KR20080083643A - Vinyl chloride resin fiber and method for producing same - Google Patents

Abstract

Disclosed is a fiber made of a vinyl chloride resin, which is excellent in heat resistance and thus hardly shrinks thermally even at a temperature higher than 100°C. Specifically disclosed is a fiber obtained by melt-spinning a resin composition containing a vinyl chloride resin and 1-300 parts by mass of a polyester resin per 100 parts by mass of the vinyl chloride resin. The vinyl chloride resin has a viscosity-average polymerization degree of 600-2500. The polyester resin is composed of a polylactic acid resin, and has a melting point of 100-300°C.

Description

Vinyl chloride resin fiber and its manufacturing method {VINYL CHLORIDE RESIN FIBER AND METHOD FOR PRODUCING SAME}

The present invention relates to a vinyl chloride resin fiber that is difficult to heat shrink and excellent in heat resistance, and a method for producing the same.

Conventionally, vinyl chloride-based resins have been used for various applications as typical general-purpose plastics because of their excellent weather resistance, transparency, flame retardancy, and chemical resistance and low cost. Since the fiber is close to natural hair in strength, elongation, texture, and the like, it is often used as an artificial hair fiber such as a hair wig or a doll hair.

However, various fiber secondary processing is carried out to bring it closer to natural hair, but as a result, there is a problem that heat shrinkage is more than necessary in a processing step such as a hair wig. As a means to solve this problem, a vinyl chloride-based fiber (see Patent Document 1) composed of a vinyl chloride resin and a chlorinated vinyl chloride resin has been proposed, but it is difficult to add a large amount of chlorinated vinyl chloride resin by this method, and thus a sufficient effect is obtained. I could not get it.

Moreover, the vinyl chloride type fiber (refer patent document 2) which added two types of specific chlorinated vinyl chloride resins is proposed. By this means, the addition amount of the chlorinated vinyl chloride resin can be increased, and it becomes possible to suppress heat shrinkage at about 100 ° C. However, in recent years, processing at higher temperatures is required by diversification and advancement of wig styles for hair ornaments, and it is difficult to cope with the above-mentioned means, resulting in poor processing characteristics.

Patent Document 1: Japanese Unexamined Patent Application Publication No. 60-18323

Patent Document 2: Japanese Patent Application Laid-Open No. 2003-193329

Challenges the invention seeks to solve

An object of the present invention is to provide a fiber made of a vinyl chloride-based resin that is difficult to heat shrink even at a temperature exceeding 100 ° C. and excellent in heat resistance, and a method of manufacturing the same.

Means to solve the problem

That is, this invention has the following summary.

(1) A vinyl chloride-based resin fiber comprising a molten spun fiber of a resin composition containing 1 to 300 parts by weight of a polyester resin with respect to 100 parts by weight of a vinyl chloride-based resin and the vinyl chloride-based resin.

(2) The vinyl chloride resin fiber according to the above (1), wherein the vinyl chloride resin has a viscosity average degree of polymerization of 600 to 2,500.

(3) The vinyl chloride resin fiber according to the above (1) or (2), wherein the melting point of the polyester resin is 100 to 300 ° C.

(4) The vinyl chloride resin fiber according to any one of the above (1) to (3), wherein the polyester resin is a polylactic acid resin.

(5) The vinyl chloride resin fiber according to any one of (1) to (4), wherein the fiber has a single fineness of 1 to 200 decitex.

(6) Artificial hair which consists of vinyl chloride type resin fiber in any one of said (1)-(5).

(7) (a) mixing a resin composition containing a vinyl chloride resin and a polyester resin;

(b) melt spinning the resin composition at a resin temperature of 150 to 200 캜 from a spinning die;

(c) drawing the melt-spun fibers at a draw ratio of 2 to 20 times in an air atmosphere at a draw processing temperature of 30 to 150 ° C;

(d) Vinyl chloride-based resin fibers having a step of thermally relaxing the fiber until the total length of the fiber becomes 99.8 to 50% before treatment in an air atmosphere maintained at the temperature of 80 to 200 ° C. Method of preparation.

