JP4228856B2 - Thermoplastic fibers, fabrics and textile products - Google Patents

Description

  The present invention relates to clothing that not only blocks ultraviolet rays and has excellent color developability, but also has excellent heat shielding properties, and is used for materials such as clothing such as sportswear, umbrellas, and tents. This gives energy saving and comfort.

  In recent years, environmental issues and energy issues have been screamed loudly, and technologies related to energy saving have been advanced. For example, infrared rays are shielded by a thermal barrier coating on the window glass of automobiles and houses, thereby increasing the cooling efficiency. Similar demands also apply to apparel and materials. For example, the fiber proposed in Patent Document 1 has a core-sheath structure, and the refractive index difference between the core and the thermoplastic fiber is large (PET 1. 5-1.7, polycapramide 1.55, titanium oxide 2.5-2.9) Further, in the visible to near-infrared region, the reflectance of the spectral reflection spectrum has a high reflectance exceeding 90%. Is shielded by reflecting light in the visible to near infrared region. On the other hand, color development is improved by using a polymer containing no titanium oxide in the sheath. When this fiber is used for, for example, a polo shirt, it can be expected that temperature rise in the clothes is suppressed by blocking radiant heat (visible to near infrared region) due to sunlight. However, since the added titanium oxide is reflected in the infrared region and also in the visible light region, it looks whitish, so-called dulling occurs, so that it is not possible to express a clear coloring property. Even if a polymer not containing titanium oxide is arranged on the sheath side, vivid color development is very difficult. In addition, since it has a core-sheath structure, a spinning machine that can supply two types of polymers must be used, the base structure is complicated, and it is difficult to meet user needs such as modified cross-sections and changes in the number of filaments. have.

  Patent Document 2 proposes shielding heat rays by containing zinc oxide or ceramic powder mainly composed of zinc oxide in an amount of 1 to 40% by weight based on polyester fiber, polyamide fiber or the like. Since the difference in refractive index between the thermoplastic fiber and zinc oxide is relatively small, transparency and clear color developability are not greatly reduced. However, although zinc oxide used in Patent Document 2 has a high reflectance in which the spectral reflection spectrum in the near infrared region exceeds 90%, the difference in refractive index between the thermoplastic fiber and zinc oxide (zinc oxide) Since 1.9 to 2.0) is relatively small, the contribution by reflection is small, and heat ray shielding has a limited effect. Similarly, the effect of scattering cannot be expected.

  On the other hand, tin-containing indium oxide (ITO) and antimony-containing tin oxide (ATO), which are used for thermal barrier coatings of automobiles and window glass, and metal or metal ions such as aluminum as described in Patent Document 3 are used. It has been proposed to absorb light in the near infrared region by applying doped conductive zinc oxide to textiles. However, since these substances are colored, there are problems that color developability and sharpness are lowered, and that cost effectiveness is difficult to obtain due to high cost.

Further, zinc oxide particles have been conventionally known to have an ultraviolet shielding effect, and in recent years, additions aimed at antibacterial action have been proposed in Patent Document 4 and Patent Document 5.
JP-A-11-217732 Japanese Examined Patent Publication No. 7-68647 JP 2000-154419 A JP-A-7-197309 JP 2003-73922 A

An object of the present invention is to provide a thermoplastic fiber, a fabric and a garment for suppressing temperature rise due to radiation by shielding light in the infrared region while maintaining color developability, and improving the environment such as clothes. It is to be.

In order to achieve the above object, the present invention adopts the following configuration. That is,
(1) it has a infrared absorbing and surface is coated with an inorganic oxide, which is further surface-treated with a silicone compound, a zinc oxide powder of primary particle size 0.01 to 0.1 m 0. 5 to 5% by weight of thermoplastic fiber, and the ratio of the number of particles of the zinc oxide powder having infrared absorbing properties in which the particle size of secondary particles exceeds 1 μm in the fiber is 0.1% or less. A thermoplastic fiber characterized by
(2) The thermoplastic fiber according to (1), wherein the zinc oxide powder having infrared absorptivity has a spectral reflectance of 90% or more at a wavelength of 500 nm and a spectral reflectance of 70% or less at a wavelength of 2400 nm. .
(3) A fabric using at least a part of the thermoplastic fiber according to ( 1) or (2) , and 0.01 to 5% by weight of zinc oxide powder having infrared absorptivity with respect to the entire fabric A fabric characterized by containing.
(4) A fabric comprising at least a portion of the thermoplastic fiber according to any one of (1) to (3), further adhered with zinc oxide powder having infrared absorptivity, and having the infrared absorptivity A fabric characterized in that the zinc oxide powder is 0.01 to 5% by weight based on the entire fabric.
( 5 ) A textile product using the fabric according to ( 3 ) or ( 4 ).
(6) The method for producing a thermoplastic fiber according to (1) or (2), wherein the primary fiber has infrared absorptivity, the surface is coated with an inorganic oxide, and is further surface-treated with a silicone compound. A production method characterized in that zinc oxide powder having a particle size of 0.01 to 0.1 μm is dispersed during polymerization or by melt kneading.

  The thermoplastic fiber or fabric or fiber product of the present invention has a conventionally known ultraviolet ray shielding effect while maintaining color developability, shields near infrared rays and suppresses an increase in skin and clothes temperature due to radiation, for example, Wear comfort can be improved when used for clothing.

  The thermoplastic fiber of the present invention contains 0.5 to 5% by weight of zinc oxide powder having infrared absorptivity.

