JP2005009024A - Boride fine particle-containing fiber and fiber product using the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a fiber having excellent transparency and hardly damaging the design of a fiber product while efficiently absorbing heat rays and having excellent heat-retaining properties; and to provide the fiber product obtained by using the fiber. <P>SOLUTION: A dispersing powder is obtained by mixing a boride fine particle with a dispersion medium and a dispersant for dispersing fine particles, carrying out the dispersion treatment thereof, and drying the dispersed product. The obtained dispersing powder is added to a thermoplastic resin pellet, and homogeneously mixed therewith, and the resultant mixture is melt-kneaded to provide a heat ray-absorbing component-containing master batch. The heat ray-absorbing component-containing master batch is mixed with a master batch which is prepared by the same method and to which the inorganic fine particles are not added, and the resultant mixture is melt-spun and drawn in series to produce a multifilament yarn. The multifilament yarn is cut to provide a staple, and a spun yarn having the heat ray-absorbing effect is produced therefrom. Knit goods having the heat-retaining properties are obtained by using the spun yarn. <P>COPYRIGHT: (C)2005,JPO&NCIPI

Description

[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a fiber containing a heat-absorbing component and a fiber product obtained by processing the fiber.
[0002]
[Prior art]
In the fiber field, fibers having various special functions are desired. One of them is a fiber with heat retention. In general, in order to increase the heat retaining property of a textile product, methods such as making the fabric thicker, making the eyes finer, or making the color darker have been employed.
[0003]
Patent Document 1 discloses that one or more inorganic fine particles such as silica or barium sulfate have a thermal conductivity of 0.3 kcal / m. ² A technique is described that uses heat ray radiating fibers containing inorganic fine particles having heat ray emission characteristics containing at least one kind of metal and metal ions of sec ° C. or higher, and improving the heat retention of the fibers.
[0004]
Patent document 2 describes that ceramic fine particles having a far-infrared radiation ability of 0.1 to 20% by weight with respect to the fiber weight are contained in the fiber to exhibit excellent heat retention. This document describes that the ceramic fine particles include fine particles having light absorption heat conversion ability and aluminum oxide fine particles to exhibit heat retention.
[0005]
Patent Document 3 proposes an infrared-absorbing processed fiber product in which an infrared absorber made of an amino compound and a binder resin containing an ultraviolet absorber and various stabilizers used as desired are dispersed and fixed.
[0006]
In Patent Document 4, fibers selected from direct dyes, reactive dyes, naphthol dyes, and vat dyes, which have a characteristic that absorption in the near infrared region is larger than that of black dyes, are combined with other dyes. There has been proposed a near-infrared absorption processing method for cellulosic fiber structures having a low spectral reflectance of 65% or less within the near-infrared wavelength range of 750 to 1500 nm by dyeing.
[0007]
[Patent Document 1]
JP-A-11-279830
[Patent Document 2]
JP-A-5-239716
[Patent Document 3]
JP-A-8-3870
[Patent Document 4]
JP-A-9-291463
[0008]
[Problems to be solved by the invention]
As described above, the fiber with heat retention according to the conventional technology has a high specific gravity of the fiber due to a large amount of the additive added to the fiber, and the clothes made with this fiber become heavy or melted. There has been a problem that it becomes extremely difficult to uniformly disperse into the spun yarn.
In addition, when an organic material or a dye is used, since the infrared absorber used is an organic material or a black dye, there is a problem that deterioration due to heat and humidity is remarkable and weather resistance is poor. Furthermore, since the fibers are colored dark by applying these materials to the fibers, they cannot be used for light-colored products, and there is a problem that usable fields are limited.
[0009]
In addition to the methods described above, a technique for improving the heat retaining property by providing a radiation reflection effect by fixing a metal powder such as aluminum or titanium to a fiber or attaching it by vapor deposition or the like is also known. . However, the application is limited due to the large change in the color of the fiber due to fixation and vapor deposition processing, the cost associated with vapor deposition processing increases, the occurrence of vapor deposition spots due to delicate handling of the fabric in the preparation process before vapor deposition processing, washing or wearing There were various problems such as a decrease in heat retention performance due to the drop of the deposited metal due to friction at the time.
[0010]
The present invention is based on the above-mentioned background, and has excellent transparency and weather resistance, a fiber containing a heat ray absorbing component that efficiently absorbs heat rays, and the use of the fiber, and has excellent heat retention. An object of the present invention is to provide a textile product that does not impair the designability.
[0011]
[Means for Solving the Problems]
As a result of repeated studies by the present inventors in order to achieve the above object, a general formula XB is used as a heat ray absorbing component capable of solving the above-mentioned problems. _m (However, X is at least one element selected from La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu, Sr, Ca, and Y. ) Boride fine particles represented by The boride fine particles possess a large amount of free electrons, but by making them fine particles, the material itself has the maximum transmittance in the visible light region and also exhibits strong absorption in the near infrared region. As a result, a phenomenon has been found in which the transmittance becomes minimum. Then, the boride fine particles are contained in the surface and / or inside of the fiber, and it is found that the fiber can be kept warm by developing strong absorption in the near-infrared region, thereby completing the present invention. It was.