(8) The manufacturing method of the vinyl chloride resin fiber as described in said (7) whose one cross-sectional area of the nozzle hole used at the said process of melt spinning is 3 mm <2> or less.

Effects of the Invention

According to the present invention, since it is difficult to heat shrink even at a temperature exceeding 100 ° C, has excellent heat resistance, less gloss, and less thread breakage during melt spinning, it is made of a vinyl chloride-based resin which is very suitable for hair decoration or fiber for artificial hair. Fibers and methods of making the same are provided.

Implement the invention  Preferred form for

The fiber made of the vinyl chloride resin of the present invention is formed from a resin composition containing 1 to 300 parts by weight of a polyester resin with respect to 100 parts by weight of the vinyl chloride resin and the vinyl chloride resin.

The vinyl chloride resin used in the present invention may be a resin obtained by bulk polymerization, solution polymerization, suspension polymerization, emulsion polymerization, or the like. However, it is preferable to use a resin produced by suspension polymerization in consideration of initial coloring properties of fibers. .

The vinyl chloride-based resin is a homopolymer resin of vinyl chloride which is a conventionally known vinyl chloride homopolymer or various conventionally known vinyl chloride copolymer resins, and is not particularly limited.

As the vinyl chloride copolymer resin, a conventionally known copolymer resin can be used. For example, copolymer resin of vinyl chloride and vinyl esters, such as a vinyl chloride vinyl acetate copolymer resin and a vinyl chloride vinyl propionate copolymer resin; Copolymer resins of vinyl chloride and acrylic acid esters such as vinyl chloride-butyl acrylate copolymer resin and vinyl chloride- 2-ethylhexyl copolymer resin; Copolymer resins of vinyl chloride and olefins such as vinyl chloride-ethylene copolymer resin and vinyl chloride-propylene copolymer resin; Vinyl chloride-acrylonitrile copolymer resin and the like are representatively exemplified. Especially preferably, it is preferable to use a homopolymer resin, a vinyl chloride-ethylene copolymer resin, a vinyl chloride-vinyl acetate copolymer resin, etc. which are homopolymers of vinyl chloride.

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

600-2,500 are preferable and, as for the viscosity average polymerization degree of the vinyl chloride type resin used for this invention, 600-1,800 are more preferable. If the viscosity average polymerization degree of vinyl chloride-type resin is less than 600, since melt viscosity falls, there exists a possibility that the fiber obtained may become easy to heat shrink. On the other hand, when the viscosity average polymerization degree exceeds 2,500, since melt viscosity becomes high, there exists a possibility that a nozzle pressure may become high and safe manufacture may become difficult. In addition, the viscosity average polymerization degree melt | dissolves 200 mg of resin in 50 ml of nitrobenzene, The specific viscosity of this polymer solution is measured in a 30 degreeC thermostat using a Uberode type viscometer, and it measures by JIS-K6720-2. It is the calculated value.

Polyester-based resin used by this invention is aromatic polyester-based resin, such as polyethylene terephthalate, polymethylene terephthalate, polybutylene terephthalate, and polyethylene naphthalate; Polylactic acid, polyhydroxy butyric acid, polycaprolactone, polybutylene succinate, polybutylene adipate, polyethylene succinate, polyglycolic acid, poly-3-hydroxy propionate, poly-3-hydroxy butyrate Aliphatic polyester resins, such as these, etc. are mentioned.

Moreover, the said polyester resin also contains the copolymer of polyester resin shown above, the block or graft polymer of polyester resin, and also the blended thing with another resin. Especially, although it does not specifically limit, From a viewpoint of mixing property with vinyl chloride-type resin, aliphatic polyester resin is preferable and polylactic acid-type resin is especially preferable.

As for the polyester resin in this invention, melting | fusing point becomes like this. Preferably it is 100-300 degreeC, Especially preferably, it is 120-250 degreeC, Most preferably, it is 130-200 degreeC, It is preferable to use what has crystallinity. When melting | fusing point of polyester-type resin is less than 100 degreeC, the heat resistance of the fiber obtained may be inferior. On the other hand, when melting | fusing point exceeds 300 degreeC, mixing with vinyl chloride-type resin may become difficult.

