JPH02133610A - Far-infrared light emitting acrylic fiber and production thereof - Google Patents

Abstract

PURPOSE:To stably obtain the subject fiber having excellent spinning properties, etc., in low cost by subjecting to conjugate spinning a spinning solution composed of acrylic polymer solution copolymerized with specific component and a spinning solution composed of said polymer solution mixed with specific infrared light emitting substance. CONSTITUTION:At first, a far-infrared light emitting substance (preferably highly purified zirconia) having >=70% in average of far-infrared emitting fraction in a region of 6-14mum at 40 deg.C is uniformly dispersed in a solvent and a solution of acrylic polymer in which >=0.2mol% sulfonic acid group-containing monomer is copolymerized is added to said solvent to prepare raw solution of master polymer. Next, said raw solution and raw solution of acrylic polymer copolymerized of >=0.2mol% sulfonic acid group-containing monomer are subjected to conjugate spinning through static mixer to afford the aimed fiber containing >=0.5wt.% the above-mentioned far-infrared light emitting substance, copolymerized of >=0.2mol% sulfonic acid-containing monomer and having >=2.5g/d tensile strength and >=1g/d knot strength.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Application Field 1] The present invention relates to far infrared emitting acrylic fiber J3 and a method for producing the same, particularly far infrared emitting acrylic fiber J3 that has effects such as heat retention, heat storage, freshness preservation, and promotion of blood circulation at room temperature. This invention relates to a river-based acrylic fiber and a method for producing the same.

[Conventional technology] In recent years, heat retention using far-infrared radiation at room temperature has become popular.

The effects of heat storage, keeping freshness up to 1 meter, and promoting blood circulation have been clarified1.Insulators coated with far-infrared radioactive materials, especially far-infrared radioactive ceramics, on the surface of fibers have been put into practical use, but these types of textile products There have been problems with the soft texture and the far-infrared emitting ceramic falling off. In order to solve these problems, a fiber kneading type has been considered, but due to process stability problems at the spinning stage), spinning, dyeability, etc., far-infrared emitting ceramic containing Most of the fibers are made of fibers with a small amount of fiber, and the only known ones are those made of fibers made by melt-spinning, such as nylon and polystyrene.

On the other hand, the core-sheath composite fibers of Nai-1-1-d3 and polyester (2) can increase the above-mentioned Relamiku content and improve culm stability, spinnability, dyeability, durability, etc. Japanese Patent Laid-Open No. 63-92720 discloses that

However, such synthetic fibers U [C also have a large]
~ Not only is it high, but it also has a long distance outside line due to wet spinning.
Dispersion of far-infrared ray film ql ceramic ↑ (1) is unsuitable as a manufacturing method for qayed acrylic fibers due to process stability in the spinning stage due to defects, spinnability and dyeability of qayed fibers, etc. .

[Problem to be Solved by the Invention 1)] The problem of the present invention is to solve the above-mentioned problems of the prior art, and to provide a far-infrared emitting acrylic fiber that is inexpensive and has excellent spinnability and dyeability, and spinning of the fiber. The object of the present invention is to provide a manufacturing method with excellent process stability in step A3.

[Means for Solving the Problems] The above-mentioned problems of the present invention are as follows: (1) far infrared radiation characteristics at 40°C have wavelengths of 6 to 1
The number of far infrared rays that is more than 70% on average in the area of 4 μm Q4
Contains 0.5% or more of a far-infrared emitting substance with characteristics, and contains monomers containing sulfonic acid groups in an amount of O62 mol%.
7 Krylic fibers with a tensile strength of 2.50/d or more, a knot strength of 1°Q O/d or more, and a far-infrared radiation amount of 2.50/d or more.

(2) The far-infrared emitting acrylic fiber according to claim (1), wherein the far-infrared emitting substance has an average particle size of less than 2.00 m.

(3) In claim (1), far infrared rays j
j'i The average particle size of the QJ substance is less than 0.1 μm, far-infrared 94t, radioactive acrylic fiber.

(4) Far infrared emissivity at J3 at 40°C is wavelength 6-1
Far infrared ray number 041 with an average of 70% or more in the 4μm area
M
A master polymer stock solution is prepared by adding a copolymerized acrylic polymer solution, and then the master polymer stock solution and sulfonic acid V are added (acrylic resin copolymerized with 0.2 mol% or more of sulfonic acid V). A method for producing far-infrared radiation acrylic fibers, which comprises performing composite spinning with Boria 1K liquid through a static mixer.

It can be solved by

That is, the far-infrared emissive acrylic fiber of the present invention (hereinafter referred to as the "invention fiber") has a far-infrared emissivity at 10°C of an average of 70% or more in the wavelength range of 6 to 14 μm, preferably 80% or more. It is necessary to contain fine particles that have far-infrared radiation properties.

