of thermal relaxation until the fiber total length is the length of 99.8 to 50% of the pretreatment, the sequentially. One of the cross-sectional area of the nozzle holes used in the step of melt spinning is 3 mm ² or less, the production method of vinyl resin fibers chloride according to claim 1. The method for producing a vinyl chloride resin fiber according to claim 1 or 2, wherein the single fineness of the vinyl chloride resin fiber is 1 to 200 dtex. The manufacturing method of the vinyl chloride resin fiber in any one of Claims 1-3 whose viscosity average polymerization degree of a vinyl chloride resin is 600-2500. The method for producing a vinyl chloride resin fiber according to any one of claims 1 to 4, wherein the polylactic acid resin has a weight average molecular weight of 10,000 to 1,000,000. The method for producing a vinyl chloride resin fiber according to any one of claims 1 to 5, wherein the vinyl chloride resin fiber is for artificial hair.