JPH04136214A - Fiber composed of shape memory resin composition, its production, artificial hair and woven fabric - Google Patents

Abstract

PURPOSE:To obtain the subject fiber useful as an artificial hair, etc., and showing shape memory properties at a relatively low temperature by treating a shape memory resin composition containing vinyl chloride resin and a polyester- based thermoplastic elastomer in a specified ratio in a specified condition. CONSTITUTION:A shape memory resin composition containing (A) 95-50wt.% vinyl chloride-based resin, (B) 5-50wt.% polyester-based thermoplastic elastomer and (C) a plasticizer (e.g. dihexyl phthalate) in an amount of 0-30wt.% based on the total amount of the components (A) and (B) and having 25-100 deg.C glass transition temperature is initially subjected to extrusion molding at a temperature of >= the melting point of the component (B). Stretching is then carried out at 30-80 deg.C, preferably 40-75 deg.C and heat treatment is subsequently carried out at 80-130 deg.C, preferably 90-120 deg.C for 1-10sec., thus obtaining the objective fiber.

Description

DETAILED DESCRIPTION OF THE INVENTION (Industrial Application Field) The present invention relates to a fiber made of a shape-memory resin composition, a method for producing the same, and artificial hair and textiles using the fiber.

(Prior art) Generally, natural fibers such as cotton, linen, silk, and wool, or synthetic R such as polyamide, polyester, and polyvinylidene chloride
For males, it was difficult to obtain shape memory properties at relatively low temperatures, from around room temperature to below 100°C.

On the other hand, wI resins with shape memory properties include polynorbornene isoprene (manufactured by Kuraray), styrene-butadiene copolymer (M Kasei II), and polyurethane (Mitsubishi Heavy Industries II).
However, it is difficult to produce single fibers in any of these, and no applications have been found for fibers that have shape memory performance at relatively low temperatures around room temperature or below 100°C. .

Fibers that have shape memory performance near room temperature can be used, for example, as hair for toys or artificial hair such as wigs, but currently there are examples of using shape memory alloys (for example, Utility Model Publication No. 137086 of 1988). (public gazette) has been reported.

(Problems to be Solved by the Invention) As a result of intensive research in order to solve the above-mentioned drawbacks, the present inventors have discovered that a shape-memory material whose main components are a vinyl chloride resin and a polyester thermoplastic elastomer with a specific composition ratio. resin,
By processing under specific conditions, temperatures ranging from around room temperature to 1
The present invention was completed by discovering that fibers having shape memory performance can be obtained at temperatures below 00°C.

(Means for Solving the Problems) Thus, according to the present invention - (1) (A) a vinyl chloride resin, (B) a polyester thermoplastic elastomer, and (C) a plasticizer are blended; ) The component amount is 95 to 50% by weight.

(B) The amount of the component is 5 to 50% by weight, (C) The amount of the component is (A
0 to 30% by weight based on the total amount of component ) and component (B)
A fiber comprising a shape memory resin composition having a glass transition temperature of 25 to 100°C.

(2) Compounded with (A) vinyl chloride resin, (B) polyester thermoplastic elastomer, and (C) plasticizer, (A) component amount is 95 to 50 weight percent, weight) component amount is 5 ~50% by weight, (C) component amount is (A) component and (B
) 0 to 30% by weight based on the total amount of the components, and 2
A shape memory resin composition having a glass transition temperature of 5 to 100°C is extruded at a temperature equal to or higher than the melting point of a polyester thermoplastic elastomer, and stretched at a temperature of 30°C or higher and lower than 80°C.

The method for producing fibers according to claim 1, 6(3), wherein the method is then heat-treated at a temperature of 80°C or higher and lower than 130°C.Claim 1
Artificial hair using the described fibers.

(4) A woven fabric using the fiber according to claim 1.

is provided.

The vinyl chloride resin used in the fiber made of the shape memory resin composition of the present invention may be any resin containing 50% by weight or more of vinyl chloride units, and may be a vinyl chloride homopolymer, copolymer, or graft polymer. include. Monomers that can be copolymerized with vinyl chloride include vinyl esters such as vinyl #acid and vinyl stearate, olefins such as ethylene and propylene, vinyl ethers such as inbutyl vinyl ether and cetyl vinyl ether, and (meth)acrylic acid. Examples include, but are not limited to, unsaturated carboxylic acid esters such as methyl, ethyl (meth)acrylate, dimethyl maleate, and diethyl maleate, and vinylidene halides such as vinylidene chloride and vinylidene fluoride. Examples of graft polymers include vinyl chloride-ethylene-vinyl acetate polymer and vinyl chloride-ethylene-vinyl acetate polymer.
Vinyl acid-carbon oxide polymer, vinyl chloride, ethylene-
Examples include (meth)acrylic acid ester polymers, vinyl chloride-urethane polymers, vinyl chloride-chlorinated polyethylene polymers, etc., but are not limited to these. The average degree of polymerization of vinyl chloride resin is not particularly limited, but is 400
-5000, preferably 500-3000.

