JP2012214955A - Heat dissipation fiber sheet and clothes using the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a heat dissipation fiber sheet having high heat dissipation, quick-drying property and cool-feeling in sweating and wetting, and giving comfort even when sweating, and clothes.SOLUTION: The heat dissipation fiber sheet of the present invention is a heat dissipation fiber sheet comprising at least one fiber sheet selected from a fabric, a knitted fabric and an unwoven fabric cloth which contain a synthetic fiber alone or a synthetic fiber; and a water soluble zirconium compound, a resin crosslinking agent, collagen and chitosan are fixed on the fiber surface constituting the above fiber sheet. The heat dissipation clothes of the present invention are heat dissipation clothes where the above fiber sheet is sewed; and a zirconium compound, a resin crosslinking agent, collagen and chitosan are fixed on the surface of the synthetic fiber.

Description

  The present invention relates to a heat-radiating fiber sheet and clothing using the same.

  Conventionally, it has been known that inorganic particles are fixed to a fiber surface together with a binder to impart various properties. Patent Document 1 proposes that a cation such as zirconium is dispersed in a collagen aqueous solution and fixed on the fiber surface to improve the texture. Patent Documents 2 to 3 propose that negative ions are generated by fixing ceramic particles such as zirconia on a fiber surface with a binder. Moreover, as a proposal for improving heat dissipation, Patent Document 4 proposes a fabric that attaches particles that enhance moisture absorption and desorption to enhance heat generation and heat dissipation. Patent Document 5 proposes a method for improving heat dissipation and heat retention by attaching a trialodine derivative to wool or cellulose fiber.

  However, Patent Documents 1 to 3 do not focus on heat dissipation, and there is a high demand for fibers having heat dissipation when sweating and getting wet. Although Patent Document 4 increases heat dissipation, heat generation also increases, so it is unsuitable for situations where the body is cooled. In addition, only moisture absorption and release, that is, the effect due to moisture in the gas phase is described, and the effect and effect due to moisture in the liquid phase are not analyzed. The fiber described in Patent Document 5 dissipates heat, but also retains heat, so it is not suitable in situations where the body is cooled in sports or the like.

JP-A-9-241514 JP 2006-305304 A Japanese Patent No. 3193653 JP 2002-180375 A JP 2007-308857 A

  In order to solve the above-mentioned conventional problems, the present invention provides a heat-dissipating fiber sheet that has high heat dissipation, quick-drying and coolness when sweated and wetted, and is comfortable to wear even when sweating and a clothing using the same. provide.

  The heat-dissipating fiber sheet of the present invention is a heat-dissipating fiber sheet comprising at least one fiber sheet selected from synthetic fibers alone or woven fabrics, knitted fabrics and nonwoven fabrics containing synthetic fibers, on the fiber surface constituting the fiber sheet A zirconium compound, a resin crosslinking agent, collagen and chitosan are fixed.

  The heat-dissipating garment of the present invention is a heat-dissipating garment in which the fiber sheet is sewn, and is characterized in that a zirconium compound, a resin cross-linking agent, collagen, and chitosan are fixed on the surface of the synthetic fiber.

  In the present invention, a zirconium compound, a resin cross-linking agent, collagen and chitosan are fixed on the surface of the synthetic fiber, so that heat dissipation, quick-drying and coolness are high when sweating and getting wet, and even when sweating. Comfortable heat radiating fiber sheet and clothing can be provided. In addition, it is possible to obtain a textile product that is antibacterial and has a soft texture.

FIG. 1A is a scanning electron microscope (SEM) enlarged photograph of the fiber surface obtained in one example of the present invention. FIG. 1B is a scanning electron microscope (SEM) enlarged photograph of the fiber surface obtained in one example of the present invention. FIG. 2A is a scanning electron microscope (SEM) enlarged photograph of the surface of a comparative example product (fiber not provided with a zirconium compound or the like on the fiber surface). FIG. 2B is a scanning electron microscope (SEM) enlarged photograph of the surface of a comparative example product (fiber not provided with a zirconium compound or the like on the fiber surface). FIG. 3 is a graph showing heat radiation data of one product of Example 1 and one product of Comparative Example of the present invention. FIG. 4 is a graph showing the results of a wearing test of a knitted shirt of an example product of the present invention and a comparative product. 5A-B are charts showing analysis data by a high-resolution field emission scanning electron microscope with elemental analysis used in one example of the present invention, and FIG. 5A is analysis data of a fiber product on which a Zr compound is fixed, FIG. 5B is analysis data of the fiber product in which the Zr compound is not fixed (blank sample).

