JP2001115331A - Polyvinyl chloride-based fiber - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a polyvinyl chloride-based fiber having a well-controlled luster and transparency without using a stabilizer containing cadmium or barium. SOLUTION: This polyvinyl chloride fiber is obtained by melt-spinning a resin composition blended with (A) 100 pts.wt. polyvinyl chloride-based resin, (B) 0.5-5 pt.wt. epoxy-based plasticizer, (C) 0.5-5 pt.wt. tin-based stabilizer, (D) 1-5 pt.wt. lubricating agent having >=10 saponification value and (E) 0.3-1 pt.wt. lubricating agent having <10 saponification value as main components.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a polyvinyl chloride fiber comprising a resin composition using a tin stabilizer, which is produced stably and whose gloss and transparency are controlled.

[0002]

2. Description of the Related Art Polyvinyl chloride resin is excellent in self-extinguishing, chemical resistance and the like, and can have excellent properties when made into fibers. Polyvinyl chloride fiber melt-spun with the agent has a unique gloss (glossy) and turbidity when glass shards reflect light, and is unnatural for glossy fiber, so improvement is needed Met.

For this reason, a cadmium / barium stabilizer is used as a currently marketed polyvinyl chloride fiber having good gloss and transparency, and such a stabilizer is generally used for human body. Its use is not preferred because its toxicity to water cannot be ignored and its impact on the environment cannot be ignored.

Further, JP-A-10-102317 and JP-A-11-100714 disclose inventions of a polyvinyl chloride fiber using a tin stabilizer, but all of them disclose matting in consideration of human hair. It is a fiber, which is a completely different technology from the fiber having excellent gloss and transparency provided by the present invention.

[0005]

SUMMARY OF THE INVENTION An object of the present invention is to provide a polyvinyl chloride fiber whose gloss and transparency are well controlled without using a stabilizer containing cadmium or barium as a main component. It is in.

[0006]

Means for Solving the Problems As a result of intensive studies to solve the above problems, the present inventors have selected a tin-stabilized polyvinyl chloride resin based on an epoxy plasticizer and a saponification value. The present invention has been completed by using an appropriate amount of the lubricant. The saponification value in the present invention is as follows. "The number of milligrams of potassium hydroxide (KOH) required to saponify 1 g of the sample, which is the sum of the acid value and the ester value. To determine the saponification value, a solution of about 0.5N potassium hydroxide in an alcohol solution is used. After saponifying the sample, 0.5
Titrate excess potassium hydroxide with N hydrochloric acid. (Dictionary of Physics and Chemistry) ".

That is, the present invention relates to (A) 100 parts by weight of a vinyl chloride resin and (B) an epoxy plasticizer of 0.5 to 0.5 parts by weight.
5 parts by weight, (C) 0.5 to 5 parts by weight of tin-based stabilizer, (D)
1 to 5 parts by weight of a lubricant having a saponification value of 10 or more, (E) a saponification value of 10
It is a polyvinyl chloride fiber obtained by melt-spinning a resin composition mainly containing a composition containing less than 0.3 to 1 part by weight of a lubricant.

The epoxy plasticizer (B) is at least one selected from the group consisting of epoxidized soybean oil, epoxidized linseed oil, octyl epoxystearate, epoxidized fatty acid butyl and epoxidized linseed oil butyl.
Preferably it is a seed. The tin-based stabilizer (C) is preferably represented by the following general formula (I).

[0009]

Embedded image [M is 1 or 2, R is C1 to C8 alkyl or ester, Y is at least one selected from the group consisting of mercaptides, maleates and carboxylate. The lubricant (D) having a saponification value of 10 or more is at least selected from the group consisting of fatty acids, fatty acid esters, fatty acid partial esters, hydroxylated fatty acids, pentaerythritol fatty acids, fatty acid partial saponified esters, tin laurate-based lubricants, and polyethylene oxide wax. One kind and preferably the lubricant (E) having a saponification value of less than 10 is preferably at least one kind selected from the group consisting of polyethylene wax, polypropylene wax, hydrocarbon wax, amide wax and metal soaps. The polyvinyl chloride fiber obtained according to the present invention can be suitably used as artificial hair having gloss and transparency.

[0010]

DETAILED DESCRIPTION OF THE INVENTION (A) used in the present invention
The vinyl chloride resin is a vinyl chloride homopolymer, a chlorinated vinyl chloride homopolymer, a copolymerizable monomer of vinyl chloride with up to 50% by weight, one kind and / or two or more kinds. A multicomponent) copolymer or a mixture thereof.
Representative examples of the copolymerizable monomer include ethylene, propylene, alkyl vinyl ether, vinylidene chloride, vinyl acetate, acrylate, and maleate.