[0012]
That is, the first means for solving the problem is:
As a heat ray absorbing component, the general formula XB _m (However, X is at least one element selected from La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu, Sr, Ca, and Y. ) Containing boride fine particles represented by:
The boride fine particle-containing fiber, wherein the fine particle is contained in the surface and / or inside of the fiber in an amount of 0.001% by weight to 30% by weight with respect to the solid content of the fiber.
[0013]
The second means is the boride fine particle-containing fiber according to the first means,
In addition, it contains far-infrared radiation
A boride fine particle-containing fiber characterized in that the far-infrared emitting substance is contained on the surface and / or inside of the fiber in an amount of 0.001% to 30% by weight based on the solid content of the fiber. .
[0014]
The third means is the boride fine particle-containing fiber according to the second means,
The far-infrared emitting material is ZrO. ₂ A boride fine particle-containing fiber characterized by being a fine particle.
[0015]
A fourth means is a boride fine particle-containing fiber according to any one of the first to third means,
The boride fine particle-containing fiber, wherein the boride fine particle has a particle size of 800 nm or less.
[0016]
A fifth means is the boride fine particle-containing fiber according to any one of the first to fourth means,
The boride fine particle-containing fiber is characterized in that the surface of the boride fine particles is coated with a compound containing at least one element selected from silicon, zirconium, titanium, and aluminum.
[0017]
A sixth means is the boride fine particle-containing fiber according to the fifth means,
The boride fine particle-containing fiber, wherein the compound is an oxide.
[0018]
Seventh means is a boride fine particle-containing fiber according to any one of the first to sixth means,
A boride fine particle-containing fiber characterized in that the fiber is a synthetic fiber, a semi-synthetic fiber, a natural fiber, a recycled fiber, an inorganic fiber, or a blended yarn, a blended yarn, a blended yarn or the like of these. is there.
[0019]
The eighth means is the boride fine particle-containing fiber according to the seventh means,
The synthetic fiber is any one selected from polyurethane fiber, polyamide fiber, acrylic fiber, polyester fiber, polyolefin fiber, polyvinyl alcohol fiber, polyvinylidene chloride fiber, polyvinyl chloride fiber, and polyether ester fiber. It is a boride fine particle-containing fiber characterized by being one or more kinds of synthetic fibers.
[0020]
A ninth means is the boride fine particle-containing fiber according to the seventh means,
The boric fine particle-containing fiber, wherein the semi-synthetic fiber is at least one semi-synthetic fiber selected from cellulose fiber, protein fiber, chlorinated rubber, and hydrochloric acid rubber.
[0021]
A tenth means is the boride fine particle-containing fiber according to the seventh means,
The boric fine particle-containing fiber, wherein the natural fiber is one or more natural fibers selected from plant fibers, animal fibers, and mineral fibers.
[0022]
The eleventh means is the boride fine particle-containing fiber according to the seventh means,
The borated fine particle-containing fiber, wherein the regenerated fiber is at least one regenerated fiber selected from cellulosic fiber, protein fiber, algin fiber, rubber fiber, chitin fiber, and mannan fiber.
[0023]
A twelfth means is the boride fine particle-containing fiber according to the seventh means,
The borate fine particle-containing fiber, wherein the inorganic fiber is one or more inorganic fibers selected from metal fibers, carbon fibers, and silicate fibers.
[0024]
A thirteenth means is a fiber product obtained by processing the boride fine particle-containing fiber according to any one of the first to twelfth means.
[0025]
DETAILED DESCRIPTION OF THE INVENTION
The fiber provided with heat retention according to the present invention is a general formula XB as a component for absorbing heat rays. _m XB ₄ , XB ₆ , XB ₁₂ It is produced by containing boride fine particles represented by the above on the surface and / or inside of a desired fiber.
Here, boride fine particles preferable as a heat ray absorbing component will be described.
First, as the component for absorbing heat rays, the general formula XB described above is used. _m It is preferable that 4 ≦ m <6.3. That is, as boride fine particles, among the boride, XB ₄ , XB ₆ Is preferred, and some XB ₁₂ May be included. Here, m is a chemical analysis of the obtained powder containing boride fine particles, and indicates the atomic ratio of B to one atom of the X element.
[0026]
Usually, the powder containing boride fine particles is actually XB ₄ , XB ₆ , XB ₁₂ And the like. For example, in the case of hexaboride which is a typical boride fine particle, even if it is judged that it is a single phase from the result of X-ray diffraction, 5.8 <m <6.2 is actually obtained, and the amount is very small. It is thought that other phases are included. Here, when m ≧ 4, XB, XB ₂ However, the reason is unknown, but the heat ray absorption characteristics are improved. On the other hand, when m <6.3, the generation of boron oxide particles in addition to the boride fine particles is suppressed. Since boron oxide particles are hygroscopic, when boron oxide particles are mixed in boride powder, the moisture resistance of the boride powder is lowered, and deterioration of heat absorption characteristics with time is increased. Therefore, it is preferable to suppress the generation of boron oxide particles when m <6.3.
[0027]
In the following description, hexaboride in the case of m = 6 will be described as an example.