The melting point of the polyester resin refers to the temperature at which the amount of heat of fusion becomes peak when the sample is heated to about 5 mg in nitrogen at a heating rate of 10 ° C./min using a differential scanning calorimeter (DSC). The value calculated by

Preferable polylactic acid-based resin in the present invention is not particularly limited. Generally, when the optical purity of polylactic acid-type resin is low, it is known that crystallinity falls and especially melting point falls. For this reason, what contains L body 70% or more, Preferably it is 80% or more, Especially preferably, 90% or more is used.

The molecular weight of the polylactic acid-based resin used in the present invention is preferably a weight average molecular weight in terms of standard polystyrene measured by gel permeation chromatography, preferably 10,000 to 1 million, more preferably 20,000 to 750,000, particularly preferred. It is 30,000-500,000. If the weight average molecular weight is small, the effect of improving the heat resistance of the fiber obtained is insufficient, and if it is large, mixing with the vinyl chloride resin may be difficult.

As the resin composition for forming the fibers of the present invention, 1 to 300 parts by weight of polyester resin, preferably 2 to 200 parts by weight, particularly preferably 100% by weight of vinyl chloride resin and 100 parts by weight of vinyl chloride resin. 5 to 150 parts by weight, most preferably 10 to 100 parts by weight. When polyester-based resin is less than 1 weight part, the heat resistance of the fiber obtained will be inferior. On the other hand, when polyester-based resin exceeds 300 weight part, the flame retardance of the fiber obtained is inferior.

In addition to the vinyl chloride-based resin and the polyester-based resin, conventionally known additives used for the vinyl chloride-based resin according to the purpose are mixed with the resin composition for forming a fiber of the present invention. Although such an additive is not specifically limited, A well-known additive is mix | blended according to the objective. For example, lubricants, heat stabilizers, processing aids, reinforcing agents, ultraviolet absorbers, antioxidants, antistatic agents, fillers, flame retardants, pigments, initial color improvers, conductive additives, surface treatment agents, light stabilizers, fragrances and the like.

Next, the manufacturing method of the vinyl chloride resin fiber of this invention is demonstrated.

The resin composition which contains the vinyl chloride type resin, polyester resin, and the additive as needed with the additive of the fiber of this invention is a conventionally well-known mixer, for example, a Henschel mixer, a super mixer, and a ribbon. It can be used as a powder compound made by mixing using a blender or the like or a pellet compound made by melting and mixing it.

Powder compound can be manufactured on conventionally well-known normal conditions. The pellet compound can be produced in the same manner as in the production of ordinary vinyl chloride pellets. For example, pellets may be used using kneaders such as single screw extruders, biaxial extruders in different directions, conical twin screw extruders, coaxial twin screw extruders, cokneaders, planetary gear extruders, roll kneaders, and the like. You can do it in compound.

In this invention, making the said resin composition into a fibrous undrawn yarn is performed by the conventionally well-known spinning method. The spinning method is not particularly limited, but a melt spinning method is preferable. When performing melt spinning, a conventionally known extruder can be used. For example, a single screw extruder, a different direction twin screw extruder, a conical twin screw extruder, etc. can be used, but especially a single screw extruder having a diameter of about 35 to 200 mm or a diameter of preferably about 35 to 150 mm is preferred. Preference is given to using conical twin screw extruders.

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

In the present invention, a multi-type nozzle hole formed by arranging a plurality of nozzle holes having a cross-sectional area of 3 mm 2 or less in one nozzle hole on a die (the number of nozzle holes is preferably 50 to 500, and the number of nozzle arrangements is preferably It is preferable to produce unstretched yarn having a single fineness of 300 decitex or less, by causing strands to flow out from the column).

Specifically, the unstretched yarn can be obtained by melt spinning the resin compound at a temperature of preferably from 150 to 200 ° C, more preferably from 155 to 195 ° C, using, for example, a pellet compound of the resin composition.

The unstretched yarn obtained by the melt spinning is subjected to a stretching treatment and a heat treatment by a known method, and it is possible to obtain fine-fiber fibers (stretched yarn) of preferably 600 decitex or less. As extending | stretching process conditions, it is preferable to extend | stretch a draw ratio 2 to 20 times preferably in the air atmosphere in which extending | stretching process temperature was maintained at the temperature of 30-150 degreeC preferably. In particular, the stretching ratio is preferably 2 to 10 times in an air atmosphere where the stretching treatment temperature is preferably 80 to 140 ° C.