  That is, the infrared-absorbing zinc oxide used in the present invention has an ultraviolet-absorbing property, has a relatively low refractive index, and is white, so that it does not inhibit color development when dyed even if dispersed in the fiber. In addition to the above-described characteristics, since it has a characteristic of absorbing infrared rays, when it is contained in a textile product, an effect of suppressing heating due to radiation can be obtained. For example, when used for clothing, it is possible to suppress the temperature rise in the clothes, and when used for umbrellas and tarp tents, it is possible to reduce the heat caused by sunlight.

  Here, absorption of infrared rays can be measured by a spectral reflection spectrum when the cell is filled with powder and measured. FIG. 1 shows a spectral reflection spectrum of zinc oxide particles having infrared absorptivity used in the present invention. In the measurement region of 200 to 2400 nm, strong ultraviolet absorption exists in the region of 200 nm to 380 nm, and high reflection is exhibited in the range of 380 to 1100 nm. Furthermore, it can be seen that the reflection is reduced and absorbed as the wavelength increases from 1100 nm to 2400 nm. The above wavelength range is an infrared region, which is smaller in energy than ultraviolet rays and visible rays, but has a large thermal effect and is called a heat ray. When the zinc oxide powder having infrared absorptivity is present in the thermoplastic fiber, the refractive index difference between the two is small, so that it can be efficiently shielded not by reflection in the spectral reflection spectrum but by absorption.

  As a comparison, FIG. 1 of Patent Document 2 describes the spectral reflectance spectrum of zinc oxide (however, the unit of the wavelength of the horizontal axis seems to be an error in nm), but unlike the zinc oxide powder of the present invention, It can be seen that the outer region has a high spectral reflectance. When zinc oxide particles having a high spectral reflectance in such a near infrared region are used, the shielding effect is small, and it is difficult to suppress heating due to radiation as in the present invention. On the other hand, since the present invention has the spectral reflection spectrum as described above, the heating due to radiation can be effectively suppressed to a degree that cannot be obtained conventionally.

  The absorption mechanism in the infrared region is presumed that the electromagnetic wave in the infrared region cannot be passed by the plasma vibration, which is a sparsely distributed vibration of the electron distribution, but is totally reflected, but is absorbed and attenuated as heat while repeating the reflection. is doing. On the other hand, zinc oxide particles that do not have infrared absorptivity do not absorb infrared rays by this mechanism. In the present invention, it is necessary to select and use zinc oxide particles having infrared absorptivity.

  Zinc oxide powder having infrared absorptivity is not subject to restrictions such as manufacturing method, doping, coating, etc., but when dispersed in fiber, due to the strength characteristics of the fiber, the smaller the particle diameter is preferable, the average from the spinning property More preferably, the particle size is 1 μm or less. Further, when doping or coating is performed, it is preferable not to color, and in general, when doping is performed, it is more preferable not to perform doping because of coloring and further cost increase. As described above, the production method is not limited. However, from the viewpoint of enhancing the transparency of the fiber as described later, a smaller particle diameter is more preferable, and a wet method or a production method utilizing thermal decomposition of zinc oxalate is preferably used. However, other production methods are not limited as long as they are obtained by a pulverization method, classification, or the like.

  The content of the zinc oxide powder in the fiber is preferably as small as possible from the strength characteristics of the fiber, but it is preferable as the absorption performance of ultraviolet rays and infrared rays, and from this balance, it should be 0.5 to 5% by weight. . If it is contained in a larger amount than this, not only the transparency and color developability of the fiber are lowered, but also the strength properties of the fiber are lowered, which is not preferable. On the other hand, when the content is less than 0.5%, the effect of infrared absorption by the fiber cannot be expected, which is not preferable.

  In order to perform infrared absorption with high efficiency while maintaining the color developability of the textile product that is the object of the present invention, the spectral reflectance of the zinc oxide powder at a wavelength of 500 nm is 90% or more, and the spectral reflectance at a wavelength of 2400 nm is It is preferable that it is 70% or less.

  That is, when the spectral reflectance is as high as 90% or more in the visible region centered at 500 nm, the thermoplasticity excellent in transparency and color clarity, coupled with the small refractive index difference between the thermoplastic fiber and zinc oxide. It can be a fiber, a fabric, or a textile product. On the other hand, a spectral reflectance of 70% or less in the near-infrared region centered at 2400 nm means that the near-infrared region is shielded by absorption, and the radiant heat is shielded. In order to be able to do this, although it depends on the addition rate of zinc oxide, it is preferable that the spectral reflectance is 70% or less.

  In addition, as the particle diameter is smaller, the spectral reflectance at a wavelength of 500 nm is higher and the spectral reflectance at a wavelength of 2400 nm tends to be lower. Therefore, in order to obtain the spectral reflectance characteristics, it is necessary to reduce the particle diameter. is there. In particular, by using ultrafine zinc oxide powder having a primary particle diameter of less than 0.1 μm, the spectral reflectance at a wavelength of 500 nm of the zinc oxide powder is 95% or more, and the spectral reflectance at a wavelength of 2400 nm is 60% or less. This is more preferable for the same reason as described above.