The (multi-component) copolymer can be polymerized by various known polymerization methods generally known. The (multi-component) copolymer may take any (multi-component) copolymer form such as random, block, and graft.

If the amount of the component other than vinyl chloride in the (multi-component) copolymer is 50% by weight or more, it is not preferable because it is softened, the heat resistance is reduced, and the cost becomes higher. As a preferred copolymer, from the viewpoint of thermal stability during heat melting processing,
It is a copolymer of ethylene, propylene, or vinyl acetate and vinyl chloride. As for the degree of polymerization of the vinyl chloride resin, the higher the degree of polymerization, the higher the strength of the obtained fiber tends to be. On the other hand, the lower the degree of polymerization, the more advantageous in terms of spinnability. From these relations, the degree of polymerization of the vinyl chloride resin is preferably about 500 to 1500, more preferably about 700 to 1300.

(A) blended with vinyl chloride resin (B)
Representative examples of the epoxy plasticizer include epoxidized soybean oil, epoxidized linseed oil, octyl epoxystearate, epoxidized fatty acid butyl, and epoxidized linseed oil fatty acid butyl. Among them, epoxidized soybean oil is preferred in terms of performance and price. The epoxy plasticizer (B) is used in an amount of 0.5 to 5 based on 100 parts by weight of the vinyl chloride resin.
Parts by weight, preferably 1 to 3 parts by weight. If the amount is less than 0.5 part by weight, breakage of single yarns and fusion of single yarns increase, and the effect of improving workability is reduced. If the amount exceeds 5 parts by weight, the compounded powder compound tends to be blocked, and stable processing becomes difficult.

(A) Compounded with vinyl chloride resin (C)
The tin-based stabilizer is represented by the following general formula (I).

[0015]

Embedded image [M is 1 or 2, R is C1 to C8 alkyl or ester, Y is at least one selected from the group consisting of mercaptides, maleates and carboxylate. As the method of use, they may be used alone or in combination of two or more.

The (C) tin-based stabilizer is used as a stabilizer for a vinyl chloride-based resin, as an antioxidant action, an HCl-scavenging action, an exchange reaction with an active Cl atom, an addition of generated mercaptan to a double bond, Function of destruction of complex consisting of polyene and HCl prevents stable reduction of production quality,
It is used for improving coloring. Specifically, mercaptotin-based heat stabilizers such as dimethyltin mercapto, dibutyltin mercapto, and dioctyltin mercapto, and malate tin-based heat stabilizers such as dimethyltinmalate, dibutyltinmalate, dioctyltinmalate, and dioctyltinmalate polymers , Dimethyltin laurate, dibutyltin laurate, dioctyltin laurate and the like, but are not limited thereto. The tin-based stabilizer (C) is used in an amount of 0.5 to 5 parts by weight, preferably 1 to 3 parts by weight, based on 100 parts by weight of the vinyl chloride resin. If the amount is less than 0.5 part by weight, the effect as a stabilizer is poor, and if it exceeds 5 parts by weight, the effect of increasing the amount is small, which is economically disadvantageous.

(A) Compounded with vinyl chloride resin (D)
Examples of the lubricant having a saponification value of 10 or more include fatty acids, fatty acid esters, fatty acid partial esters, hydroxylated fatty acids, pentaerythritol fatty acids, fatty acid partial saponified esters, tin laurate-based lubricants, and polyethylene oxide wax.
As the method of use, they may be used alone or in combination of two or more.

The lubricant (D) having a saponification value of 10 or more is used in an amount of 1 to 5 parts by weight, preferably 1.5 to 4 parts by weight, per 100 parts by weight of the vinyl chloride resin. If the amount is less than 1.0 part by weight, since the particle disintegration is insufficient, a large amount of unevenness remains on the fiber surface, and good gloss cannot be obtained. If the amount exceeds 5 parts by weight, the gelation is accelerated, and the increase in melt viscosity becomes large, so that stable production becomes difficult.

(A) Compounded with vinyl chloride resin (E)
Lubricants having a saponification value of less than 10 include polyethylene wax, polypropylene wax, hydrocarbon wax, amide wax, and metal soaps. The usage method is
Used alone or in combination of two or more.