At this time, far-infrared cytoray radioactive fine particles 1, 40℃, wavelength 6~
The average far infrared emissivity at 14 μm is 70%.Kiman has a small amount of far infrared radiation and does not exhibit sufficient effects such as keeping warm, stupefying and promoting blood circulation. , t less than 2.011 m, more preferably less than 1.0 am, particularly preferably 0.
It is less than 1 μm. When this average particle size is within the range specified above, there will be almost no problems such as clogging of the spinning nozzle during spinning, a decrease in the strength and knot strength of the product yarn, and various problems during spinning, which are related to operability. When the average particle size is less than 0.1 μm, the dyeability of the product yarn is good.

The above-mentioned far-infrared emissive particles include oxide ceramics,
Examples include carbide ceramics and nitride ceramics, but particularly preferred far-infrared emitting fine particles are oxide ceramics. Among these oxide ceramics, preferred are zirconia (ZrO) and silica (ZrO).
Si 02 >Alumina (△9203), and more preferred is high purity zirconia.

In addition, the fiber of the present invention contains the above-mentioned far-infrared radiation 11 fine particles in the fiber at a maximum of 0.5% by weight or more, preferably 2.0 to 20.0%.
Impregnated with 1N% illustrator. This amount of fine particles is 0.5%
If the amount is less than that, the amount of far-infrared radiation will be insufficient, and the effects of heat retention, vinegar fever, and promotion of blood circulation will not be achieved.

Furthermore, the fiber of the present invention can be used as a dispersant for the above-mentioned far-infrared emissivity ceramic. ; As the acrylic polymer that fulfills the function 11, it is necessary to combine 0.2 mol% or more of a monomer having a sulfonic acid group, preferably 0.3 to 1.0 mol% (13). Monoma darkness is 0
．． If the amount is less than 2 mol %, the far-infrared copper has poor ramic dispersibility, [] metal clogging is likely to occur, and the physical properties of the product yarn are poor, resulting in poor spinnability.

Examples of the sulfonic acid group-containing monomer include sodium allylsulfonate, methallylsulfone sulfonate, sodium p-styrenesulfonate, sodium methacrylpropanesulfonate, and ammonium acrylamide-2-methylbu[]panesulfonate. can.

The acrylic polymer in the present invention contains sulfonic acid (1) [In addition to sulfonic acid, if necessary, acrylic acid, methacrylic acid and their lower alkyls, itaconic acid, acrylamide, methacrylamide, vinyl acetate, Vinyl compounds such as vinyl chloride, styrene, and nylidene chloride can be copolymerized.

Furthermore, the fiber of the present invention has a tensile strength of 2.5 g/d or more.

It is necessary to maintain mechanical properties of preferably 3.0 s76 or more, knot strength 1.0 g/d or more, preferably 1.5 q/d or more.

At this time, if the tensile strength is less than 2.59/fi, the spinnability will be poor. On the other hand, the nodule strength is 1. If it is less than Og/d, spinnability will be significantly reduced. In addition, the elongation is 20% or more,
Preferably, when it is 7% or more, spinnability is good.

The far-infrared emissivity<d3 and particle diameter) of the far-infrared emitting ceramic in the fiber of the present invention 43 is measured as follows.

Far-infrared emissivity: BrukC! "It was measured using an FT-IR instrument.

Particle diameter: Measured using a scanning electron
The J Lysis System was used.

Next, the production example of the above-mentioned fiber of the present invention will be explained. r1, and can be obtained by known small methods such as solution Φ-polymerization using a radical initiator, emulsification method, suspension polymerization, etc.

The solvent used for the acrylic polymer may be any solvent that can dissolve the heptacrylic polymer in terms of active water. For example, dimethylformamide, dimethylacetamide, dimethylsulfoxide (DMSO),
These include nitric acid, zinc chloride aqueous solution, and sodium diocyanate aqueous solution.

The spinning raw material of the acrylic polymer) (The polymer concentration may be appropriately selected depending on the molecular weight of the polymer and the properties of the solvent, but it is usually 10 to 25% by weight, preferably 12 to 23% by weight. be.

The temperature of the spinning dope is 40 to 100°C, preferably 50°C.
It is desirable to heat it to ~80°C.

On the other hand, a predetermined amount of far-infrared emitting ceramic is mixed into a part of the spinning stock solution to prepare a master polymer stock solution, and at this time, the far-infrared emitting ceramic is 0.5% by weight or more based on the acrylic polymer. shall be. Further, the temperature of the spinning dope is preferably 40 to 100°C, preferably 50 to 80°C.

A master polymer stock solution of the above-mentioned far-infrared emitting ceramic-containing acrylic polymer and a spinning stock solution of an acrylic polymer copolymerized with 0.2 mol% or more of a monomer having a sulfonic acid group are mixed into "Scare Miki υ-" (manufactured by Sakura Seisakusho). Composite spinning is carried out through a static mixer such as the Hi-Mixer (manufactured by Toshi). By adopting such a revival method, dyeability and physical properties are improved. In particular, in terms of physical properties, the tensile strength is 2.5q/d or more, and the knot strength is 2.59, which satisfies the physical properties for stable production, high-order processing, and especially the spinning process.
A fiber having physical properties of /d or more can be obtained.

