JP3023390B2 - Endothermic, exothermic composite fiber - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION The present invention relates to an endothermic material suitable for clothing,
The present invention relates to a heat-generating conjugate fiber.

[0002]

2. Description of the Related Art Synthetic fibers such as polyester, nylon and acrylic fibers are widely used for clothing. In recent years, however, there has been a demand for clothing fibers having a special function. One of them is endothermic and exothermic fibers.

[0003] Conventionally, as the animal heat insulating fiber, those containing or adhering a substance having a far-infrared radiation ability have been proposed and put into practical use. However, this fiber exhibits a heat retaining effect only after absorbing sunlight, and does not generate or absorb heat in response to a change in outside temperature. Further, there is a problem that the use of the fiber is restricted because the fiber becomes black depending on a substance to be contained or attached thereto.

[0004]

SUMMARY OF THE INVENTION An object of the present invention is to provide an endothermic or exothermic fiber which absorbs or generates heat due to changes in body temperature or outside temperature.

[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, have used a thermoplastic polymer having a high melting point or a high softening point on the surface of a fiber to obtain a specific melting point and crystallinity. When a conjugate fiber using a thermoplastic polymer having a oxidizing property as the interior of the fiber is used, the fiber retains the necessary properties as a fiber for clothing, and finds that a fiber having endothermic and exothermic properties can be obtained. Reached.

That is, the gist of the present invention is as follows. Three different thermoplastic polymers (Polymer A,
B, C), wherein the polymer A covers the fiber surface.
Synthetic fiber, polymer A has a melting point or softening point of 110 ° C.
Above thermoplastic polymer, polymer B, the melting point is 15 ~ 50 ℃,
A thermoplastic polymer having a heat of fusion of 10 mJ / mg or more, polymer C is
The crystallization temperature is 40 ℃ or less and the heat of crystallization is 10mJ / mg or more.
Endothermic and exothermic composite characterized by being a thermoplastic polymer
Synthetic fiber.

In the present invention, the melting point and crystallization characteristics are as follows:
The measurement is performed under the following conditions using a differential scanning calorimeter DSC-2 manufactured by Perkin Elmer. That is, in a nitrogen stream, the temperature is raised from −30 ° C. to 280 ° C. at a temperature rising rate of 10 ° C./min, held for 5 minutes, and then lowered to −30 ° C. at a rate of 10 ° C./min and held for 3 minutes 280 ° C at 10 ° C / min.
Measure the temperature up to

[0008] The peak of the melting temperature at the time of re-heating, the melting point Tm,
The melting peak area at that time is defined as the heat of fusion ΔHf, the peak of the crystallization temperature at the time of cooling is defined as the cooling crystallization temperature Tc, and the crystallization peak area is defined as the crystallization heat ΔHc.

The softening point is AMP-1 manufactured by Yanagimoto Seisakusho.
Using an automatic softening point measuring device, the temperature rise rate from 30 ° C to 10 ° C /
Measure in minutes.

The fiber of the present invention exhibits endothermic properties due to heat of fusion absorbed when polymer B is melted, and exothermic properties due to heat of crystallization generated when polymer C is crystallized. The polymer C having polymer B and the heating capacity with the endothermic ability not exposed on the fiber surface, since the fiber surface is covered with polymer A refractory or high softening point, required as clothing fibers It has excellent characteristics and exhibits endothermic and exothermic abilities.

The polymer B of the present invention has a melting point of 15 to 50.
° C, preferably 20-45 ° C.
° C, optimally 30-40 ° C. If the melting point is too low, it will be in a molten state at room temperature, and if it is too high, it will not melt at body temperature or outside temperature, so that the object of the present invention cannot be achieved.

The polymer B must have a heat of fusion of 10 mJ / mg or more, preferably 30 mJ / mg or more, and most preferably 50 mJ / mg or more. Heat of fusion is 10mJ
When the amount is less than / mg, an endothermic effect cannot be substantially obtained.

On the other hand, the polymer C has a cooling crystallization temperature of 40 ° C.
It is necessary that the temperature be as follows, preferably 35 ° C. or lower, and most preferably 30 ° C. or lower. Naturally, crystallization occurs at a temperature lower than the melting point.However, when the temperature of the outside air moves from a high place to a low place, the fiber needs to generate heat by crystallization, so the temperature drop crystallization temperature is low.
It must be below 40 ° C.

Further, the polymer C has a heat of crystallization of 10 mJ / mg.
It is necessary to have the above, preferably 30 mJ /
mg or more, optimally 50 mJ / mg or more. When the heat of crystallization is less than 10 mJ / mg, substantially no exothermic effect can be obtained.