  When you sweat in the liquid phase, the heat dissipation is large and the body cools down. During exercise, the human body instinctively sweats to cool the body. Heat dissipation increases by changing from liquid phase to vapor phase sweat. Most of the components of sweat are water. Liquid sweat evaporates and cools the body with latent heat of vaporization. This is effective sweating. If liquid sweat is dripped from the surface of the body or remains on the clothes or skin surface in the form of water droplets, there is little effect on cooling the body and invalid sweating occurs. Therefore, in order to increase the amount of heat release, it is important to improve the heat dissipation, quick-drying and coolness of the fibers constituting the clothing.

  As a result of studying to increase the heat dissipation, quick-drying and coolness of the fiber, the present inventors have surprisingly achieved by fixing a zirconium compound, a resin cross-linking agent, collagen and chitosan on the surface of the synthetic fiber. I understood.

(1) Modification process The heat-dissipating fiber sheet of the present invention is processed in a sheet state. The fiber sheet is a woven fabric, a knitted fabric, or a non-woven fabric. The fiber sheet is brought into contact with a mixed aqueous solution containing a water-soluble zirconium compound, a resin crosslinking agent, collagen, and chitosan. The specific means for contacting may be any means such as dipping, padding, spraying, roll coating and the like. It heat-crosslinks in the state which made the fiber sheet contact the said mixed aqueous solution. In the case of the immersion method, the heating temperature is preferably 100 to 150 ° C., and the heating time is preferably 20 to 90 minutes. In the case of pad dry cure, the mixed aqueous solution is padded with a fiber sheet at a drawing rate of 60 to 80%, and then dried at 100 to 150 ° C., more preferably 100 to 120 ° C., and 140 to 180 ° C. Cure for 30 seconds to 5 minutes. Thereby, a zirconium compound, a resin crosslinking agent, collagen, and chitosan are fixed to the fiber surface. By the treatment, zirconium becomes insoluble in water.

  Water-soluble zirconium compounds include zirconium oxychloride, zirconium hydroxide, zirconium sulfate, zirconium nitrate, zirconium phosphate, zirconium carbonate, zirconium acetate and fatty acid zirconium, and sodium, potassium, magnesium, lithium and magnesium salts of these compounds. Examples thereof include salts, calcium salts, and ammonium salts. More specifically, trade names: Zirconic acid salt, Zircozole ZC, Zircozole ZC-20, Zircozole ZC-2, Zirconium sulfate, Zircozol ZN, Zircozol AC-7, Zircozol AC-20, Examples include zircozole acetate, zircozol ZA-20, zircozol ZA-30, zirconium stearate, zirconium octylate, and silver zirconium phosphate. It is preferable to fix the zirconium compound to the fiber sheet in an amount of 0.1 to 20% owf (owf is an abbreviation for on the weight of fiber). More preferably, it is 2 to 15% owf.

  As a method for examining the amount of the fixed zirconium compound, there is an analysis by a high resolution field emission scanning electron microscope with elemental analysis. This apparatus is composed of a high-resolution field emission scanning electron microscope and an energy dispersive X-ray analyzer, and can perform elemental analysis and quantitative measurement of the fiber surface. By depositing carbon on the fiber fixed with the zirconium compound and performing X-ray analysis, the spectrum of the element present on the fiber surface can be measured, and the weight ratio of each element can be determined from the peak value. When the fiber sheet of the product of the present invention is analyzed by this method and the weight ratio of each element of the substance fixed on the fiber surface is measured, the weight ratio of the zirconium element is 0.1 to 20%, more preferably 2 ~ 15%.

The resin crosslinking agent is preferably a synthetic fiber resin crosslinking agent such as an aldehyde resin crosslinking agent, an epoxy resin crosslinking agent, an isocyanate resin crosslinking agent, or an unsaturated carboxylic acid resin crosslinking agent. For example, resin crosslinkers containing unsaturated carboxylic acids such as acrylic acid, methacrylic acid, maleic acid, aldehyde resin crosslinkers containing aldehydes such as malondialdehyde, glutaraldehyde, terephthalaldehyde, acrolein, ester groups -C (R) (Meth) acrylic acid alkyl ester having ═CH ₂ (R is an alkyl group such as a hydrogen atom, a halogen atom, or a methyl group) and a carboxyl group is formed by hydrolysis of the ester group during the reaction can also be used. .

