JP2001131823A - Fiber composed of polyvinyl chloride-based resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a technique by which a polyvinyl chloride-based fiber composed of a resin composition containing a tin-based stabilizer and excellent in a luster and a transparent feeling can highly stably be obtained. SOLUTION: This polyvinyl chloride-based fiber is composed of a composition obtained by compounding (A) a vinyl chloride-based resin, (B) a processability improver for vinyl chloride resin in an amount of 0.2-5 pts.wt., (C) a tin-based stabilizer in an amount of 0.5-10 pts.wt., (D) one or more kinds of lubricants having >=10 saponification value in a total amount of 1.5-5 pts.wt., (E) one or more kinds of lubricants having <10 saponification value in a total amount of 0.3-1 pt.wt. and (F) a plasticizer in an amount of 0.5-8 pts.wt. based on the 100 pts.wt. of (A) the vinyl chloride-based resin.

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 containing a tin-based stabilizer and having a controlled gloss and transparency.

[0002]

2. Description of the Related Art Polyvinyl chloride resin is self-extinguishing,
It is excellent in chemical resistance and the like, and when it is made into a fiber, it can have its excellent properties, but polyvinyl chloride fiber melt-spun with a tin stabilizer compound, which is generally called non-toxic compound, is There is a distinctive luster (gloss) and turbidity when the fragments reflect light rays, and it is unnatural for glossy fibers. Cadmium / barium-based stabilizers have been used for conventionally used polyvinyl chloride-based fibers having good gloss and transparency, but such stabilizers generally have toxicity to the human body. Use is not preferred because it cannot be ignored and the load on the environment cannot be ignored.

Further, JP-A-10-102317 and JP-A-11-100714 disclose the invention of polyvinyl chloride fibers using a tin stabilizer. It is a fiber, which is a completely different technology from the fiber having excellent gloss and transparency provided by the present invention.

[0004]

SUMMARY OF THE INVENTION An object of the present invention is to produce a polyvinyl chloride fiber comprising a resin composition using a tin-based stabilizer and having a gloss and transparency that are well controlled. It is an object of the present invention to provide a technology that can be obtained with high stability.

[0005]

Means for Solving the Problems The inventors of the present invention have conducted intensive studies to solve the above-mentioned problems, and as a result, a tin-stabilized polyvinyl chloride resin was added with a specific processability improver for a vinyl chloride resin. The present invention has been completed by using appropriate amounts of a lubricant selected from saponification values and a plasticizer.

The saponification value as used herein means "the number of milligrams of potassium hydroxide (KOH) required to saponify 1 g of a sample. It corresponds to the sum of the acid value and the ester value. After saponifying the sample in an alcoholic solution of 0.5N potassium hydroxide, excess potassium hydroxide is titrated with 0.5N hydrochloric acid (physical science dictionary). That is, the present invention relates to (A) vinyl chloride resin 1
(B) 0.2 to 5 parts by weight of a processability improver for a vinyl chloride resin, (C) 0.5 to 10 parts by weight of a tin-based stabilizer, and (D) a lubricant 1 having a saponification value of 10 or more. 1.5 to 5 parts by weight in total of at least one kind, (E) 0.3 to 1 part by weight of at least one kind of lubricant having a saponification value of less than 10, (F) 0.5 to 8 parts of plasticizer
It is a polyvinyl chloride fiber comprising a composition in which parts by weight are blended.

The polyvinyl chloride fiber obtained according to the present invention can be suitably used as artificial hair having gloss and transparency.

[0008]

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 using various generally known polymerization methods. 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. Preferred copolymers are copolymers of ethylene, propylene, or vinyl acetate with vinyl chloride from the viewpoint of thermal stability during heat melt processing. 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)
The processability improver for vinyl chloride resin is a homo- or copolymer of alkyl (meth) acrylate, styrene and α-methylstyrene, and has a polymerization degree of 5000.
It is preferable that the alkyl ester of the alkyl (meth) acrylate has 1 to 10 carbon atoms.

The (B) processability improver for vinyl chloride resin stably promotes gelation of the vinyl chloride resin at the time of melt spinning, and improves the tensile strength at high temperatures, thereby stabilizing it. Used to ensure spinnability.
The polymer (B) can be obtained by radical polymerization of an alkyl (meth) acrylate in the presence of a radical initiator, but the polymerization method is not limited to this, and is generally known. It can be polymerized using various known polymerization methods. The copolymer may be in any copolymer form such as a random copolymer, a block copolymer, and a graft copolymer. As the alkyl (meth) acrylate in these (B) copolymers, those having 1 to 10 carbon atoms in the alkyl ester portion are used.
When the one having 11 or more carbon atoms is used, the compatibility with the vinyl chloride resin decreases, and the strength of the obtained fiber tends to decrease. In this respect, the number of carbon atoms is preferably 8 or less.