Further, under the air atmosphere in which the stretched fiber is preferably maintained at a temperature of 80 to 200 ° C., the total length of the fiber is preferably 99.8 to 50%, more preferably 99.8 to 70% before the treatment. The thermal contraction rate can reduce the thermal contraction rate. The heat relaxation treatment may be carried out in conjunction with the stretching treatment, or may be performed separately.

In addition, in the present invention, it is possible to freely combine a technique related to conventionally known melt spinning, for example, a technique related to various nozzle cross-sectional shapes, a technique related to a heating tube, a technique related to heat treatment, and the like.

The fibers subjected to the stretching and heat treatment of the unstretched yarn preferably have a single fineness of 1 to 200 decitex, more preferably 5 to 150 decitex, particularly preferably 10 to 100. It is a decitex. Here, even if the fiber is thin or thick, it is separated from the natural product and the natural feeling is damaged.

A decitex is the value which measured the weight of 20 fibers (bones) of length 100cm, and made the average weight per 10,000 (bones) 10,000 times.

Although it does not specifically limit in this invention, The said fiber does not necessarily need to be uniform in single fineness, In some cases, it is also possible to mix (blend) and use several fibers with different single fineness in a spinning process or after spinning. 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 weight of a vinyl chloride resin (TH-1000 made by TAIYO VINYL CORPORATION, a viscosity average degree of polymerization of 1,000) and 50 parts by weight of a polylactic acid-based resin (Termac TE-4000 manufactured by Unitica, melting point 170 ° C) , A mixture containing 1 part by weight of a hydrotalcite complex thermal stabilizer (CP-410A manufactured by Nissan Chemical Co., Ltd.), and 0.75 part by weight of an ester lubricant (EW-100 manufactured by Riken Vitamin Co., Ltd.) using a Henschel mixer A 40 mm single screw extruder controlled at 175 to 185 ° C using a step of raising the temperature by stirring to a temperature to obtain a resin composition, and (b) the resin composition using an annular nozzle, a nozzle hole cross-sectional area of 0.05 mm 2, and a spinneret having 180 nozzle holes. To melt spinning at a mold temperature of 190 ° C. and an extrusion amount of 15 kg / hr to obtain undrawn yarn with an average fineness of 150 decitex, and (c) to stretch the melt-spun fibers to 300% in an air atmosphere at 105 ° C. And (d) said stretched Through a process of thermal relaxation treatment until the entire length of the fiber is contracted to a length of 75% prior to treatment in the air atmosphere at 140 ℃ oil in order to obtain a single fineness of 65 decitex fibers.

(Examples 2 to 10)

Fibers were obtained in the same manner as in Example 1 using the compounding amounts of the vinyl chloride resin and the 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 low vinyl chloride resin (TH-700 manufactured by Ocean Salt Co., Ltd., viscosity average polymerization degree 700).

(Example 12)

Fibers were obtained in the same manner as in Example 1 except that the vinyl chloride-based resin was changed to a vinyl chloride resin having high polymerization degree (TH-2000 manufactured by Ocean Salt Co., Ltd., viscosity average polymerization degree 2000).

(Example 13)

A fiber was obtained in the same manner as in Example 1 except that the vinyl chloride resin was changed to a vinyl chloride-ethylene copolymer resin (E-1050 manufactured by Ocean Salts Co., Ltd., 98 wt% of vinyl chloride content, viscosity average degree of polymerization 1050).

(Example 14)

Fibers were obtained in the same manner as in Example 1 except that the vinyl chloride-based resin was changed to a vinyl chloride-vinyl acetate copolymer resin (TV-800 manufactured by Ocean Salts Co., Ltd., 93 wt% of vinyl chloride, viscosity average degree of polymerization 780).

(Example 15)

The fiber was obtained like Example 1 except having changed polylactic acid-type resin into crystalline polyester resin (Byron GM-925 by Toyo Spinning Co., Ltd., melting point 166 degreeC).