The heat-retaining fiber of the present invention is a hexaboride XB as a component for absorbing heat rays. ₆ (X is at least one selected from La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu, Sr, Ca, Y) It is produced by containing it on the surface and / or inside of the fiber.
The hexaboride used in the present invention includes LaB ₆ , CeB ₆ , PrB ₆ , NdB ₆ , SmB ₆ , EuB ₆ , GdB ₆ , TbB ₆ , DyB ₆ , HoB ₆ , ErB ₆ , TmB ₆ , YbB ₆ , LuB ₆ , SrB ₆ , CaB ₆ And YB ₆ Is mentioned.
[0028]
The hexaboride fine particles used in the present invention are preferably not oxidized on the surface, but usually they are slightly oxidized, and surface oxidation occurs to some extent during the fine particle dispersion process. Inevitable. However, even in that case, there is no change in the effectiveness of expressing the solar radiation absorbing effect. In addition, the higher the completeness of the crystal, the greater the effect of solar radiation absorption. However, even if the crystallinity is low and a broad diffraction peak is generated by X-ray diffraction, the basic inside of the microparticle Bond is cubic CaB ₆ If it has a structure of the type, it will exhibit solar radiation absorption effect. In addition, hexaboride microparticles are excellent in weather resistance because they are inorganic substances.
[0029]
These hexaboride fine particles are powders such as dark blue-violet and green, but the particle size is sufficiently smaller than the visible light wavelength, and the fine particles having this small particle size are dispersed on the surface and / or inside of the fiber. In the state of being contained, visible light permeability is generated, but the heat ray absorbing ability can be kept sufficiently strong. This is because the amount of free electrons in the hexaboride fine particles is large, and the absorption energy of plasmon absorption and indirect band-to-band transition due to free electrons inside and on the fine particles is just in the vicinity of visible to near-infrared light. This is thought to be because heat rays in this wavelength region are selectively reflected and absorbed. According to experiments, in a film in which these hexaboride fine particles are sufficiently finely and uniformly dispersed, the transmittance has a maximum value between wavelengths of 400 to 700 nm and a minimum value between wavelengths of 700 to 1800 nm. found. Therefore, the same wavelength characteristic of transmittance can be obtained even in a fiber containing the hexaboride fine particles on the surface and / or inside of the fiber.
Here, considering that the human visible light wavelength is 380 to 780 nm and the visibility is a bell-shaped peak having a peak around 550 nm, the fiber containing such hexaboride fine particles effectively makes visible light visible. It is understood that it transmits and effectively reflects and absorbs other heat rays.
[0030]
Moreover, the heat ray absorption capability per unit weight of the hexaboride fine particles is very high, and the effect can be exerted with a use amount of 40 to 1/100 or less as compared with ITO or ATO. Therefore, even if the amount of fine particles added to the desired fiber is small, a sufficient heat ray absorbing ability can be ensured, and there is an advantage that the physical properties of the fiber are not impaired. Of course, a large amount can be added if desired, and the content of hexaboride fine particles on the surface and / or inside of the fiber is 0.001% to 30% by weight with respect to the solid content of the fiber. You can select by range. Furthermore, from the viewpoint of considering the weight of the fiber after addition of hexaboride fine particles and raw material cost, it is preferably in the range of 0.005 wt% to 15 wt%, more preferably in the range of 0.005 wt% to 10 wt%. It is good to select with. If the added amount is 0.001% by weight or more, a sufficient heat ray absorbing effect can be obtained even if the fabric is thick, and if it is less than 30% by weight, it is possible to clog the filter or break the yarn in the spinning process. A decrease in spinnability can be avoided. If it is less than 15% by weight, the spinnability can be further stabilized, and if it is less than 10% by weight, it is more preferable.
[0031]
In addition, it is also preferable that fine particles of a substance having a capability of emitting far-infrared rays are included in the surface and / or inside of the fiber together with the hexaboride fine particles. As the fine particles of the far-infrared emitting material, for example, ZrO ₂ , SiO ₂ TiO ₂ , Al ₂ O ₃ , MnO ₂ , MgO, Fe ₂ O ₃ , Metal oxides such as CuO, carbides such as ZrC, SiC, TiC, ZrN, Si ₃ N ₄ And nitrides such as AlN.
[0032]
The hexaboride fine particles have the property of absorbing light energy such as sunlight having a wavelength of 0.3 to 2 μm, and selectively absorb and re-radiate light in the near infrared region near the wavelength of 1 μm. Or convert to heat. The above-mentioned fine particles of the far-infrared emitting material have the ability to receive the energy absorbed by the hexaboride fine particles, convert it into thermal energy of the middle and far-infrared wavelengths, and emit it. For example, ZrO ₂ The fine particles convert the heat absorbed by the hexaboride fine particles into heat energy having a wavelength of 2 to 20 μm and radiate it. Therefore, since the absorbed energy is exchanged between the fine particles and efficiently emitted, more effective heat retention is achieved.