Specific examples of the alkyl (meth) acrylate include methyl acrylate, ethyl acrylate, n-propyl acrylate, i-propyl acrylate, n-butyl acrylate, t-butyl acrylate, methyl methacrylate, ethyl methacrylate,
Examples thereof include n-propyl methacrylate, n-butyl methacrylate, and t-butyl methacrylate, and these are used alone or in combination of two or more.

The degree of polymerization of the copolymer (B) is 500
It is preferably from 000 to 4,000,000. If the degree of polymerization is less than 500,000, the spinnability during spinning decreases, and
If it is more than 000000, the gelling property cannot be improved, the discharge amount fluctuates, and the freshness of the obtained fiber greatly fluctuates.

The polymer (B) is used in an amount of 0.2 to 5 parts by weight, more preferably 0.2 to 3 parts by weight, based on 100 parts by weight of the vinyl chloride resin. If the amount is less than 0.2 parts by weight, the effect of improving the processability is small, and if it exceeds 5 parts by weight, the increase in viscosity becomes large, and stable production becomes difficult. The (C) tin-based stabilizer to be blended with the (A) vinyl chloride-based resin is preferably a compound represented by the following general formula (I).

[0014]

Embedded image

Wherein m is 1 or 2, R is a C1 to C8 alkyl or ester (--CH2CH2COOR ': R'
Is a C1-C8 alkyl), and Y is at least one selected from the group consisting of mercaptides, maleates, and carboxylate. ] Specifically, mercaptotin-based thermal stabilizers such as dimethyltin mercapto, dibutyltin mercapto, and dioctyltin mercapto; and malate tin-based thermal stabilizers such as dimethyltinmalate, dibutyltinmalate, dioctyltinmalate, and dioctyltinmalate polymers. And laurate tin-based heat stabilizers such as dimethyltin laurate, dibutyltin laurate, and dioctyltin laurate, but are not limited thereto. As a usage method, it is used alone or in combination of two or more bases.

The tin-based stabilizer (C) is used as a stabilizer for a vinyl chloride-based resin. It is used for stable production, prevention of deterioration in quality, improvement of coloring, etc., by functions such as destruction of a complex comprising polyene and HCL.

The tin stabilizer (C) is used in an amount of 0.5 to 10 parts by weight, more preferably 1.0 to 5 parts by weight, per 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 10 parts by weight, the effect of further increasing the amount is poor, 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 partially saponified esters, tin laurate-based lubricants, and acid value polyethylene 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 PV
Since it has a relatively good compatibility with C, it acts as an internal lubricant and promotes the disintegration of PVC particles.
It is used to increase the smoothness of the fiber surface by reducing unevenness caused by the C particles, and to develop good gloss.

The lubricant (D) having a saponification value of 10 or more is 1.5 to 5 parts by weight based on 100 parts by weight of the vinyl chloride resin.
More preferably, 1.5 to 4 parts by weight is used. If the amount is less than 1.5 parts by weight, a large amount of unevenness on the fiber surface remains due to insufficient particle disintegration, 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 PV
Since it has relatively poor compatibility with C, it is used to act as an external lubricant, reduce the adhesiveness between metal and resin, and perform stable production.

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 is not exhibited, and stable production becomes difficult. 1
If the amount is more than 10 parts by weight, the compatibility will be poor, giving a turbid feeling, and a fiber having good transparency cannot be obtained.

(A) blended with vinyl chloride resin (F)
Examples of the plasticizer include phthalates, linear dibasic esters, phosphates, epoxidized vegetable oil, polyester plasticizer, trimellitic plasticizer, and pyromellitic plasticizer.

The plasticizer (F) enhances segment mobility by assisting the micro-Brownian movement of PVC molecules and imparts fluidity at high temperatures, thereby exerting a great effect on improving yarn breakage during spinning. Used for

The plasticizer (F) is a vinyl chloride resin 1
1 to 8 parts by weight, more preferably 1.
5 to 5 parts by weight are used. If the amount is less than 1 part by weight, the effect of improving spinnability is poor, and if it exceeds 8 parts by weight, the heat shrinkage of the obtained fiber increases, which is not preferable. 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 as it is in a powder state and can be heated and melted by spinning. However, it is preferable to granulate with 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 normal single-screw or twin-screw extruder, and spun from a fine-hole nozzle. Can be issued. The spinning raw material related to the fiber of the present invention exhibits excellent spinnability as it is, but a heated spinning cylinder is provided in the fiber axis direction immediately below the nozzle, and the spun molten yarn is instantaneously heated to a high degree. It is also possible to spin. 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, instantaneously heat it 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.