  As described above, it is explained that by reducing the particle size of zinc oxide powder, it is possible to obtain stable operability during yarn production, maintenance of fiber strength characteristics, transparency in the visible light region and high absorption in the infrared region. However, it is preferable that the particle diameter is small in order to maintain color developability. That is, scattering by particles smaller than the wavelength of light is expressed by Rayleigh scattering, but the magnitude of the scattering is proportional to the sixth power of the particle size, and thus is an important factor for reducing scattering. Therefore, the primary particle diameter of the zinc oxide powder in the thermoplastic fiber is 0.01 to 0.1 μm, and the ratio of the number of secondary particles of the zinc oxide powder exceeding 1 μm is 0.1% or less. Preferably there is.

  Zinc oxide is known to have an excellent ultraviolet absorption performance, but is also known to have a photoactive catalytic action due to this ultraviolet absorption, and its action is strengthened especially when the particle diameter is reduced. While the deodorizing action and antibacterial properties are obtained by the photoactive catalytic action, the polymer of the thermoplastic fiber is also deteriorated, resulting in a decrease in strength and coloring. Therefore, in order to maintain practical strength and maintain excellent color developability, the zinc oxide powder is more preferably coated with an inorganic oxide such as silica or alumina. Thereby, photocatalytic activity can be completely eliminated. At the same time, it suppresses secondary aggregation and contributes to improvement of dispersibility in the polymer. Here, the film thickness of the inorganic oxide film is more effective with an extremely thin film of about 3 nm.

  As described above, when the primary particles are finely divided, agglomeration becomes a problem when dispersed in the fiber. When the secondary particles become large due to aggregation, the transparency is lowered no matter how small the primary particles are. Therefore, when the zinc oxide powder is dispersed in the thermoplastic fiber, it is preferable that the surface of the zinc oxide powder is hydrophobized because the dispersibility is excellent and aggregation can be suppressed. Furthermore, acid or alkali resistance is promoted by hydrophobization, which is preferable. That is, when performing scouring and alkali weight reduction treatment of the fabric, zinc oxide easily reacts with acid / alkali and is easily eluted, so that zinc oxide powder dispersed in the fiber is prevented from being eluted by dyeing. Is also preferable.

  Here, the method for hydrophobizing is not particularly limited, and examples thereof include surface treatment with a silicone compound. For example, examples of the silicone compound include dimethylpolysiloxane, methylhydrogenpolysiloxane, methylphenylpolysiloxane, methylpropylpolysiloxane, propylhydrogenpolysiloxane, perfluorodimethylpolysiloxane, and the like. Absent. The addition rate is preferably 0.1 to 30% by weight based on the zinc oxide powder.

  In addition, the surface treatment with the silicone compound is more preferably performed after the formation of the inorganic oxide film.

As described above, by dispersing 0.5 to 5 wt% of the zinc oxide powder having infrared absorptivity in the thermoplastic fiber, not only ultraviolet absorption but also infrared shielding effect can be obtained, and the temperature inside the clothes can be prevented by blocking radiation. Rise is suppressed.
In order to express the effect of suppressing the temperature rise in the clothes due to radiation as a fabric, at least a part of the thermoplastic fiber containing 0.5 to 5% by weight of the aforementioned zinc oxide powder having infrared absorptivity was used. A fabric is used. Furthermore, it is necessary to contain 0.01 to 5% by weight of zinc oxide powder having infrared absorptivity with respect to the weight of the fabric. That is, in a fabric having a multilayer structure such as a double woven fabric, it is possible to dispose thermoplastic fibers in which 0.5 to 5% by weight of zinc oxide powder having infrared absorptivity is dispersed on the surface exposed to the sun. More preferred.

  In addition, the thermoplastic fiber containing the zinc oxide powder having infrared absorptivity is used as at least a part of the fabric, and the zinc oxide powder having infrared absorptivity is attached to the surface of the fabric by post-processing to reduce the weight of the fabric. The same effect can be obtained even when the zinc oxide powder having infrared absorptivity is 0.01 to 5% by weight. By attaching zinc oxide powder having infrared absorptivity to the fabric by post-processing, it can be efficiently disposed on the surface that hits the sun, which is advantageous in terms of cost. Further, by making the particle diameter fine, it is possible to suppress a decrease in color developability of the fabric, and it is possible to suppress rough hardening of the texture together with appropriate use of the binder.

  The content of the zinc oxide powder having infrared absorptivity with respect to the fabric weight depends on the thickness, fabric weight, porosity, etc. of the fabric, but it must be 0.01 to 5% by weight. If the amount is less than% by weight, the effect of infrared absorption cannot be expected, and if the amount exceeds 5% by weight, the effect becomes close to saturation and the cost is high. Since the adverse effect of rough hardening appears, it is not preferable.

  As a post-processing method for adhering to the fabric surface, a liquid in which an infrared absorbing zinc oxide powder and a binder are dispersed can be adhered to the fabric using a pad-cure-dry method or a coating method.

  Here, the binder is a resin that serves to adhere the zinc oxide powder to the fabric, and is not particularly limited, but it is acrylic, polyurethane, silicone, fluorine, melamine based on texture and washing durability. Glyoxal resin may be used.

  In the present invention, in order to deposit the zinc oxide powder on the fabric surface, a dispersion of zinc oxide powder and a binder dispersion are mixed to obtain a processing liquid. After impregnating the fabric with this processing liquid, it is squeezed to a certain amount with a mangle roll or the like, and then subjected to a dry curing process, or this processing liquid is adjusted to an appropriate viscosity and applied with a knife coater, gravure roll coater, textile printing, etc. After that, a method of fixing at a temperature of 200 ° C. or lower can be used.