In the composite fiber of the present invention, the polymer B
The coalesced C is a polymer different from each other, and in order to exhibit the endothermic and exothermic ability using both, the heat of fusion of the polymer B and the heat of crystallization of the polymer C or the polymer B It is necessary that the heat of crystallization and the heat of fusion of the polymer C be in a calorific range in which they do not cancel each other.

As the polymer B, there is a polymer obtained from a linear aliphatic dicarboxylic acid component and a linear aliphatic diol component, and specifically, polyethylene adipate, polypentamethylene adipate, polytetramethylene glutarate, Examples include polytrimethylene suberate, polyethylene pimerate and the like.

As the polymer C, there is a polymer obtained from a linear aliphatic dicarboxylic acid component and a linear aliphatic diol component, and specifically, polytetramethylene adipate, polypentamethylene sebacate, polynonamethylene. Glutarate, polypentamethylene dodecane dicarboxylate, polypentamethylene pimerate and the like.

Further, two or more dicarboxylic acid components and two or more diol components in the polymer B and the polymer C may be used in combination, and terephthalic acid, isophthalic acid, and Sodium sulfoisophthalic acid, succinic acid, trimellitic acid, hydroxybenzoic acid, decane-1,10-dicarboxylic acid, octadecane-1,
Even if 18-dicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, diethylene glycol, 1,4-cyclohexanedimethanol, etc. are used in combination as a copolymer component, or additives such as matting agents, stabilizers, and coloring agents are added. Good.

Such a linear aliphatic polyester can be produced by a conventional method. That is, it can be produced by subjecting a dicarboxylic acid component and a diol component to esterification or transesterification and then performing a polycondensation reaction.

The crystallization temperature of the polymer C when the temperature is lowered can be controlled by adding a nucleating agent.

Examples of the crystal nucleating agent include fine particles of inorganic compounds such as talc, silica, glass chopped strand, titanium dioxide, calcium silicate and antimony trioxide, and fine particles of organic acid salts such as magnesium stearate and sodium benzoate; Fine particles of an organic compound such as an ethylene oxide adduct of disodium sulfobisphenol A, a fluororesin, an organic silicone, a crosslinked polyacrylic acid, a crosslinked polystyrene, or a polyarylate may be used, and two or more kinds may be used in combination. .

When a crystal nucleating agent is contained, it is suitably contained in an amount of 0.01 to 3.0% by weight. If the content is too small, the effect as a crystallization accelerator is poor.On the other hand, if it is too large, the fiber is likely to be cut at the time of spinning or drawing, and the life of the spinneret pack filter is shortened. In addition, fibers cannot be stably manufactured.

The nucleating agent may be added at the time of esterification or transesterification, or may be added at the stage of the polycondensation reaction.

Next, the polymer A has a melting point or softening point of 110
C. or higher, preferably 170 ° C.
C. or higher, optimally 210.degree. C. or higher. If the melting point or the softening point is less than 110 ° C., the fibers cannot withstand hot water or cannot be ironed, which is not suitable for practical use.

Examples of the polymer A include polyesters, polyamides, polyolefins and the like, and most preferred are polyethylene terephthalate, polybutylene terephthalate and polyesters mainly composed of these.

The composite fiber of the present invention comprises a polymer A, a polymer B
And the polymer C can be produced by compound spinning by a conventional method so that the polymer A covers the fiber surface. In spinning, it is necessary to consider the melting point and melt viscosity of the polymer used, and to adopt the optimal conditions,
Usually, spinning is performed at a spinning temperature of 180 to 300 ° C, preferably 200 to 280 ° C.

The composite form is a sea-island type in which the polymer A is an ocean and the polymers B and C are islands, and a multilayer in which the polymers B and C are arranged in layers in the polymer A. And the like, but the sea-island type is most preferable. The cross-sectional shape of the fiber is not limited to a circular shape, but may be an irregular cross-section such as a triangle or a quadrangle.

Further, the polymer A, the polymer B and the polymer C
Composite ratio [A: (B + C)
C)] is suitably 1: 4 to 4: 1 by weight ratio. When the proportion of the polymer A is too small, the polymer B and the polymer C are exposed on the fiber surface, or the strength of the fiber is lowered, which is not preferable. On the contrary, the proportion of the polymer B and the polymer C is too small. Endothermic and exothermic abilities.

The ratio between the polymer B and the polymer C is suitably 1: 2 to 2: 1 in terms of weight ratio. When heat absorption is important, the amount of the polymer B is increased and heat generation is important. In this case, the amount of the polymer C is increased.

The fibers of the present invention may have, if necessary,
A moisture absorbing agent, a wetting agent, a coloring agent, a stabilizer, a flame retardant, an antistatic agent and the like can be contained.