The lubricant (E) having a saponification value of 10 or less is used in an amount of 0.3 to 1 part by weight based on 100 parts by weight of the vinyl chloride resin. If the amount is less than 0.3 parts by weight, a sufficient effect as an external lubricant cannot be exhibited, and stable production becomes difficult. If the amount exceeds 1 part by weight, the fiber has poor compatibility and exhibits a turbidity, and a fiber having a good transparency cannot be obtained. In addition, other components can be appropriately mixed with the fiber of the present invention as required for the production method and quality. For example, an antistatic agent, an ultraviolet absorber, a pigment, a dye, or the like can be blended. In addition, the resin composition for melt-spinning the fiber of the present invention can be obtained by mixing at ordinary temperature or by heating using a usual powder mixer such as a ribbon blender or a Henschel mixer. The obtained resin composition can be directly poured into an extruder in the form of a powder and subjected to hot melt spinning. However, it is preferable that the resin composition is granulated by a kneading roll, a kneader or an extruder to obtain a spinning raw material. Since the spinning raw material obtained as described above is excellent in processability, it is heated and melted at a temperature of about 150 to 200 ° C. using a usual single-screw or twin-screw extruder, and is spun from a fine hole nozzle. Can be issued. The spinning raw material related to the fiber of the present invention exhibits excellent spinnability even as it is, but a heating cylinder is provided in the fiber axis direction immediately below the nozzle,
It is also possible to introduce the spun molten yarn, heat it instantaneously, and draw it to a high degree. In the case of polyvinyl chloride fiber, which is more likely to be thermally decomposed than polyester or polyolefin, it is better to operate the extruder at a relatively low temperature, heat it instantaneously with this heating cylinder, and draw it to a high degree. This is preferable because thermal degradation can be suppressed and continuous operation can be performed for a long time.
In general, the spun yarn is further subjected to a drawing heat treatment under a known method and conditions to obtain a final polyvinyl chloride fiber.

[0021]

Next, the present invention will be described in more detail by way of examples of melt spinning, but this does not limit the scope of the present invention. The evaluation method and the like will be described below before the embodiment. (1) Evaluation of spinnability At the stage of melt spinning, the occurrence of yarn breakage was visually observed and evaluated as follows. Thread break is less than 1 time / 1 hour ...... "5" Thread break is 2-3 times / 1 hour ... "4" Thread break is 4-6 Times / 1 hour ...... "3" Thread breaks 6 to 15 times / 1 hour ... "2" Thread breaks 15 times or more / 1 hour ... ... "1" (2) Evaluation of gloss and transparency Fibers after melt spinning were visually observed and evaluated as follows. The surface is smooth, glossy over the entire surface, and transparent. ... [4] Although the surface is smooth and glossy over the entire surface, there is no transparency. ... [3] The surface is slightly uneven and has low gloss, but has a transparent feeling. ... [2] The surface has fine irregularities, poor gloss and no transparency. ... [1] (3) Thermal shrinkage ratio Twelve multifilaments having a length of 20 cm are suspended in a gear oven (constant temperature dryer) at 90 ° C, and the shrinkage ratio [%] of each sample after 15 minutes is measured. Of these, the average of 10 intermediate values was taken as the heat shrinkage. The heat shrinkage is preferably 10% or less. (4) Fiber strength tensile tester (INTESCO MODEL201)
Measured by The measuring method is based on JIS chemical fiber filament test method L1013.

(Examples 1 to 3, Comparative Examples 1 to 3) A vinyl chloride resin, an epoxy plasticizer, a tin stabilizer, a lubricant (D) and a lubricant (E) were prepared according to the following formulas shown in Table 1 below. The mixture was stirred at 110 ° C. for 40 minutes using a ribbon blender and then extruded at a cylinder temperature of 140 ° C.
At a die temperature of 145 ° C. This resin pellet was placed in a 30 mmφ extruder with L / D = 20 and a hole diameter of 0.
A nozzle having a diameter of 5 mm and a number of holes of 60 was installed, and extruded under conditions of good spinnability in each case in the range of cylinder temperature of 150 to 180 ° C and nozzle temperature of 180 ± 15 ° C. About 0.5 ~
Heat-treated for 1.5 seconds and spun with the first take-off roll. Next, the film was stretched 2.5 times with a second stretching roll through a hot air circulation box at 110 ° C. Further, the wire is drawn between two pairs of conical rolls installed in a box adjusted to a temperature of 115 ° C., a relaxation treatment of 25% is continuously performed, and the single-fiber fineness is 6%.
The multifilament of 7 dtex was wound. At this time, the processability (spinning property) and the physical properties of the multifilament obtained in each example were measured by the above-described methods. The results are shown in Table 1.