  Specific examples of the epoxy resin crosslinking agent include ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, sorbitol polyglycidyl ether, polyglycerol polyglycidyl ether, diglycerol polyglycidyl ether. Glycerol polyglycidyl ether, trimethylolpropane polyglycidyl ether, and the like. The brand name includes Denasel manufactured by Nagase ChemteX, and Epolite manufactured by Kyoeisha Chemical.

  Examples of the isocyanate resin crosslinking agent include 4-tolylene diisocyanate, methylene bisphenyl isocyanate, hexamethylene isocyanate, and methylene bis-4-cyclohexyl isocyanate.

  A preferable amount of the resin crosslinking agent is 1 to 20% owf, more preferably 5 to 20% owf with respect to the fiber sheet. When using a catalyst, 1 to 10% owf is preferable.

The preferred amount of collagen is 1 to 10% owf, more preferably 1 to 5% owf, with respect to the fiber sheet.
The preferred amount of chitosan is 1 to 30% owf, more preferably 3 to 20% owf with respect to the fiber sheet.

(2) Flexible processing It is preferable that after the modification processing, dyeing processing is performed, and then soft processing is performed. Alternatively, the flexible processing may be performed simultaneously with the dyeing processing. Thereby, it becomes a fiber sheet of a preferable texture. In the flexible processing, an aqueous solution containing a surfactant is brought into contact with the fiber sheet. The soft processing improves water absorption and contributes to improvement of heat dissipation. The water absorption is preferably within 10 seconds, more preferably within 3 seconds, in the measurement method of JIS L1907 dropping method.

  The softening process uses a surfactant-type softening agent. Specifically, nonionic surfactants and / or anionic surfactants are preferred. These surfactants are preferred because they have less influence on the functional group of the fiber than cationic surfactants and amphoteric surfactants.

  A surfactant type softening agent is applied to the fiber by dipping or padding. In the case of the immersion method, a preferable processing temperature is 40 to 150 ° C., and a preferable processing time is 10 to 180 minutes. A preferable amount of the softening agent is 0.5 to 10% owf, more preferably 1 to 5% owf with respect to the fiber sheet. In the case of the pad method, the treatment temperature may be about room temperature, and the preferred amount of the softening agent is 0.5 to 10% soln., More preferably 1 to 5% soln. (Soln. Stands for solution).

  The fiber sheet shown in FIGS. 1A and 1B is obtained as described above. 2A and 2B, it can be seen that a zirconium compound, a resin cross-linking agent, collagen, and chitosan are fixed on the fiber surface. When this fiber sheet is used to make clothing such as a shirt, when it sweats and gets wet, it has high heat dissipation, quick-drying, and coolness, and is comfortable even when sweating. In addition, it is antibacterial and has a soft texture. 1A and 1B and FIGS. 2A and 2B are SEM photographs with different magnifications.

(3) Fiber material The heat-dissipating fiber sheet of the present invention includes yarns, fabrics and nonwoven fabrics made of synthetic fibers such as polyester, polyamide (nylon), and acrylic fibers, as well as blended yarns of natural fibers and synthetic fibers, and synthetic fibers. Fabrics woven / knitted with natural fibers and non-woven fabrics mixed with synthetic fibers and natural fibers are also applicable, and the mixing ratio when blended / woven / knitted / knitted / mixed can be in any range. . Preferably, the heat dissipation is improved when the yarn or the fabric contains 50% by mass or more of synthetic fiber. Synthetic fibers may include polylactic acid, acetate fibers, polyurethane fibers, and fibers containing ethylene vinyl alcohol resin (trade name: manufactured by Sofista Kuraray Co., Ltd.). The acrylic fiber may be a copolymer fiber with an acrylate such as methyl acrylate.

  The heat-dissipating clothing of the present invention includes textile shirts, knit shirts, sports clothing, uniforms, insoles, socks, shoe linings, shoe linings, underwear, underwear, inner garments, outer garments, outer garments, linings, and futons. Sides, chairs, hats, gloves, sweaters, slacks, skirts, etc. The fibers of the present invention are preferably arranged on the skin side.

  Hereinafter, the present invention will be described more specifically with reference to examples. The present invention is not limited to the following examples.

<Measurement of heat dissipation>
It was measured using a product name “KES-F7 precision rapid thermophysical property measuring apparatus Thermolab II” manufactured by Kato Tech. An electronic balance was installed under the heat retention measuring unit, and the history of weight change was recorded while measuring the amount of heat released. At a temperature of 20 ° C and a relative humidity of 65%, 1 g of water is applied so that the entire sample is uniformly moistened, and installed in a heat retention measuring unit set at a temperature of 40 ° C to measure the amount of heat radiation and the amount of moisture change. did. The sample size was 100 mm vertically and 100 mm horizontally.