  When zinc oxide powder is attached to the fabric surface by post-processing as described above, water repellents, softeners, UV shielding agents, hydrophilic agents, protective agents are optimized by optimizing binders, solvents, dispersants, etc. It can be combined with post-processing materials required for products such as soil finishing agents.

  As described above, a textile product using a fabric containing or adhering 0.01 to 5% by weight of zinc oxide powder having infrared absorptivity with respect to the fabric weight exhibits infrared shielding performance while suppressing a decrease in color development. Can be expressed. That is, for example, when used as clothing, it suppresses color development deterioration while particles are present in the fiber or on the surface of the fiber, and further suppresses an increase in temperature in the clothes as well as sunburn by expressing ultraviolet absorption and infrared shielding performance. And wear comfort is improved. Moreover, when it uses for material applications, such as a tent place and an umbrella, it becomes possible to suppress a sunburn and a temperature rise, maintaining color developability similarly to clothing.

  Here, when infrared rays are shielded and absorbed by the zinc oxide powder having infrared absorptivity distributed inside or on the fiber surface, the temperature of the fabric rises, for example, the temperature inside the clothes rises. However, since the surface area of the fiber is extremely large, heat can be dissipated quickly, and the increase in skin temperature can be clearly suppressed as compared with the case where infrared rays directly heat the skin.

  The thermoplastic fiber of the present invention is not limited to long fibers or short fibers, and examples thereof include polyester fibers, polyamide fibers, polyvinyl alcohol fibers, polyvinyl chloride fibers, polyvinylidene chloride fibers, polypropylene fibers, and cellulose fibers. A fiber etc. can be used individually or in combination of 2 or more types. Of these, polyester fibers and polyamide fibers are more preferable in terms of strength and texture. Here, the polyester is preferably a polyethylene terephthalate polymer containing 80% or more of ethylene terephthalate units. In this ethylene terephthalate, as copolymerization components, for example, dibasic acids such as adipic acid, sebacic acid, isophthalic acid, diphenyldicarboxylic acid, naphthalene dicarboxylic acid, oxyacids such as oxybenzoic acid, and diethylene glycol, propylene glycol, polyethylene glycol, etc. One or two or more of glycols, 5-sodium sulfoisophthalic acid and the like can be copolymerized. A small amount of a matting agent such as titanium oxide, a micropore forming agent such as kaolinite, an antistatic agent, or the like may be added to these polyesters.

  Polyamide is a high molecular weight product in which a so-called hydrocarbon group is connected to the main chain via an amide bond, and the type is not particularly limited, but preferably has excellent dyeability, washing fastness, and mechanical properties. From the above, it is preferable that the polyamide is mainly composed of polycapramide or polyhexamethylene adipamide. The term “mainly” as used herein means 80 mol% or more, more preferably 90 mol% or more, as a capramide unit or a hexamethylene adipamide unit. Other components are not particularly limited. For example, polydodecanoamide, polyhexamethylene adipamide, polyhexamethylene azelamide, polyhexamethylene sebacamide, polyhexamethylene dodecanoamide, polymetaxylylene azide Examples thereof include units such as aminocarboxylic acid, dicarboxylic acid, and diamine, which are monomers constituting pamide, polyhexamethylene terephthalamide, polyhexamethylene isophthalamide, and the like. Furthermore, a light stabilizer, a heat stabilizer, an antioxidant, an antistatic agent, a terminal group modifier, a dyeability improver, and the like may be added as necessary.

  Of course, the fiber shape of the fiber, for example, the fineness, the number of filaments, the cross-sectional shape, the dyeing property, and the gloss are not limited. Further, various yarns such as spun yarn, composite yarn of short fiber and long fiber, false twisted yarn, air entangled yarn, crimped yarn, and the like can be formed using the fiber of the present invention.

  The method for dispersing the zinc oxide powder having infrared absorptivity in the thermoplastic fiber is possible by conventional addition during polymerization or kneading into a thermoplastic resin, and is not particularly limited. However, it is preferable to suppress secondary agglomeration in order to prevent a decrease in yarn strength and a deterioration in yarn production. Further, it is also preferable to add titanium oxide to the extent that transparency is not inhibited simultaneously with zinc oxide having infrared absorptivity, or to simultaneously disperse a substance imparting hygroscopicity (for example, hygroscopic polymer).

  In addition, a fiber can be obtained by employ | adopting a well-known method as a method of spinning the fiber which disperse | distributed the zinc oxide powder which has infrared absorptivity in a thermoplastic fiber. For example, a master chip is obtained by melting and kneading nylon 6 and a twin screw extrusion kneader at 265 to 275 ° C. so that the zinc oxide powder is 5 to 40% by weight. This master chip and nylon 6 are chip-blended so that the zinc oxide powder weight is 0.5 to 5% by weight. Using this chip blend polymer, the spinning temperature is set to 265 to 280 ° C., the material is discharged from a spinneret having round or irregular discharge holes, cooled, lubricated, taken up, continuously drawn, and then heat treated at 140 to 170 ° C. Then, a method of winding at 3500 to 5000 m / min to wind up the polyamide multifilament can be mentioned.