[0033]
The content of fine particles of the far-infrared emitting material in the fiber surface and / or inside is preferably used between 0.001 wt% and 30 wt% with respect to the solid content of the fiber. If the amount used is 0.001% by weight or more, sufficient heat energy radiation effect can be obtained even if the fabric is thick, and if it is 30% by weight or less, the filter may be clogged or broken in the spinning process. A decrease in spinnability can be avoided.
[0034]
Next, preferable particle diameters of the hexaboride fine particles and the far-infrared emitting fine particles will be described.
Generally, it is important that the particle size of the inorganic fine particles contained in the fiber does not cause a problem during the fiberizing process such as spinning and drawing. From this viewpoint, the average particle size is 5 μm or less. Preferably, it is 3 μm or less. If the average particle size is 5 μm or less, it is possible to avoid problems such as clogging of the filter in the spinning process and deterioration of spinnability due to thread breakage, and also avoid problems such as thread breakage in the drawing process. can do. Furthermore, if the average particle diameter is 5 μm or less, the inorganic fine particles can be easily uniformly mixed and dispersed in the spinning raw material.
[0035]
Furthermore, from the viewpoint of design properties such as dyeability of textile materials such as clothing, it is required to efficiently shield near infrared rays while maintaining transparency. However, if the particle size of the inorganic fine particles is large, the light in the visible light region of 400 to 780 nm is scattered by geometrical scattering or diffraction scattering to become a frosted glass, and it becomes difficult to obtain clear transparency. Therefore, when the particle size of the hexaboride fine particles according to the present invention is made smaller than 800 nm, visible light is not shielded, so that near infrared rays can be shielded efficiently while maintaining transparency in the visible light region.
Further, when the inorganic fine particle diameter is 200 nm or less, the scattering is reduced and a Mie scattering or Rayleigh scattering region is obtained. In particular, when the particle size is reduced to the Rayleigh scattering region, the scattered light is reduced in inverse proportion to the sixth power of the dispersed particle size, so that scattering is reduced and transparency is improved as the particle size is reduced. Further, when the thickness is 100 nm or less, the scattered light is preferably very small. Therefore, particularly when the transparency in the visible light region is emphasized, the inorganic fine particle diameter is preferably 200 nm or less, more preferably 100 nm or less.
[0036]
In addition, in order to improve the weather resistance of the hexaboride fine particles, it is also preferable to coat the surface of the fine particles with a compound containing one or more elements selected from silicon, zirconium, titanium, and aluminum. These compounds are basically transparent, and the visible light transmittance is not reduced by covering the hexaboride fine particles, so that the design of the fiber is not impaired. Further, these compounds are preferably oxides. Since these oxides have a high far-infrared radiation ability, the heat retention effect is also improved.
[0037]
The fibers used in the present invention can be variously selected according to the application, including synthetic fibers, semi-synthetic fibers, natural fibers, regenerated fibers, inorganic fibers, or mixed yarns of these blended yarns, synthetic yarns, mixed fibers, etc. Either one can be used. From the viewpoints of containing inorganic fine particles such as hexaboride fine particles and far-infrared emitting fine particles in the fibers by a simple method and maintaining heat retention, synthetic fibers are preferable.
The synthetic fiber is not particularly limited. For example, polyurethane fiber, polyamide fiber, acrylic fiber, polyester fiber, polyolefin fiber, polyvinyl alcohol fiber, polyvinylidene chloride fiber, polyvinyl chloride fiber, polyether ester. System fibers and the like.
Here, examples of the polyamide fiber include nylon, nylon 6, nylon 66, nylon 11, nylon 610, nylon 612, aromatic nylon, and aramid.
Examples of the acrylic fiber include polyacrylonitrile, acrylonitrile-vinyl chloride copolymer, modacrylic and the like.
Examples of the polyester fiber include polyethylene terephthalate, polybutylene terephthalate, polytrimethylene terephthalate, and polyethylene naphthalate.
Examples of the polyolefin fiber include polyethylene, polypropylene, and polystyrene.
Moreover, as a polyvinyl alcohol-type fiber, vinylon etc. are mentioned, for example.
Examples of the polyvinylidene chloride fiber include vinylidene.
Examples of the polyvinyl chloride fiber include polyvinyl chloride.
Examples of the polyether ester fiber include Lexe and Success.
[0038]
When the fiber used in the present invention is a semi-synthetic fiber, for example, cellulose fiber, protein fiber, chlorinated rubber, hydrochloric acid rubber and the like can be mentioned.
Examples of cellulosic fibers include acetate, triacetate, and oxide acetate.
Here, as a protein fiber, a promix etc. are mentioned, for example.
[0039]
When the fiber used for this invention is a natural fiber, a vegetable fiber, an animal fiber, a mineral fiber etc. are mentioned, for example.
Here, examples of the plant fiber include cotton, kapok, flax, hemp, jute, manila hemp, sisal hemp, New Zealand hemp, arabic hemp, palm, rush and straw.
Examples of animal fibers include wool such as wool, goat hair, mohair, cashmere, alpaca, angora, camel, vicuuna, silk, down, feather and the like.
Examples of the mineral fiber include asbestos and asbestos.
[0040]
When the fiber used in the present invention is a regenerated fiber, for example, cellulose fiber, protein fiber, algin fiber, rubber fiber, chitin fiber, mannan fiber and the like can be mentioned.