<Measurement of antibacterial properties>
Evaluation was performed according to the JIS L 1902 2008 Bacterial Absorption Method (Test Bacteria: Staphylococcus aureus). Two types of samples were prepared before washing and after 10 washings. The washing method was in accordance with JIS L 0217 103 (however, using JAFET standard detergent).

<Quantitative determination of zirconium>
As a method for examining the amount of the fixed zirconium compound, there is an analysis by a high resolution field emission scanning electron microscope with elemental analysis. This apparatus is composed of a high-resolution field emission scanning electron microscope and an energy dispersive X-ray analyzer, and can perform elemental analysis and quantitative measurement of the fiber surface. By depositing carbon on the fiber fixed with the zirconium compound and performing X-ray analysis, the spectrum of the element present on the fiber surface can be measured, and the weight ratio of each element can be determined from the peak value. The fiber sheet of this example is analyzed by this method, the weight ratio of each element of the substance fixed on the fiber surface is measured, and the weight ratio of the zirconium element is calculated.

<Measurement of water absorption>
Water absorption was measured by the JIS L1907 dropping method. The measurement cotton was the back side.

<How to wash>
The washing method was in accordance with JIS L0217 103.

Example 1
Nylon-6 multifilament (total fineness 78dtex, number of fibers 48) knitted with a circular knitting machine (weighing weight 130g / m ² ) 5kg is set in a Wins dyeing machine so that the bath ratio is 1:20. 100 kg of water was added. Then the next drug was added.
(1) 6% owf of zirconium acetate as a water-soluble zirconium compound
(2) 10% owf of the product name “Epolite 40E” manufactured by Kyoeisha Chemical Co., Ltd. as an epoxy resin crosslinking agent
(3) 2% owf made by Asahi Chemical Industry Co., Ltd.
(4) Chitosan 10% owf
(5) Other: CIBA as a degassing agent, trade name “ALBEGAL FFA” 1% owf, as a leveling agent, Nikka Chemical Co., Ltd., trade name “Nikka Sun Salt 7000” 6% owf, zinc borofluoride as a catalyst 3% owf, formic acid 3% owf

  The temperature was raised to 130 ° C. at 2 ° C./min and heated and circulated for 60 minutes. Subsequently, it was cooled to 80 ° C., drained, washed with water in the usual manner, and soaped and washed with water.

  Then, it dye | stained by the conventional method and then softened using the softening agent. As a softener, 2% owf of the product name “Nicepol PR9000” manufactured by Nikka Chemical Co., Ltd. was used. After dyeing, the softening agent was put in the same bath, kept at 80 ° C., then the temperature was lowered, and the waste liquid was discharged.

  The processed product obtained as described above and the knitted fabric (comparative example 1 product) not subjected to the above treatment were measured for heat release and moisture content change (fast drying property). The results are shown in Table 1 and FIG. The heat release and moisture content changes in Table 1 are the average values in a stable state from 1 minute to 4 minutes after the start of measurement.

  As shown in Table 1, the heat release amount of the product of Example 1 was 0.98 J / sec higher than that of the product of Comparative Example 1. The amount of evaporation of 1 g of water was 540 cal, and the heat of evaporation was calculated from this value. The product of Example 1 was 0.76 J / sec higher than the product of Comparative Example 1. The actual amount of heat release is higher than the heat of vaporization because it is not always possible to capture and measure all the heat of vaporization of water in the heat release amount measurement. However, measuring the amount of heat released is considered to be a measure of quick drying with changes in water content. For these reasons, it can be evaluated that the product of Example 1 has quick drying properties and high heat dissipation and coolness. The fibers of Example 1 were observed in SEM as shown in FIGS. 1A and 1B, and those of Comparative Example 1 were shown in FIGS. 2A and 2B.

  Further, when antibacterial properties of the product of Example 1 and the product of Comparative Example 1 were measured, they were as shown in Table 2.

  Furthermore, the product of Example 1 was compared with the summer clothing products currently on the market. As a comparative example, the product “Ice Touch” warp knitted product of the applicant and products a, b and c of Company A were taken up. The amount of heat release is compared as shown in Table 3 below.

  It can be seen from Table 3 that the heat release amount of the product of Example 1 is high.

(Example 2)
Example 4 is the same as Example 1 except that a knitted fabric (weighing 140 g / m ² ) obtained by knitting a multifilament made of nylon-6 (total fineness 111 dtex, 60 fibers) with a circular knitting machine is used. It processed on the conditions shown and measured the heat release. The results are shown in Table 4.