  As another example, as a method for obtaining a polyester highly oriented undrawn yarn, for example, polyethylene terephthalate (hereinafter PET) having an intrinsic viscosity of about η0.65 and biaxial extrusion so that the zinc oxide powder is 5 to 40% by weight. A master chip is obtained by melt-kneading with a kneader. Feed and knead PET chips and master chips at the entrance of an extrusion kneader (cylinder temperature 285 ° C.) so that the zinc oxide powder weight is 0.5 to 5% by weight, and set the spinning temperature to around 290 ° C. , Discharged from a spinneret with round or irregular discharge holes, cooled, lubricated, taken at 1GD speed 3000-4000m / min, 2GD set to the same speed, winder while relaxing about 5% It can be achieved by winding it on

  Furthermore, as an example of false twisting the highly oriented undrawn yarn, using an existing false twister (spindle false twister, triaxial twister or belt nip is possible), a processing speed of 300 to 1000 m / min, a draw ratio Is set so that the residual elongation is 18 to 35% (PET) and 25 to 40% (nylon) in the range of 1.2 to 2.0 times, although it varies depending on the elongation of the highly oriented undrawn yarn. Then, false twisting is performed under the conditions of a heater temperature of 180 to 230 ° C. (PET) and 160 to 200 ° C. (nylon), and entanglement is imparted by an interlace nozzle before winding, and winding is performed with improved convergence. It is obtained by.

  The fabric in the present invention is a structure having a plane composed of fibers, and there is no problem even if it is a woven fabric, a knitted fabric, a nonwoven fabric or a composite material thereof. As a method of obtaining the fabric, it can be obtained by adopting a known method such as a woven or knitted fabric or a nonwoven fabric. For example, using the polyamide multifilament of the present invention for warp and weft, weaving plain weave, twill weave, satin weave and its change weave, double weave, pile fabric, scouring, intermediate set, dyeing, which is a normal dyeing process, There is a method of final setting.

  Furthermore, a textile product is a product using the above-described fabric, and includes materials such as outerwear, innerwear, and hats, as well as tents and umbrellas. These fiber products can also be obtained by employing known production methods. However, it is efficient for the heat shielding property to adopt a surface where more zinc oxide powder having infrared absorptivity exists as a surface irradiated with sunlight.

  Hereinafter, the present invention will be described more specifically with reference to examples.

  In addition, each measured value in an Example and a comparative example was obtained with the following method.

A. Spectral reflectance of powder First put barium sulfate (standard reagent) as a standard product (for zero point alignment) into a cylindrical cell with one side of a circular flat surface open, and then press it sufficiently with a glass plate etc. Smooth out. After performing a blank scan with barium sulfate, the spectral reflectance spectrum of the sample was measured. As a measuring apparatus, UV-3100S manufactured by SHIMADZU (Shimadzu) was used.

B. Measurement of primary particle diameter The diameter of primary particles is determined as follows. That is, after dissolving the particles in a solvent such as ethanol, the particles are spread evenly on the support film and the solvent is blown off, and then photographed using a transmission electron microscope (hereinafter referred to as TEM), and the photograph is taken as image processing software (WINROOF). Was used to determine the diameter of primary particles in terms of a circle. At this time, in order to measure the primary particle diameter, among the photographed particles, 100 or more randomly extracted particles were used among all the reflected particles.

C. Measurement of secondary particle diameter in fiber The diameter of secondary particles in the fiber is determined as follows. That is, by using a microtome, a cross-sectional thin film having a thickness of about 0.1 μm is cut in a direction perpendicular to the fiber axis, a cross-sectional photograph of the fiber is taken by TEM, and image processing software is used for particles appearing on five randomly extracted photographs. The diameter of the particles in terms of a circle was determined using (WINROOF).

D. 98% sulfuric acid relative viscosity (ηr)
(A) A sample is weighed and dissolved in 98% by weight concentrated sulfuric acid so that the sample concentration (C) is 1 g / 100 ml.
(B) The solution (a) is measured for the number of seconds (T1) dropped at 25 ° C. using an Ostwald viscometer.
(C) The falling seconds (T2) at 25 ° C. of 98 wt% concentrated sulfuric acid in which the sample is not dissolved are measured in the same manner as in the item (2).
(D) The 98% sulfuric acid relative viscosity (ηr) of the sample is calculated by the following equation. The measurement temperature is 25 ° C.
(Ηr) = (T1 / T2) + {1.891 × (1.000−C)}.

E. Intrinsic viscosity [η]
A sample polymer was dissolved in orthochlorophenol (hereinafter abbreviated as OCP), and a relative viscosity ηr at a plurality of points was obtained using an Ostwald viscometer at a temperature of 25 ° C. and extrapolated to an infinite dilution.

F. Heat ray shielding evaluation A sample fixed in a stationary state is placed on a 20 x 20 cm vertical and horizontal metal frame at a position 50 cm away from an infrared lamp (250 W, manufactured by Toshiba), and a heat insulating material is sandwiched between the metal frame. Black paper was pasted, and a thermo camera was placed. Therefore, the black drawing paper is heated by the light passing through the fabric by irradiation from the infrared lamp, and the surface temperature of the drawing paper is measured by the thermo-tracer (DP-ID TH3100 series, manufactured by NEC) arranged on the opposite side. The difference between the maximum temperature at 3 minutes after irradiation with the infrared lamp and after irradiation with the infrared lamp was taken as ΔT.

F. Evaluation of wearing pantyhose with heat shield Wearing pantyhose, subject sits on a chair, irradiates infrared lamp (250W, manufactured by Toshiba) from 90cm from kneecap, and measures skin temperature from knee to shin with thermotracer (DP-ID TH3100 series, manufactured by NEC), and the maximum temperature in the measurement region was defined as ΔTp before and after the infrared lamp irradiation. In addition, since the pantyhose has a coarse knitted fabric, the temperature captured by the thermotracer is equal to the temperature of the skin.