Here, examples of the cellulosic fiber include rayon, viscose rayon, cupra, polynosic, copper ammonia rayon, and the like.
Examples of the protein fiber include casein fiber, peanut protein fiber, corn protein fiber, soybean protein fiber, and regenerated silk thread.
[0041]
When the fiber used for this invention is an inorganic fiber, a metal fiber, carbon fiber, a silicate fiber etc. are mentioned, for example.
Here, as a metal fiber, a metal fiber, a gold thread, a silver thread, a heat-resistant alloy fiber etc. are mentioned, for example.
Examples of the silicate fiber include glass fiber, mineral fiber, and rock fiber.
[0042]
The cross-sectional shape of the fiber used in the present invention is not particularly limited, and examples thereof include a circle, a triangle, a hollow shape, a flat shape, a Y shape, and a star shape. The fine particles can be included in the surface and / or inside of the fiber in various forms. For example, in the case of a core-sheath type fiber, the fine particles can be contained in the core portion of the fiber or in the sheath portion. It doesn't matter. The shape of the fiber used in the present invention may be a filament (long fiber) or a staple (short fiber).
[0043]
In addition, it is also preferable to add an antioxidant, a flame retardant, a deodorant, an insecticide, an antibacterial agent, an ultraviolet absorber, etc. to the fibers used in the present invention, as long as the performance is not impaired as desired. It is.
[0044]
Next, a method of uniformly containing inorganic fine particles such as hexaboride fine particles and far infrared radiation fine particles on the surface and / or inside of the fiber used in the present invention will be described.
The method for uniformly containing inorganic fine particles on the surface and / or inside of the fiber is not particularly limited, and examples thereof include the following methods.
(1) A method in which the inorganic fine particles are directly mixed and spun into a raw material polymer of a synthetic fiber.
(2) A method in which a masterbatch in which the inorganic fine particles are contained in a high concentration in a part of the raw polymer in advance is manufactured, and this masterbatch is diluted to a predetermined concentration at the time of spinning and then spun.
(3) The inorganic fine particles are uniformly dispersed in the raw material monomer or oligomer solution in advance, and the target raw material polymer is synthesized using the dispersion solution, and at the same time, the inorganic fine particles are uniformly dispersed in the raw material polymer. A method of spinning after caulking.
(4) A method in which the inorganic fine particles are adhered to the surface of a desired fiber obtained by spinning in advance using a binder or the like.
[0045]
Here, a preferred example of the method of spinning the master batch described in the above (2) after producing the master batch and adjusting the dilution during spinning will be described in more detail.
The method for producing the masterbatch is not particularly limited. For example, a hexaboride fine particle dispersion, a thermoplastic resin granule or pellet, and other additives as necessary, a ribbon blender, tumbler, now Uniform while removing the solvent using a mixer such as a turmixer, Henschel mixer, super mixer, planetary mixer, and kneaders such as a banbury mixer, kneader, roll, kneader ruder, single screw extruder, twin screw extruder Thus, a mixture in which fine particles are uniformly dispersed in a thermoplastic resin can be prepared.
[0046]
Furthermore, a method of removing the solvent of the hexaboride fine particle dispersion by a known method, and uniformly melting and mixing the obtained powder and thermoplastic resin granules or pellets and other additives as required. It is also possible to prepare a mixture in which fine particles are uniformly dispersed in a thermoplastic resin. In addition, a method in which hexaboride fine particle powder is directly added to a thermoplastic resin and uniformly melt-mixed can also be used.
[0047]
A heat-absorbing component-containing masterbatch can be obtained by kneading the mixture obtained by the above-described method with a vented uniaxial or biaxial extruder and processing into a pellet.
[0048]
Here, the method of (1)-(4) which makes the fiber used for this invention contain inorganic fine particles uniformly demonstrates a specific example.
Method (1), (2): For example, when polyester fiber is used as the fiber, the hexaboride fine particle dispersion is added to polyethylene terephthalate resin pellets, which are thermoplastic resins, and mixed uniformly with a blender to remove the solvent. Then, it is melt-kneaded with a twin screw extruder to prepare a hexaboride fine particle-containing master batch. This hexaboride fine particle-containing masterbatch and the target amount of a masterbatch made of polyethylene terephthalate containing no fine particles are melt-mixed around the melting temperature of the resin and spun in accordance with a conventional method.
Method (3): For example, when urethane fiber is used as the fiber, a polymer diol containing hexaboride fine particles and an organic diisocyanate are reacted in a twin-screw extruder to synthesize an isocyanate group-terminated prepolymer. A chain extender is reacted here to produce a polyurethane solution (raw polymer). It is spun according to a conventional method.
Method (4): For example, in order to attach inorganic fine particles to the surface of natural fibers, hexaboride fine particles are made of at least one binder resin selected from acrylic, epoxy, urethane, and polyester, and a solvent such as water. The natural fiber is immersed, or the natural fiber is impregnated with the treatment liquid by padding, printing, spraying, or the like, and dried to obtain hexaboride fine particles on the natural fiber. Can be attached.