The polyester thermoplastic elastomer used in the fibers of the shape memory resin composition of the present invention is a polyester having both (a) a soft segment mainly composed of a polyether structure and (b) a hard segment mainly composed of a polyether structure. is a polymer, preferably (a) is 60
5-90% by weight of long-chain ester units or soft segments derived from at least one poly(alkylene oxide) glycol having a molecular weight of 0-6000 and at least one low-molecular weight dicarboxylic acid having a molecular weight of less than 300 and (b) A polyester copolymer consisting of 95 to 10% by weight of short chain ester units or hard segments derived from at least one low molecular weight diol having a molecular weight of less than 250 and at least one low molecular weight dicarboxylic acid having a molecular weight of less than 300. be. A representative example of this is commercially available from DuPont under the trade name "Hytrel" and is generally available.

The plasticizer used in the fiber made of the shape memory resin composition of the present invention can be a plasticizer generally used for soft purposes of vinyl chloride resin, such as di-2-ethylhexyl phthalate, di-n- Phthalate esters such as octyl phthalate, diisodecyl phthalate, dibutyl phthalate, and dibutyl phthalate; Linear dibasic acid esters such as dioctyl adipate and dioctyl sebacate; Trimellitic acid ester, polyester polymer plasticizer; Epoxidized soybean oil, epoxy Epoxy plasticizers such as linseed oil: Phosphate plasticizers such as triphenyl phosphate and tricresyl phosphate may be used alone or in combination of two or more.

The composition ratio of (A) vinyl chloride resin, (B) polyester thermoplastic elastomer, and (C) plasticizer used in the fiber made of the shape memory resin composition of the present invention is (A)
) Vinyl chloride resin 95 to 50% by weight; (B) FF polyester-based mature thermoplastic elastomer - 5 to 501% The composition should be 0 to 30% by weight based on the total component amount. (A) Vinyl chloride resin exceeds 95% by weight - (B)
If the content of the FF polyester-based thermoplastic elastomer is less than 5% by weight, the molding as a fiber will be inverted, and the temperature will be around room temperature to 1%.
It is difficult to fully exhibit shape recovery characteristics at temperatures below 00°C. Additionally, if (A) the vinyl chloride resin is less than 50% by weight and (B) the polyester thermoplastic elastomer is more than 50% by weight, the shape recovery temperature will be lower than room temperature, making it difficult to maintain the deformed shape at room temperature. Become. Furthermore (C
) A plasticizer may be added as necessary, but if it exceeds 30% by weight, the shape recovery temperature will be less than 30° C., and the shape will not be able to be maintained at room temperature.

These resin compositions contain stabilizers, lubricants, fillers, 5W1 inhibitors, ultraviolet absorbers, anti-GI additives, etc., as in general vinyl chloride resins. Various additives such as tja processing aid, nonflammable agent, coloring agent (CMl material, dye), etc. can be added as necessary. Further, other polymers may be mixed within a range that does not impair the effects of the present invention.

In producing fibers made of the shape memory resin composition of the present invention, an extruder used for g-manufacturing of resins, for example, is operated at a temperature higher than the melting point of the polyester thermoplastic elastomer, which is the component (B) of the resin composition. using 0.2~3■
The resin composition is extruded through a nozzle with a diameter of 30~
After stretching 1.5 to 10 times at 80°C, preferably 40 to 75°C, further stretching to 80 to 130°C, preferably 90 to 75°C.
1 2 By heat treatment at 0℃ for 1 to 10 seconds, 0
, 01 to 2-0+m diameter fibers with low aging shrinkage and high strength can be obtained.

If the stretching temperature is less than 30°C, the resin composition will be hard and will break, and if it exceeds 80°C, the resin composition will be too soft to be stretched.

Generally speaking, if the heat treatment temperature is less than 80°C, a sufficient heat treatment effect cannot be obtained, and if the temperature exceeds 130°C, the fibers will fuse together.

When the fibers made of the shape memory resin composition obtained according to the present invention are used for artificial hair such as dolls, animal toys, wigs, etc., hair that has been memorized as straight hair is warmed and curled with a hair dryer, and then cooled. By doing so, the curly hair shape is maintained.

By heating this again, the hair returns to its straight shape. It is also possible to store one hair in a curled shape in advance. These can be repeated and are expected to be effectively used for playing with one-doll hair, training hairdressers using wigs, etc.

Furthermore, when the fibers are used in woven or knitted fabrics, planar objects can be transformed and fixed into free three-dimensional shapes, and can return to their original planar shape simply by heating. Due to this.

It can be used for fabrics that can be easily wrinkled, fabrics that can be fixed into any shape, etc.