  It can be seen from Table 4 that the knitted fabric having the composition of Example 2 has a high heat radiation amount.

(Example 3)
Example 5 is the same as Example 1 except that a knitted fabric (weight per unit area: 145 g / m ² ) knitted with a multi-filament made of nylon-6 (total fineness: 111 dtex, number of fibers: 60) with a circular knitting machine is shown in Table 5 as a comparative example. It processed on the conditions shown and measured the heat release. The results are shown in Table 5.

  As shown in Table 5, when the softening agent was used, an effect of improving the heat radiation amount was recognized, and the texture was also improved.

  Next, the water absorption of the knitted fabrics of Example 3 and Comparative Examples 4 to 5 was measured. The results are shown in Table 6.

  As is apparent from Table 6, it can be seen that the example product absorbs water faster and absorbs more water than the comparative product.

(Example 4)
100% knitted fabric shirt with the same basis weight as the Example 6 product and Comparative Example 1 product, 100% polyester knitted fabric shirt with the same basis weight as the Comparative Example 6 product, and 100% cotton knitted fabric shirt with the same basis weight as the 7th Comparative Example product A wearing test was conducted using The wear test selects 10 men from the healthy 20s to 40s, wears the shirt on summer days when the maximum temperature in August-September exceeds 30 ° C, and evaluates the items shown in Table 7 on a five-point scale. The average value was calculated.

  Table 8 shows the results of the wearing test of the product of Example 1.

  Table 9 shows the results of the wearing test of one comparative example.

  Table 10 shows the results of the wearing test of the six comparative examples.

  Table 11 shows the results of the wearing test of the seven comparative examples.

  The results of the five-stage evaluation of the above wearing test are shown together in FIG. As is clear from FIG. 4, the highest evaluation result was obtained for any of the products of Example 1.

(Example 5)
The knitted fabric obtained in Example 3 and the knitted fabric obtained in Comparative Example 5 were washed 10 times, dried, and then analyzed by a high-resolution field emission scanning electron microscope with elemental analysis. FIG. 5A is a chart showing analytical data of the knitted fabric obtained in Example 3, and FIG. 5B is analytical data of the knitted fabric with no Zr compound fixed (Comparative Example 5: untreated product). The data shown in Table 12 is calculated from FIGS. 5A-B.

  From Table 12, it is clear that the presence of zirconium can also be analyzed from the knitted fabric.

Claims (8)

A heat-dissipating fiber sheet comprising at least one fiber sheet selected from synthetic fibers alone or woven fabrics, knitted fabrics and nonwoven fabrics containing synthetic fibers,
A heat-dissipating fiber sheet, characterized in that a zirconium compound, a resin cross-linking agent, collagen, and chitosan are fixed to the fiber surface constituting the fiber sheet.   The heat dissipating fiber sheet according to claim 1, wherein the heat dissipating fiber sheet is dyed and softened.   The heat-dissipating fiber sheet according to claim 2, wherein the softening process is a process of bringing an aqueous solution containing a surfactant into contact with the fiber sheet.   Fixation of the zirconium compound, the resin cross-linking agent, collagen and chitosan to the fiber surface is manifested by bringing the fiber sheet into contact with a mixed aqueous solution containing a water-soluble zirconium compound, resin cross-linking agent, collagen and chitosan, followed by heat cross-linking. The heat-radiating fiber sheet according to any one of claims 1 to 3.   The resin cross-linking agent is at least one resin cross-linking agent for synthetic fibers selected from aldehyde resin cross-linking agents, epoxy resin cross-linking agents, isocyanate resin cross-linking agents and unsaturated carboxylic acid resin cross-linking agents. The heat-dissipating fiber sheet as described.   The water-soluble zirconium compound is zirconium oxychloride, zirconium hydroxide chloride, zirconium sulfate, zirconium nitrate, zirconium phosphate, zirconium carbonate, zirconium acetate and fatty acid zirconium, and sodium, potassium, magnesium, lithium salts of these compounds, It is 1 or more types chosen from the group which consists of magnesium salt, calcium salt, and ammonium salt, The heat-radiating fiber sheet of any one of Claims 1-5.   The heat-radiating fiber sheet according to any one of claims 1 to 6, wherein the zirconium compound is fixed at 0.1 to 20% owf with respect to the fiber sheet. A heat dissipating garment in which the fiber sheet according to claim 7 is sewn,
A heat-dissipating garment characterized in that a zirconium compound, a resin cross-linking agent, collagen and chitosan are fixed on the surface of a synthetic fiber.