Furthermore, since natural crimp occurs, mechanical crimp can be reduced, and buckling due to mechanical crimp can be prevented. The preferred number of crimps is 8 to 12/25 mm, and the degree of crimp is 19 to 18%.

The spinneret used for this composite spinning has a pore diameter of 0.05 to 0.2
A diameter of about 0 mm is preferable.

Examples of the coagulation bath at this time include 1-toluene, dichloromethane, methanol, ethanol, acetone, acrylonitrile, water and/or (51), mixtures thereof, or mixtures of these and the above-mentioned polymer solvents.

The jqed coagulated yarn is heated in a hot water bath at 60 to 100°C for 4 hours.
The film is stretched twice, preferably 6 to 8 times, and then washed with water, or washed with water, stretched, and dried.

The fiber of the present invention can be produced by a spinning method similar to that used for general acrylic fibers.

[Example 1 The present invention will be explained in more detail with reference to Examples below.

In addition, in this example, the heat radiation of the fibers causes two body temperature increases.

The spectral emissivity 8 and heat storage properties at a wavelength of 6 to 14 μm were measured according to the following measurement method.

Hanging for heat dissipation: The sample was heated to 40°C and measured using FT-IH manufactured by Blker.

Temperature upper back: Processed sample into gloves to allow sunlight to enter 20
The temperature rise in the surface layer of the hand was measured 1 hour after wearing it at Tokyo Metropolitan Government Building at 65% R1+.

Heat storage properties: After leaving the sample on a hot plate at 40°C for 1 minute, remove it from the hot plate and use thermal vision (Japanese Manufactured by Avionics.

Confirmed using thermal image or -TIP 1400).

To Example 1/5, Comparative Examples 1 to 3 A spinning stock solution of a sodium methallylsulfonate copolymerized acrylic polymer having (7')3=1.2 is prepared in a conventional manner. The viscosity of this spinning dope was 500 voids (45°C).

On the other hand, zirconia (ZrO2) is dispersed in DMSO, and a portion of the acrylic polymer spinning stock solution is added thereto to prepare a zirconia-containing master polymer stock solution of 100 voids (45°C).

The above-mentioned acrylic polymer spinning stock solution and zirconia-containing master polymer stock solution were multi-layered in a 5-stage high mixer, extruded through a nozzle with a hole diameter of 0.08 mmφ and 100 holes, and heated at 30°C with a 55% DMSO aqueous solution. After that, it was coagulated in a vacuum chamber, then stretched 6 times in hot water, washed with water, and dried to a single yarn fineness of 3. I got Od's.

For comparison, instead of performing multilayer composite spinning using an acrylic polymer spinning stock solution and a zirconia-containing master polymer stock solution using a Pahy mixer, both stock solutions were mixed at 60°C for 1 hour.
After uniformly stirring and mixing for 0 hours, the mixture was made into fibers by wet spinning (Comparative Example 3).

The properties of the obtained fibers are shown in the table below.

(Hereinafter, blank) [Effects of the invention] 2) Hoheto d3, this defense fiber has a far infrared number Q4
Far-infrared emissivity, particle size, and particle ω.

By limiting the sulfonic acid group-containing 1-U thread and the mechanical properties of the fiber, we have created an inexpensive Acnol fiber with excellent far-infrared emissivity, such as spinnability, dyeability, and durability.
It was possible to provide a manufacturing means with excellent stability in the spinning process. Also, when this fiber 4+ffL is used for sweaters, socks, underwear, etc., it retains heat and stores heat.

It not only promotes blood circulation, but also has remarkable effects in the field of far-infrared emitting fibers, such as being effective in preserving freshness when used in vegetable storage bags.

Claims (4)

[Claims] (1) Far infrared emissivity at 40°C is wavelength 6-14μ
Tensile strength 2 containing 0.5% by weight or more of a far-infrared emitting substance that has far-infrared radiation properties of 70% or more on average in the region m, and copolymerizing 0.2% or more of a monomer having a sulfonic acid group. .5g/d or more, knot strength 1.0g/
Acrylic fiber that emits far infrared radiation of d or more. (2) The far-infrared emitting acrylic fiber according to claim (1), wherein the far-infrared emitting substance has an average particle size of less than 2.0 μm. (3) The far-infrared emitting acrylic fiber according to claim (1), wherein the far-infrared emitting substance has an average particle size of less than 0.1 μm. (4) Far-infrared emissivity at 40°C wavelength is 6 to 14μ
A far-infrared emitting substance having an average far-infrared radiation characteristic of 70% or more in the region m is uniformly dispersed in a solvent, and an acrylic polymer solution copolymerized with 0.2 mol% or more of a monomer having a sulfonic acid group is added. A master polymer stock solution is prepared, and then the master polymer stock solution and an acrylic polymer stock solution copolymerized with 0.2 mol% or more of a monomer having a sulfonic acid group are subjected to composite spinning through a static mixer. A method for producing far-infrared emitting acrylic fiber.