(Example) The present invention will be described in more detail with reference to Examples below, but the present invention is not limited thereto. Note that parts and percentages in Examples and Comparative Examples are based on weight unless otherwise specified.

(Examples 1 to 7) With the compositions shown in the upper row of Table 1, seven types of compositions consisting of vinyl chloride resin, polyester thermoplastic elastomer, and plasticizer were added, each containing 5 parts of heat stabilizer, 1.6 parts of lubricant, Add 15 parts of W* resistance aid and 3 parts of processing aid, mix in a mixer, and then transfer the mixture to a 65+im diameter single screw extruder (1
It was extruded into pellets at 60 to 170°C. These 7
40 mm diameter single screw extruder (17 mm)
A nozzle die with a diameter of 1 liter was attached at a temperature of 0 to 220° C.), and fibers of a predetermined diameter were obtained by extrusion and drawing. In addition, as a comparative example, fibers were prepared using a composition consisting of a vinyl chloride resin or a thermoplastic elastomer alone, and were also evaluated. The evaluation was based on workability, shape recovery temperature, and shape retention temperature.

The results are shown in the lower part of Table 1. In Table 1, the evaluation index for processability is as follows: (1) ○ means that fibers of a specified diameter are formed with good surface texture, (2) △ means that fibers are formed but surface texture is poor, and ( 3) Cases in which fibers could not be formed were marked as ×.

In addition, the shape recovery temperature is -i linear fiber at 50℃ 10-■
The fiber was wound around a zelkova with a diameter of (5@5IR), cooled and fixed, and when the temperature was raised again, the lowest temperature at which the fiber recovered to 100 mm R was set.

Furthermore, the shape retention temperature is 101 for straight fibers at 50℃.
The fibers were wound around a rod having a diameter of 51 .mu.R, cooled and fixed, and then heated again to reach the highest temperature at which the fibers retained their shape within loIIIR.

The following margins (Examples 8 to 12) Using the fiber of Example 4, a drawing furnace and a heat treatment furnace were installed between three sets of roll stands under the processing conditions shown in Table 2, and the rotational take-up speed of the roll stands was changed. Five types of fibers were prepared by stretching and heat treatment, and the tensile strength and heat shrinkage rate of each fiber were measured. In addition, five types of fibers were prepared as comparative examples and similar measurements were conducted. The results are shown in Table 2. It can be seen that the tensile strength of the fibers has been greatly improved, and the heat shrinkage rate has been slightly improved. The heat shrinkage rate is calculated as follows: (fiber length before heating) - (fiber length before heating) - (fiber after heating) length)].

Margin below (Example 13) The fibers treated in Example 11 were implanted as hair for dolls. Using this doll, the hair was curled with a hair dryer, and when cooled to room temperature, it was fixed in that shape and a doll with one hair curled was obtained.

Even when the hair was combed, the curls did not unravel.When the hair was heated again with a hair dryer, the curls returned to their straight form. This was repeated three times, and the same phenomenon was reproduced.

Similar play was attempted with an existing doll (hair made of polyvinylidene chloride am fiber), but such shape changes could not be achieved.

(Example 14) A plain woven fabric was prepared using the fibers treated in Example 11 as warp and weft yarns. This woven fabric was heated with hot air at 30 to 80° C., and the center portion was stretched into a circular shape to form a hat shape, and when cooled, the woven fabric was fixed in the hat shape. When the hat-shaped fabric was heated again with warm air, it returned to its original state of plain fabric. A similar change in shape could be obtained even if the process was repeated.

Such a fabric is easy to transport and store, and can be used as a flexible hat that can be transformed into a three-dimensional hat when in use.

Claims (4)

[Claims] (1) Compounded with (A) vinyl chloride resin, (B) polyester thermoplastic elastomer, and (C) plasticizer, (A) component amount is 95 to 50% by weight, (B) component amount is 5%.
~50% by weight, the amount of component (C) is 0 to 30% by weight based on the total amount of components (A) and (B), and 25 to 1% by weight.
A fiber made of a shape memory resin composition having a glass transition temperature of 00°C. (2) Compounded with (A) vinyl chloride resin, (B) polyester thermoplastic elastomer, and (C) plasticizer, (A) component amount is 95 to 50% by weight, (B) component amount is 5%.
~50% by weight, the amount of component (C) is 0 to 30% by weight based on the total amount of components (A) and (B), and 25 to 1% by weight.
A shape memory resin composition having a glass transition temperature of 00°C is extruded at a temperature equal to or higher than the melting point of the polyester thermoplastic elastomer, stretched at 30°C or higher and lower than 80°C, and then heat treated at 80°C or higher and lower than 130°C. The method for producing fibers according to claim 1, characterized in that: (3) Artificial hair using the fiber according to claim 1. (4) A woven fabric using the fiber according to claim 1.