(Example 16)

Fibers were obtained in the same manner as in Example 1 except that the polylactic acid resin was changed to crystalline polyester resin (Byron GA-5410 manufactured by Toyo Spinning Co., Ltd., melting point 117 ° C).

(Comparative Example 1)

Fibers were obtained in the same manner as in Example 1 except that no polylactic acid-based resin was included.

(Comparative Example 2 and Comparative Example 3)

The fiber was obtained in the same procedure as Example 1 using the compounding quantity shown in Table 2 instead of polylactic acid-type resin, chlorinated vinyl chloride resin (HA-24K by Sekisui Chemical Co., Ltd.).

The results of Examples 1 to 16 and Comparative Examples 1 to 3 are summarized in Table 1 and Table 2, respectively.

In Table 1, "radioactivity" shows the moldability at the time of melt-spinning a resin composition. In the radioactivity test, the number of yarn breakage occurrences of the fibers when 120 (bones) fibers were simultaneously extruded from a spinning die (measured by the phenomenon of breaking several fibrous bodies in the middle during melt extrusion) The time is 30 minutes and the number of measurements is three times).

In Table 1, "thermal contraction (%)" shows the thermal contraction rate which arises when the test body is heat-treated. Specifically, 12 test specimens of the fiber adjusted to a length of 100 mm were left to stand in a gear oven at 130 ° C. for 15 minutes, and the ratio of the lengths of the test specimens before and after standing was determined ((length before standing-length after standing). / Length before standing) x 100. In addition, a numerical value is the average value of ten (bones) except the maximum value and the minimum value among 12 (bones).

In Table 1, "glossy" was evaluated by visually judging 24,000 fibers (bones) and visually in a room exposed to direct sunlight and under a fluorescent lamp. Evaluation criteria are as follows.

Superior: smoothness, less gloss

Amount: Less smoothness but less gloss

A: uneven and less glossy, or smooth and slightly glossy

Poor: Large unevenness or strong luster

As is clear from Table 1 and Table 2, it can be seen from the present invention that fibers having excellent heat shrinkability, less gloss, and less yarn breakage during melt spinning can be easily obtained.

The fiber obtained using the resin composition of this invention can be used suitably for the life-related fiber products, such as a double | fiber-fiber product, such as socks, a rug, a curtain, and a towel, especially a hair decoration and an artificial hair fiber, for example.

In addition, the JP Patent application 2006-051859, the claim, and all the content of the abstract for which it applied on February 28, 2006 are referred here, and it introduces as an indication of the specification of this invention.

Claims (8)

A vinyl chloride resin fiber comprising a melt spun fiber of a resin composition containing 1 to 300 parts by weight of a polyester resin with respect to 100 parts by weight of a vinyl chloride resin and 100 parts by weight of the vinyl chloride resin. The method according to claim 1, The vinyl chloride resin fiber whose viscosity average degree of polymerization of vinyl chloride resin is 600-2,500. The method according to claim 1 or 2, Polyvinyl chloride resin fiber whose melting point of polyester-type resin is 100-300 degreeC. The method according to any one of claims 1 to 3, Vinyl chloride-type resin fiber whose polyester-type resin is polylactic acid-type resin. The method according to any one of claims 1 to 4, Vinyl chloride resin fiber having a single fineness of 1 to 200 decitex. The artificial hair which consists of vinyl chloride resin fiber of any one of Claims 1-5. (a) mixing a resin composition comprising a vinyl chloride resin and a polyester resin; (b) melt spinning the resin composition at a resin temperature of 150 to 200 캜 from a spinning die; (c) drawing the melt-spun fibers at a draw ratio of 2 to 20 times in an air atmosphere at a draw processing temperature of 30 to 150 ° C; (d) Vinyl chloride-based resin fibers having a step of thermally relaxing the fiber until the total length of the fiber becomes 99.8 to 50% before treatment in an air atmosphere maintained at the temperature of 80 to 200 ° C. Method of preparation. The method according to claim 7, The manufacturing method of the vinyl chloride type resin fiber whose one cross-sectional area of the nozzle hole used at the said process of melt spinning is 3 mm <2> or less.