[0049]
The inorganic fine particles such as hexaboride fine particles and far infrared radiation fine particles may be dispersed by any method as long as the inorganic fine particles are uniformly dispersed in the liquid. For example, a medium stirring mill, a ball mill, a sand mill, There are methods such as ultrasonic dispersion. The dispersion medium of the inorganic fine particles is not particularly limited, and can be selected according to the fibers to be mixed. For example, various common organic solvents such as water, alcohol, ether, ester, ketone, and aromatic compound can be used. Further, it may be directly mixed with a desired fiber or a polymer as a raw material thereof. Moreover, you may adjust pH by adding an acid and an alkali as needed. In order to further improve the dispersion stability of the fine particles, it is also preferable to add various surfactants and coupling agents.
[0050]
As described in detail above, according to the present invention, by using hexaboride fine particles as a heat-absorbing component, and further using fine particles that emit far-infrared rays as desired, the amount of inorganic fine particles added can be contained in the fiber. Even if there is little, it became possible to provide the fiber excellent in heat retention. Further, since the amount of inorganic fine particles added is small, it is possible to avoid impairing the basic physical properties of the fiber such as the strength and elongation of the fiber. And the fiber which concerns on this invention can be used for various uses, such as textile materials, such as the clothing for cold protection which requires heat retention, sports clothing, stockings, a curtain, and other industrial textile materials.
[0051]
【Example】
Hereinafter, the present invention will be described in detail with reference to examples. However, the present invention is not limited to the following examples.
[0052]
(Example 1)
LaB as boride fine particles ₆ Fine particles (specific surface area 30m ² / G) 200 g, 730 g of toluene as a dispersion medium, and 70 g of a dispersing agent for dispersing fine particles are mixed and dispersed in a medium agitating mill. ₆ 1 kg of a fine particle dispersion was prepared (solution A). Furthermore, remove the toluene of (A liquid) using a spray dryer, and LaB ₆ Dispersed powder (A powder) was obtained.
The obtained (A powder) is added to polyethylene terephthalate resin pellets which are thermoplastic resins, mixed uniformly with a blender, melt-kneaded with a twin screw extruder, and the extruded strands are cut into pellets, LaB, a heat ray absorbing component ₆ A master batch containing 30% by weight of fine particles was obtained.
This LaB ₆ A polyethylene terephthalate masterbatch containing 30% by weight of fine particles was mixed with a polyethylene terephthalate masterbatch prepared by the same method to which inorganic fine particles were not added at a weight ratio of 1: 1. LaB ₆ The average particle diameter of the fine particles was observed to be 20 nm from a dark field image formed by a single diffraction ring using a TEM (transmission electron microscope) (hereinafter referred to as dark field method).
This LaB ₆ A mixed master batch containing 15% by weight of fine particles was melt-spun, followed by stretching to produce a polyester multifilament yarn. The obtained multifilament yarn was cut to produce a polyester staple, and a spun yarn was produced using the polyester staple. Using this spun yarn, a knit product having heat retention was obtained.
The spectral characteristics of the manufactured knit product were measured by the transmittance of light having a wavelength of 200 to 2100 nm using a spectrophotometer manufactured by Hitachi, Ltd., and the solar absorptance was calculated according to JIS A 5759. (Here, the solar reflectance was 8% for all samples, and was calculated from the solar absorptance (%) = 100% -solar transmittance (%)-solar reflectance (%).) 45%.
Next, the temperature rise effect on the back side of the fabric of the produced knit product was measured as follows.
Under an environment of 20 ° C. and 60% RH, a solar-beam approximate spectrum lamp (Sellic Corporation XL-03E50 modified) is irradiated from a distance of 30 cm from the fabric, and every certain time (0 seconds, 30 seconds, The temperature of the back surface of the cloth at 60 seconds, 180 seconds, 360 seconds, and 600 seconds) was measured with a radiation thermometer (HT-11 manufactured by Minolta Co., Ltd.). This result is shown in FIG. 1 which is a list of temperature measurement results on the back of the fabric of the knit product for each irradiation time of sunlight approximate light. Moreover, in FIG. 1, the temperature rise effect of the fabric back surface of the knit product obtained in Examples 2 to 7 and Comparative Example 1 is also shown.
[0053]
(Example 2)
LaB ₆ Fine particles and ZrO ₂ A master batch of polyethylene terephthalate containing 10% by weight of fine particles at a ratio of 1: 1.5 was prepared in the same manner as in Example 1. LaB ₆ Fine particles and ZrO ₂ The average particle diameter of the fine particles was observed to be 20 nm and 30 nm, respectively, by dark field method using TEM.
A multifilament yarn was produced in the same manner as in Example 1 using the masterbatch containing the two kinds of fine particles. The obtained multifilament yarn was cut to produce a polyester staple, and a spun yarn was produced in the same manner as in Example 1. A knit product was obtained using this spun yarn.
The spectral characteristics of the manufactured knit product were measured in the same manner as in Example 1. The solar absorptivity was 43.38%. In addition, the temperature rise effect on the back surface of the fabric was measured by the same method as in Example 1. The result is shown in FIG.