[0027]

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 is visually observed,
The evaluation was as follows. Thread breaks once or less / 1 hour ... "5" Thread breaks 2-3 times / 1 hour ... "4" Thread breaks 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 The fiber after spinning was visually observed and evaluated as follows. The surface is smooth, glossy over the entire surface, and transparent. ... [4] The surface is smooth and glossy over the entire surface, but there is no transparency. [3] The surface has fine irregularities and poor 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

Examples 1 to 3 and Comparative Examples 1 to 3 A vinyl chloride resin, a processability improver, a tin stabilizer, a lubricant (D), a lubricant (E) and a plasticizer are shown in Table 1 below. The mixture was mixed at a predetermined ratio as shown and stirred and mixed at 110 ° C. for 40 minutes using a ribbon blender.
At a die temperature of 145 ° C. This resin pellet was attached to a 30 mmφ extruder with L / D = 20, equipped with a nozzle having a hole diameter of 0.5 mmφ and a number of holes of 60. Extruded under good conditions, and heat-treated for about 0.5 to 1.5 seconds in a heated spinning cylinder provided directly below the nozzle (in a 200 to 300 ° C. atmosphere with good spinnability in each case),
It was spun by the first take-off roll. Next, through a hot air circulation box at 110 ° C. between the second drawing roll and 2.
The film was stretched 5 times. Further, the wire was drawn between two pairs of conical rolls installed in a box adjusted to a temperature of 115 ° C., continuously subjected to a 25% relaxation treatment, and a multifilament having a single yarn fineness of 67 dtex was wound up. 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. The comparative example was a lubricant system according to JP-A-11-100714.

[0029]

[Table 1]

As is evident from the results in Table 1, gloss and transparency are excellent by using an appropriate amount of a vinyl chloride resin, a processability improver, a tin stabilizer, a lubricant D, a lubricant E, and a plasticizer. Fibers can be melt spun with high stability. On the other hand, as shown in the comparative example,
With the blending system according to 4, only fibers with insufficient gloss were obtained.

Examples 4 to 9 Multifilaments were wound in the same manner as in Examples 1 to 3, except that the type of plasticizer was changed. The results are shown in Table 2.

[0032]

[Table 2]

As is evident from the results in Table 2, even if the type of the plasticizer is changed, the spinnability is also significantly improved, and the quality does not deteriorate.

[0034]

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. Further, since melt spinning can be performed with high stability, productivity is high and production can be carried out at low cost, and it can be applied to industrial materials other than artificial hair.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI theme coat ゛ (reference) C08L 27/06 C08L 27/06 27/24 27/24 F term (reference) 4J002 AE033 BB03 BB123 BC032 BC042 BC092 BD041 BD051 BD181 BG042 BG052 EG017 EH037 EH047 EH057 EH098 EH148 EW048 EZ046 EZ047 EZ076 FD022 FD028 FD036 FD173 FD177 GC00 4L035 BB32 BB52 BB89 BB91 CC07 DD14 FF01 FF04 GG03

Claims (6)

[Claims] (A) 0.2 to 5 parts by weight of (B) a processability improver for vinyl chloride resin, and (C) 0.5 to 10 parts by weight of a tin stabilizer with respect to 100 parts by weight of vinyl chloride resin. Parts, (D) 1.5 to 5 parts by weight in total of one or more lubricants having a saponification value of 10 or more, and (E) 0.1 to 5 parts by weight in total of one or more lubricants having a saponification value of less than 10.
A fiber comprising a polyvinyl chloride resin composition, comprising a composition in which 3 to 1 part by weight and (F) 0.5 to 8 parts by weight of a plasticizer are blended. 2. The processability improver (B) for vinyl chloride resin comprises:
(Meth) acrylic acid alkyl ester, styrene, and α-methylstyrene homo- or copolymer,
(Meth) acrylic acid alkyl ester is methyl acrylate, ethyl acrylate, n-propyl acrylate, i-propyl acrylate, n-butyl acrylate, t-butyl acrylate, methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, n-butyl The fiber comprising the polyvinyl chloride resin composition according to claim 1, which is at least one selected from the group consisting of methacrylate and t-butyl methacrylate. 3. The fiber comprising the polyvinyl chloride resin composition according to claim 1, wherein the tin stabilizer (C) is a compound represented by the following general formula (I). Embedded image [Wherein m is 1 or 2, R is C1-C8 alkyl or ester (-CH2CH2COOR ': R' is C1-C8
Alkyl), 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 according to claim 1, wherein 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 acid value polyethylene wax is used. Fiber comprising a resin composition. 5. The lubricant 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. The fiber which consists of a polyvinyl chloride resin composition of the above. 6. The plasticizer (F) is a phthalate, a linear dibasic ester, a phosphate, an epoxidized vegetable oil, a polyester plasticizer, a trimellitic plasticizer, or a pyromellitic plasticizer. The fiber comprising the polyvinyl chloride resin composition according to claim 1, wherein at least one selected from the group consisting of agents is used.