[Example 1]
Nanomax FP-101 (manufactured by Showa Denko KK) was used as the zinc oxide powder having infrared absorptivity. This is because the surface of the zinc oxide fine particles forms a silica film at a rate of 18.1% by weight with respect to the weight of the fine particles (film thickness of 2 to 3 nm), and further dimethyl at a rate of 6.9% by weight with respect to the fine particle weight. Hydrophobizing treatment (film thickness 3 to 4 nm) with polysiloxane is performed.

  The spectral reflectance of the zinc oxide fine particles at a wavelength of 500 nm was 98%, and the spectral reflectance at a wavelength of 2400 nm was 56%. FIG. 1 shows a spectral reflection spectrum of the zinc oxide powder. Moreover, the primary particle diameter of the zinc oxide powder was distributed to 0.02 to 0.07 μm. Table 1 summarizes the properties of the added particles and the surface treatment at each level.

  A master chip was obtained by melting and kneading at 270 ° C. with a polycapramide (hereinafter nylon 6) chip (ηr = 2.7) and a twin screw extruder kneader so that the zinc oxide powder was 20% by weight. The master chip and the nylon 6 were chip-blended so that the weight of zinc oxide powder was 0.5%.

  Using this chip blend polymer, the spinning temperature was set to 270 ° C., and the polymer was discharged from a spinneret having a round discharge hole, cooled, lubricated, and taken, and subsequently stretched to an elongation of 44%. After heat treatment at 155 ° C., it was wound up at 4000 m / min to wind up 78 dtex 68 filament polyamide multifilament.

  The particle size of the secondary particles of the zinc oxide powder in the yarn cross section was distributed in the range of 0.03 to 0.3 μm, and there were no coarse particles exceeding 1 μm.

  Using this polyamide multifilament for warp and weft, weaving a plain woven fabric with a warp density of 180 / 2.34 cm and a weft density of 96 / 2.34 cm, and scouring, an intermediate set (170 ° C), which is a normal dyeing process Then, dyeing with a liquid flow dyeing machine (dyeing temperature 90 ° C.) and final setting (130 ° C.) were performed. In the finished product, the warp density was 190 / 2.34 cm, and the weft density was 100 / 2.34 cm. Table 2 summarizes the particles added to each level of thermoplastic fibers, the constituent polymers, and the fabrics and properties finished using the particles.

[Example 2]
Spinning was performed under the same conditions as in Example 1 except that this master chip and polycapramide chip were chip-blended so that the weight of zinc oxide powder was 1.0%, and a polyamide multifilament having the same fineness and the same filament was obtained. The same plain fabric was obtained under the same conditions.

  In addition, the particle size of the secondary particles of the zinc oxide powder in the yarn cross section was distributed in the range of 0.03 to 0.3 μm, and there were no coarse particles exceeding 1 μm.

[Example 3]
Spinning was carried out under the same conditions as in Example 1 except that this master chip and polycapramide chip were chip-blended so that the weight of zinc oxide powder was 3.0% by weight. A similar plain woven fabric was obtained under the same conditions.

  In addition, the particle size of the secondary particles of the zinc oxide powder in the yarn cross section was distributed in the range of 0.03 to 0.3 μm, and there were no coarse particles exceeding 1 μm.

[Example 4]
Using the same zinc oxide powder as in Example 1 and polyethylene terephthalate (hereinafter referred to as PET) containing no additive particles having an intrinsic viscosity of η0.65 to 0.66, a 20 wt% master chip was melt-kneaded with a biaxial extrusion kneader. Obtained in advance. The above PET chip and master chip are kneaded in an extrusion kneader (cylinder temperature 285 ° C.) so that the weight of zinc oxide powder is 0.5% by weight, and the spinning temperature is 290 ° C. Spinning having a round discharge hole It is discharged from the die, cooled, lubricated, taken up at a 1 GD speed of 3000 m / min, taken up at a 2 GD speed of 3000 m / min, taken up at 3015 m / min, 156 dtex, 36 filaments with a high elongation of 188% A drawn yarn (hereinafter referred to as POY) was obtained.

  The particle size of the secondary particles of the zinc oxide powder in the yarn cross section was distributed in the range of 0.03 to 0.3 μm, and there were no coarse particles exceeding 1 μm.

  The above-mentioned POY is false twisted using a false twisting machine (Murata Kikai MACH-33H) under the conditions of a working speed of 600 m / min, a draw ratio of 1.86 times, and a heater temperature of 220 ° C. To obtain an 84 dtex-36 filament false twisted yarn that was entangled and improved in convergence.

  Using this false twisted yarn for warp and weft, weaving a plain woven fabric at a warp density of 90 / 2.34 cm and a weft density of 78 / 2.34 cm, and scouring and intermediate set (180 ° C), which is a normal dyeing process ), Dyeing with a liquid dyeing machine (dyeing temperature 130 ° C.), and final setting (160 ° C.). In the finished product, the warp density was 96 / 2.34 cm, and the weft density was 85 / 2.34 cm.

[Example 5]
The PET false twisted yarn used in Example 4 was used for warp and weft, and finished to the same density through the same dyeing and finishing process as Example 4.

  Except that the hydrophobization treatment with dimethylpolysiloxane was not performed on the particles of Example 1 as zinc oxide powder having infrared absorptivity, and this was applied to a wet disperser using sodium hexametaphosphate as a dispersant. And dispersed. The amount of sodium hexametaphosphate (dispersant) added to this dispersion was 5%, and the amount of zinc oxide powder added was 20%. This processing agent was used as processing liquid A.