[0054]
Example 3
CeB ₆ Fine particles and ZrO ₂ A master batch of polyethylene terephthalate containing 30% by weight of fine particles at a ratio of 1: 1.5 was prepared in the same manner as in Example 1. CeB ₆ Fine particles and ZrO ₂ The average particle size of the fine particles was observed to be 25 nm and 30 nm, respectively, by dark field method using TEM.
A multifilament yarn was produced in the same manner as in Example 1 using the masterbatch containing the two kinds of fine particles. The obtained multifilament yarn was cut to produce a polyester staple, and a spun yarn was produced in the same manner as in Example 1. A knit product was obtained using this spun yarn.
The spectral characteristics of the manufactured knit product were measured in the same manner as in Example 1. The solar absorptivity was 39.21%. In addition, the temperature rise effect on the back surface of the fabric was measured by the same method as in Example 1. The result is shown in FIG.
[0055]
(Example 4)
PrB ₆ Fine particles and ZrO ₂ A master batch of polyethylene terephthalate containing 30% by weight of fine particles at a ratio of 1: 1.5 was prepared in the same manner as in Example 1. PrB ₆ Fine particles and ZrO ₂ The average particle diameter of the fine particles was observed to be 25 nm and 30 nm, respectively, using TEM and dark field method.
A multifilament yarn was produced in the same manner as in Example 1 using the masterbatch containing the two kinds of fine particles. The obtained multifilament yarn was cut to produce a polyester staple, and a spun yarn was produced in the same manner as in Example 1. A knit product was obtained using this spun yarn.
The spectral characteristics of the manufactured knit product were measured in the same manner as in Example 1. The solar absorptivity was 32.95%. In addition, the temperature rise effect on the back surface of the fabric was measured by the same method as in Example 1. The result is shown in FIG.
[0056]
(Comparative Example 1)
A multifilament yarn was produced in the same manner as in Example 1 using the master batch of polyethylene terephthalate not added with the inorganic fine particles described in Example 1. The obtained multifilament yarn was cut to produce a polyester staple, and a spun yarn was produced in the same manner as in Example 1. A knit product was obtained using this spun yarn.
The spectral characteristics of the manufactured knit product were measured in the same manner as in Example 1. The solar absorptivity was 3.74%. In addition, the temperature rise effect on the back surface of the fabric was measured by the same method as in Example 1. The result is shown in FIG.
[0057]
(Example 5)
Except for using nylon resin pellets as the thermoplastic resin, LaB ₆ Fine particles and ZrO ₂ A master batch of nylon 6 containing 10% by weight of fine particles in a ratio of 1: 3 was prepared, and mixed with a master batch of nylon 6 prepared by the same method to which inorganic fine particles were not added at a weight ratio of 1: 1. LaB ₆ Fine particles and ZrO ₂ The average particle diameter of the fine particles was observed to be 20 nm and 30 nm, respectively, using a TEM and using a dark field method.
This LaB ₆ Fine particles and ZrO ₂ A mixed masterbatch containing 5% by weight of fine particles was melt-spun and subsequently drawn to produce a nylon multifilament yarn. The obtained multifilament yarn was cut to produce a nylon staple, and a spun yarn was produced using the nylon staple. Using this spun yarn, a nylon fiber product having heat retaining properties was obtained.
The spectral characteristics of the produced nylon fiber product were measured in the same manner as in Example 1. The solar absorptivity was 44.01%. In addition, the temperature rise effect on the back surface of the fabric was measured by the same method as in Example 1. The result is shown in FIG.
[0058]
(Example 6)
Except for using acrylic resin pellets as the thermoplastic resin, the same method as in Example 1, LaB ₆ Fine particles and ZrO ₂ A masterbatch of polyacrylonitrile containing 20% by weight of fine particles in a ratio of 1: 3 was prepared, and mixed with a masterbatch of polyacrylonitrile prepared by the same method to which inorganic fine particles were not added at a weight ratio of 1: 1. LaB ₆ Fine particles and ZrO ₂ The average particle diameter of the fine particles was observed to be 20 nm and 30 nm, respectively, using a TEM and using a dark field method.
This LaB ₆ Fine particles and ZrO ₂ A mixed master batch containing 10% by weight of fine particles was spun and subsequently drawn to produce an acrylic multifilament yarn. The obtained multifilament yarn was cut to produce an acrylic staple, and a spun yarn was produced using this. Using this spun yarn, an acrylic fiber product having heat retention was obtained.
The spectral characteristics of the produced acrylic fiber product were measured in the same manner as in Example 1. The solar absorptivity was 42.57%. In addition, the temperature rise effect on the back surface of the fabric was measured by the same method as in Example 1. The result is shown in FIG.
[0059]
(Example 7)
LaB ₆ Fine particles and ZrO ₂ Polytetramethylene ether glycol (PTG2000) containing 10% by weight of fine particles at a ratio of 1: 1.5 was reacted with 4,4-diphenylmethane diisocyanate to prepare an isocyanate group-terminated prepolymer. Next, 1,4-butanediol and 3-methyl-1,5-pentanediol were reacted with the prepolymer as a chain extender to carry out polymerization, thereby producing a thermoplastic polyurethane solution. LaB ₆ Fine particles and ZrO ₂ The average particle diameter of the fine particles was observed to be 20 nm and 30 nm, respectively, using a TEM and using a dark field method.