[0023]

[Table 1] As is clear from the results in Table 1, vinyl chloride resin, epoxy plasticizer, tin stabilizer, lubricant (D), lubricant (E)
By using an appropriate amount of, a fiber excellent in gloss and transparency can be stably melt-spun.However, when 6 parts of an epoxy plasticizer is used, a fiber excellent in gloss and transparency is obtained. The powder compound bridged in the hopper and became difficult to flow down to the extruder, so that the discharge fluctuation became large and stable melt spinning was impossible. or,
When 0.1 part of the epoxy-based plasticizer is used, a fiber having excellent gloss and transparency is obtained, but the pressure fluctuation in the nozzle becomes large and the yarn breaks, so that stable melt spinning was impossible.

(Examples 4 to 6, Comparative Examples 4 to 6) As shown in Table 2 below, spinning was carried out in the same manner as in Example 1 except that a resin composition having a different compounding agent was used. The results are shown in Table 2.

[0025]

[Table 2] As is clear from the results in Table 2, vinyl chloride resin, epoxy plasticizer, tin stabilizer, lubricant (D), lubricant (E)
, A fiber having excellent gloss and transparency can be stably melt-spun. However, when 6 parts of a lubricant (D) having a saponification value of 10 or more is used, a fiber having excellent gloss and transparency can be obtained. Although it can be obtained, the gelation proceeds rapidly,
The fluctuation of the torque of the extruder became large, and stable melt spinning was impossible. When 0.1 part and 0.5 part of the lubricant (D) having a saponification value of 10 or more are used, the PVC particles do not sufficiently disintegrate, the surface irregularities of the obtained fiber remain, and the gloss is insufficient. Only fibers were obtained.

(Examples 7 to 9 and Comparative Examples 7 to 9) As shown in Table 3 below, spinning was carried out in the same manner as in Example 1 except that a resin composition having a different compounding agent was used. The results are shown in Table 3.

[0027]

[Table 3] As is clear from the results in Table 3, vinyl chloride resin, epoxy plasticizer, tin stabilizer, lubricant (D), lubricant (E)
, A fiber having excellent gloss and transparency can be stably melt-spun. However, when 1.1 parts and 2 parts of the lubricant (E) having a saponification value of 10 or less are used, transparency is lost. Only the obtained fiber was obtained. When 0.1 part of the lubricant (E) having a saponification value of 10 or less was used, the resin was fused and stayed in the nozzle, and stable melt spinning was impossible.

[0028]

As described above, the polyvinyl chloride fiber according to the present invention has excellent gloss and transparency, and can be suitably used for artificial hair. In addition, since stable melt spinning is possible, productivity is high and production can be performed at low cost, and it can be applied to fields of industrial materials other than artificial hair.

Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat II (Reference) C08L 27/06 C08L 27/06 // (C08L 27/06 (C08L 27/06 23:26 23:26 91:06) 91:06) F term (reference) 4J002 AE034 BB034 BB124 BB253 BD041 BD051 BD061 BD071 BD081 BD091 BD101 BD181 CD162 EF058 EH038 EL026 EP019 EZ047 EZ048 EZ067 FD022 FD026 FD037 FD173 FD037 BB 173 FD174 G JJ15

Claims (5)

[Claims] 1. An epoxy plasticizer (B) 0.5 to 5 parts by weight based on 100 parts by weight of a vinyl chloride resin (A).
0.5 to 5 parts by weight of a tin-based stabilizer, (D) 1 to 5 parts by weight of a lubricant having a saponification value of 10 or more, and (E) 0.3 of a lubricant having a saponification value of less than 10.
A polyvinyl chloride fiber obtained by melt-spinning a resin composition mainly containing a composition blended in an amount of 1 to 1 part by weight. 2. The epoxy plasticizer (B) is at least one selected from the group consisting of epoxidized soybean oil, epoxidized linseed oil, octyl epoxystearate, epoxidized fatty acid butyl and epoxidized linseed oil fatty acid butyl. The resin composition for a vinyl chloride fiber according to claim 1, wherein 3. The polyvinyl chloride fiber according to claim 1, wherein the tin stabilizer (C) is represented by the following general formula (I). [M is 1 or 2, R is C1 to C8 alkyl or ester, Y is at least one selected from the group consisting of mercaptides, maleates and carboxylate. ] 4. A lubricant (D) having a saponification value of 10 or more is a fatty acid,
The polyvinyl chloride fiber according to claim 1, which is at least one selected from the group consisting of a fatty acid ester, a fatty acid partial ester, a hydroxylated fatty acid, a pentaerythritol fatty acid, a fatty acid partially saponified ester, a tin laurate-based lubricant, and an oxidized polyethylene wax. . 5. The poly according to claim 1, wherein the lubricant (E) having a saponification value of less than 10 is at least one selected from the group consisting of polyethylene wax, polypropylene wax, hydrocarbon wax, amide wax and metal soaps. PVC fiber