  The spectral reflectance of the zinc oxide fine particles at a wavelength of 500 nm was 98%, and the spectral reflectance at a wavelength of 2400 nm was 56%. Moreover, the primary particle diameter of the zinc oxide powder was distributed to 0.02 to 0.07 μm.

  Next, the PET fabric is immersed in a treatment solution having the following composition, then drawn with a mangle (drawing rate 80%), dried at 130 ° C. for 2 minutes, and then subjected to a dry heat treatment with a pin tenter at 180 ° C. for 30 seconds to provide a functionalized processed fabric A was obtained. At this time, the adhesion amount of the inorganic substance was 0.8% by weight with respect to the fiber fabric, and the acrylic resin (T-23M, manufactured by Kyoeisha Chemical Co., Ltd.) was 0.5% by weight.

Treatment liquid formulation (water dispersion)
Processing fluid A (concentration 20%) 50 g / l
Acrylic binder (concentration 45%) 15g / l
[Example 6]
The same master chip as in Example 1 and nylon 6 were used, and chip blending was performed so that the weight of zinc oxide powder was 0.5% by weight.

  Using this chip blend polymer, the spinning temperature is set to 270 ° C., and the nozzle is discharged from a spinneret having a discharge hole having a narrowed inner side compared to a square, cooled, lubricated, and taken out. After stretching to a degree of 44%, it was heat treated at 155 ° C. and then wound up at 4000 m / min. Polyamide multifilament with a 9 dtex 5 filament shown in Example 5 in Table 1 and having a square cross section was wound. I took it.

  The particle size of the secondary particles of the zinc oxide powder in the yarn cross section was distributed in the range of 0.03 to 0.3 μm, and there were no coarse particles exceeding 1 μm.

  These drawn yarns are used as covering yarns, “Lycra” manufactured by Toray DuPont (registered trademark), 178C type, fineness of 20 dtex is set as the core yarn, the covering draft is set to 2.9 times, and the S twist and Z twist directions, respectively. A single covering yarn (SCY) was produced at a twist number of 2200 t / m.

  These SCY and S twists are alternately supplied to the yarn feeder of the knitting machine, and the pantyhose used for the leg part is knitted (MODEL P-482 manufactured by Nagata Seiki Co., Ltd. (number of needles: 400)). The pantyhose product was prepared by presetting, dyeing, finishing and setting the template.

[Comparative Example 1]
Using only the nylon 6 chip used in Example 1, the polyamide multifilament of 78 dtex 68 filament shown in Comparative Example 1 of Table 1 was wound under the same spinning conditions as in Example 1 without adding zinc oxide particles. It was.

  This polyamide multifilament was used for warps and wefts, woven at the same density as in Example 1, and finished to the same density through the same dyeing process.

[Comparative Example 2]
The master chip and nylon 6 chip used in Example 1 were blended to obtain a zinc oxide powder weight of 6.0% by weight.

  Using this chip blend polymer, polyamide multifilaments of 78 dtex 68 filaments shown in Comparative Example 2 of Table 1 were wound up under the same spinning conditions as in Example 1. However, in this spinning process, the increase in the filtration pressure of the base pack is three times faster than in Examples 1 to 3, the base pack replacement cycle is shortened, and the single yarn fluff that was not seen in Examples 1 to 3 Occurred in 10% of drums.

  Therefore, when the above-mentioned polyamide multifilament was used for warp and weft, and weaving at the same density as in Example 1, five times as many threads as in Examples 1 to 3 were generated. Then, it finished to the same density through the dyeing process similar to Example 1.

  The particle size of the secondary particles of the zinc oxide powder in the yarn cross section was distributed in the range of 0.03 to 1.2 μm, and there were 0.12% of coarse particles exceeding 1 μm.

[Comparative Example 3]
At the time of polymerization, titanium oxide powder (TA-500 manufactured by Fuji Titanium Industry Co., Ltd.) was added as a slurry to obtain a full dull chip (amount of titanium oxide added: 1.8% by weight, ηr = 2.2). Using this chip, a polyamide multifilament of 78 dtex 68 filaments shown in Comparative Example 3 of Table 1 was wound up under the same spinning conditions as in Example 1.

  This polyamide multifilament was used for warps and wefts, woven at the same density as in Example 1, and finished to the same density through the same dyeing process.

[Comparative Example 4]
The PET false twist plain weave before post-processing in Example 5 was used as Comparative Example 4.

[Comparative Example 5]
Using only the nylon 6 tip used in Example 1 and without adding zinc oxide particles, the 9 dtex 5 filament shown in Comparative Example 1 in Table 1 under the same spinning conditions as in Example 6 and having a square cross-sectional shape Polyamide multifilament was wound up.

  A pantyhose similar to that of Example 6 was obtained using this polyamide multifilament as a covering yarn.