The obtained polyurethane solution was spun as a spinning dope, followed by stretching to obtain polyurethane elastic fibers. A urethane fiber product having heat retaining properties was obtained using this fiber.
The spectral characteristics of the produced urethane fiber product were measured in the same manner as in Example 1. The solar absorptivity was 43.02%. In addition, the temperature rise effect on the back surface of the fabric was measured by the same method as in Example 1. The result is shown in FIG.
[0060]
(Evaluation)
When Examples 1 to 7 and Comparative Example 1 were compared, hexaboride fine particles and ZrO were added to various fibers. ₂ By containing fine particles, the back surface temperature of the fabric made from the fibers became higher on average by 14 ° C. or more than the comparative example after 30 seconds, and it was found that excellent heat retention was imparted. did.
From the above, by incorporating hexaboride fine particles and optionally far-infrared emitting materials into various fibers, excellent transparency, good weather resistance, low cost, and a small amount of fine particles added, It was possible to obtain fibers that efficiently absorb heat rays from sunlight and the like and have heat retention properties, and fiber products that have excellent heat retention properties that are produced from the fibers and that do not impair the design.
And the above-mentioned fiber and the textile product using this are, from its excellent characteristics, such as cold weather clothing that requires heat retention, sports clothing, stockings, textile materials such as curtains, and other industrial textile materials, It can be used for various purposes.
[0061]
【The invention's effect】
As detailed above, the general formula XB is used as the heat-absorbing component according to the present invention. _m (However, X is at least one element selected from La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu, Sr, Ca, and Y. ) Containing boride fine particles represented by:
A boride that absorbs heat rays efficiently while having excellent transparency by containing 0.001% to 30% by weight of the fine particles with respect to the solid content of the fiber on the surface and / or inside of the fiber. A fine particle-containing fiber could be obtained.
[Brief description of the drawings]
BRIEF DESCRIPTION OF DRAWINGS FIG. 1 is a list of temperature measurement results on the back side of a knit product for each irradiation time of approximate sunlight.

Claims (13)

The heat ray absorbing component is selected from the general formula XB _m (where X is La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu, Sr, Ca, Y) At least one element selected from the group consisting of boride fine particles represented by:
A boride fine particle-containing fiber, wherein the fine particle is contained in the surface and / or inside of the fiber in an amount of 0.001 wt% to 30 wt% with respect to the solid content of the fiber. The boride fine particle-containing fiber according to claim 1,
In addition, it contains far-infrared radiation
A boride fine particle-containing fiber, wherein the far-infrared emitting substance is contained in the surface and / or inside of the fiber in an amount of 0.001 to 30% by weight based on the solid content of the fiber. The boride fine particle-containing fiber according to claim 2,
A boride fine particle-containing fiber, wherein the far-infrared emitting material is ZrO ₂ fine particles. The boride fine particle-containing fiber according to any one of claims 1 to 3,
A boride fine particle-containing fiber, wherein the boride fine particle has a particle size of 800 nm or less. The boride fine particle-containing fiber according to any one of claims 1 to 4,
The boride fine particle-containing fiber, wherein the boride fine particle surface is coated with a compound containing at least one element selected from silicon, zirconium, titanium, and aluminum. The boride fine particle-containing fiber according to claim 5,
A boride fine particle-containing fiber, wherein the compound is an oxide. The boride fine particle-containing fiber according to any one of claims 1 to 6,
A boride fine particle-containing fiber, wherein the fiber is any one of a synthetic fiber, a semi-synthetic fiber, a natural fiber, a regenerated fiber, an inorganic fiber, or a blended yarn, a mixed yarn, a blended fiber, or the like. The boride fine particle-containing fiber according to claim 7,
The synthetic fiber is any one selected from polyurethane fiber, polyamide fiber, acrylic fiber, polyester fiber, polyolefin fiber, polyvinyl alcohol fiber, polyvinylidene chloride fiber, polyvinyl chloride fiber, and polyether ester fiber. A boride fine particle-containing fiber characterized by being one or more synthetic fibers. The boride fine particle-containing fiber according to claim 7,
The boride fine particle-containing fiber, wherein the semi-synthetic fiber is at least one semi-synthetic fiber selected from cellulose fiber, protein fiber, chlorinated rubber, and hydrochloric acid rubber. The boride fine particle-containing fiber according to claim 7,
The boride fine particle-containing fiber, wherein the natural fiber is at least one natural fiber selected from plant fiber, animal fiber, and mineral fiber. The boride fine particle-containing fiber according to claim 7,
A boride fine particle-containing fiber, wherein the regenerated fiber is at least one regenerated fiber selected from cellulosic fiber, protein fiber, algin fiber, rubber fiber, chitin fiber, and mannan fiber. The boride fine particle-containing fiber according to claim 7,
The boride fine particle-containing fiber, wherein the inorganic fiber is one or more inorganic fibers selected from metal fibers, carbon fibers, and silicate fibers. A fiber product obtained by processing the boride fine particle-containing fiber according to any one of claims 1 to 12.

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