[0031]

Next, the present invention will be described in more detail with reference to examples. In addition, the measurement and evaluation method in an example are as follows. (a) Intrinsic viscosity Measured at a temperature of 20 ° C. using an equal weight mixture of phenol and ethane tetrachloride as a solvent. (b) Endothermic and exothermic capacity A plain fabric of the sample fiber and a plain fabric of polyethylene terephthalate fiber were stuck on a metal plate, the temperature was raised from room temperature, and the temperature was maintained at 40 ° C. The temperature of the fabric was lowered to ° C., and the surface temperature of the fabric was observed with an infrared imager (thermoviewer JTG-IB / IBT type manufactured by JEOL Ltd.), and the surface temperature difference between the two fabrics was determined and evaluated.

Example 1 Glutaric acid and 1.6-fold moles of 1,4-butanediol were subjected to an esterification reaction by a conventional method, and the esterification reaction product was added in an amount of 3 × 10 ^-4 mol per mol of glutaric acid. Was added as a catalyst, and a polycondensation reaction was performed at 270 ° C. and 1 torr for 3 hours to obtain a polyester (B). The obtained polyester (B) has an intrinsic viscosity of 0.60, T
m 32 ° C., Tc 10 ° C., ΔHf 50 mJ / mg, ΔHc 48 mJ / mg. Also, adipic acid and 1.6 times its molar amount of 1,4-butanediol are subjected to an esterification reaction by a conventional method,
The esterification reaction product was added 3 × to 1 mol of adipic acid.
10 ^-4 mol of tetrabutyl titanate was added as a catalyst,
A polycondensation reaction was performed at 270 ° C. and 1 torr for 3 hours to obtain a polyester (C). The obtained polyester (C) had an intrinsic viscosity of 0.61, Tm of 58 ° C., Tc of 27 ° C., ΔHf of 58 mJ / mg, ΔHc of
It was 60 mJ / mg. These polyesters (B) and (C) are used as island components, and polyethylene terephthalate (A) having an intrinsic viscosity of 0.68 as a sea component. A):
A 75d / 36f filament yarn having a weight ratio of (B) :( C) of 1: 1: 1 was obtained. A plain woven fabric was woven using the obtained filament yarn, and the heat absorption and heat generation ability were evaluated.

Examples 2 to 8 Polyesters having the composition and characteristic values shown in Table 1 were obtained as polyesters (polymer B and polymer C) having eight island components.
And the same test as in Example 1 was performed. (However, in Example 8, a fiber having a triangular cross section was used.)

The results of the examples are summarized in Table 1.

[0035]

[Table 1]

Comparative Examples 1 to 7 As the polyester (polymer B and polymer C) of the island component, those having the composition and the characteristic values shown in Table 1 were obtained.
And the same test as in Example 1 was performed.

Table 2 shows the results of the comparative examples.

[0038]

[Table 2]

In Tables 1 and 2, the symbols of the acid component and the diol component indicate the following. GA: glutaric acid PA: pimelic acid EG: ethylene glycol AA: adipic acid TA: terephthalic acid PD: 1,3-propanediol SUA: suberic acid IA: isophthalic acid BD: 1,4-butanediol SEA: sebacic acid PTD: 1,5-pentanediol DDA: dodecanedioic acid HD: 1,6-hexanediol ND: 1,9-nonanediol

[0040]

According to the present invention, there is provided an endothermic fiber which absorbs heat or generates heat due to a change in body temperature or outside air temperature, which is suitable as a fiber for clothing.

──────────────────────────────────────────────────続 き Continuation of the front page (56) References JP-A-6-41818 (JP, A) JP-A-4-11006 (JP, A) JP-A-59-5919 (JP, A) JP-A-58-58 4819 (JP, A) JP-A-51-11909 (JP, A) (58) Fields investigated (Int. Cl. ⁷ , DB name) D01F 8/00-8/16 D01F 6/62 306 D01D 5/34

Claims (2)

(57) [Claims] 1. Three different thermoplastic polymers
(Polymer A, B, C), the polymer A
The covering conjugate fiber, wherein the polymer A has a melting point or softness.
The melting point of the thermoplastic polymer having a melting point of 110 ° C. or higher and polymer B is
Is a thermoplastic polymer having a heat of fusion of 10 mJ / mg or more,
Polymer C has a temperature-reducing crystallization temperature of 40 ° C. or less and a crystallization heat of 10
characterized in that it is a thermoplastic polymer of mJ / mg or more.
Heat and exothermic composite fibers. 2. The polymer A is a polyethylene terephthalate, a polybutylene terephthalate or a polyester mainly composed of these, and the polymer B is a linear aliphatic polyester having a melting point of 30 to 40 ° C. and a heat of fusion of 50 mJ / mg or more. 2. The endothermic and exothermic composite fiber according to claim 1, wherein C is a linear aliphatic polyester having a crystallization temperature of 30 ° C. or less and a crystallization heat of 50 mJ / mg or more.