  Using the woven fabrics of Examples 1 to 3 and Comparative Examples 1 to 3, a windbreaker was sewed using a commercially available paper pattern, and evaluation was performed by three experts in textile product evaluation. First, as for the color developability of the fabric, the comparative example was most excellent in sharpness, but had a slightly lustrous gloss. On the other hand, in the case of using the woven fabric of Example, when using the woven fabric of Example 1, an excellent level although the sharpness is slightly lowered as compared with the case of using the woven fabric of Comparative Example 1. It had a high-class feeling with a mild luster. Even when the fabric of Example 2 was used, when the fabric of Example 1 was used, the color development was excellent at the next level, and a mild gloss was obtained. When the fabric of Example 3 was used, the sharpness was inferior to that of the other samples, but the level was high and the gloss was the mildest. On the other hand, when the fabric of Comparative Example 2 was used, it had a so-called semi-dull level dull feeling, and the sharpness was inferior. Further, when the fabric of Comparative Example 3 was used, it was a pastel color and was the worst in terms of sharpness.

  Next, heat ray shielding evaluation was implemented using the said textile fabric. In the case of using the fabric of Comparative Example 1, the temperature was quickly raised by an infrared lamp, and the maximum temperature ΔT in the measurement region after 3 minutes was the highest at 8.3 ° C. On the other hand, in the case where the woven fabrics of Examples 1 to 3 and Comparative Examples 2 and 3 were used, near infrared rays were shielded by the additive particles, and ΔT was lower than that of Comparative Example 1. After actually wearing a windbreaker directly on the skin and applying the same infrared lamp to the back to conduct a sensory evaluation of the increase in skin temperature, only when the fabric of Comparative Example 1 was used, the heat was jerky. On the other hand, when the fabrics of Examples 1 to 3 and Comparative Examples 2 and 3 were used, the time when the temperature started to feel hot was also delayed, and in the same time, it was felt in the chilly heat I couldn't.

  Furthermore, when texture evaluation by three texture evaluation experts was carried out, when the fabric of Comparative Example 1 was used, a slime feeling peculiar to nylon was felt, whereas Examples 1 to 3 and Comparative Examples 2 and 3 In the case of using the woven fabric, there was a light touch feeling, especially when the woven fabrics of Example 3 and Comparative Examples 2 and 3 were used, and at the same time, the feeling of contact cooling was also felt relatively strong.

  Umbrellas were prepared using the fabrics of Examples 4 and 5 and Comparative Example 4, and evaluated in the same manner as in Examples 1 to 3 and Comparative Examples 1 to 3. First, regarding the color developability of the fabric, although Example 5 did not reach the other level, all had clear color developability.

  Next, heat ray shielding evaluation was implemented using the said textile fabric. In Comparative Example 4, the temperature was quickly raised by the infrared lamp, and the maximum temperature ΔT in the measurement region after 3 minutes was the highest at 7.9 ° C. On the other hand, in Examples 4 and 5, near infrared rays were shielded by the added or adhered particles, and ΔT was lower than that of Comparative Example 4. When sensory evaluation was performed by irradiating an infrared lamp from above with an umbrella actually attached, only Comparative Example 4 felt a chilly heat on the cheek, whereas in Examples 4 and 5, the temperature The time when I started to feel hot was also slowed down, and I couldn't feel it in the same time.

  Using Example 6 and Comparative Example 5, evaluation was performed by three specialists of fiber product evaluation. First, as for color developability, Example 6 was slightly whitish compared to Comparative Example 5, and the level as a product was high although transparency and clarity of color development were slightly inferior. In addition, when five women evaluated the appearance of the toe peticure using pantyhose with no toe turning, it was evaluated that there was no difference in the appearance.

  When heat ray shielding wearing evaluation of pantyhose was carried out, ΔTp was as high as 2.1 ° C. in Comparative Example 5, whereas in Example 6, the temperature rise was suppressed to 1.2 ° C. As an evaluation, there was a difference of almost 1 minute when it started to get hot. In Comparative Example 5, it was felt hot, but in Example 6, it did not reach that point.

2 is a spectral reflection spectrum of zinc oxide powder added to Example 1.

Claims (8)

Have a infrared absorbing and surface is coated with an inorganic oxide, which is further surface-treated with a silicone compound, a zinc oxide powder of primary particle size 0.01 to 0.1 m 0. 5 to 5% by weight of thermoplastic fiber, and the ratio of the number of particles of the zinc oxide powder having infrared absorbing properties in which the particle size of secondary particles exceeds 1 μm in the fiber is 0.1% or less. A thermoplastic fiber characterized by 2. The thermoplastic fiber according to claim 1, wherein the infrared-absorbing zinc oxide powder has a spectral reflectance at a wavelength of 500 nm of 90% or more and a spectral reflectance at a wavelength of 2400 nm of 70% or less. The thermoplastic fiber according to claim 1 or 2, wherein the thermoplastic fiber is a polyamide fiber or a polyester fiber . A fabric using at least a part of the thermoplastic fiber according to any one of claims 1 to 3, comprising 0.01 to 5% by weight of zinc oxide powder having infrared absorptivity with respect to the entire fabric. A fabric characterized by having A fabric comprising at least a part of the thermoplastic fiber according to any one of claims 1 to 3 and further attached with zinc oxide powder having infrared absorptivity, wherein the zinc oxide powder having infrared absorptivity is A fabric characterized by being 0.01 to 5% by weight based on the entire fabric. A textile product comprising the fabric according to claim 4 or 5 .   It is a manufacturing method of the thermoplastic fiber in any one of Claims 1-3, Comprising: The primary particle which has infrared absorptivity, the surface is coat | covered with the inorganic oxide, and is further surface-treated with the silicone compound. A production method characterized in that zinc oxide powder having a diameter of 0.01 to 0.1 μm is dispersed during polymerization or by melt kneading. 8. The method according to claim 7, wherein chip blending is performed using a master chip made of zinc oxide powder.

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