JP5667733B2 - Carbon nanotube thermal storage feather and cold clothing using the same - Google Patents

Description

  The present invention relates to a heat storage and insulation feather. More specifically, the present invention relates to a heat storage and heat insulation feather having a heat storage and heat retention effect by coating the surface of a duck feather named down with a carbon nanotube composition liquid and a cold protection clothing using the same. About.

  If a textile fabric or garment can absorb heat and store heat inside it, various advantages due to the heat retaining effect can be obtained. In particular, when the textile fabric for clothing and the internal material have a heat storage and heat retention effect, not only can various costs due to heating be saved, but also a more comfortable life can be achieved. Efforts are being made to develop fibers, woven fabrics, or clothing having heat storage and heat retention functions for such purposes.

  Korean Patent No. 2001-0100222 discloses a product having a heat storage and heat insulation effect by impregnating a fabric or clothing with a phase change composition liquid. Korean Patent No. 2002-0059047 discloses a heat storage and heat insulation coated fabric having a multi-layer structure, in which an adhesive layer is formed on a substrate and a heat insulation foam layer is formed thereon. Further, a method for producing a heat-retaining and heat-retaining coated fabric by forming a surface endothermic layer thereon and heat-treating the resultant product is disclosed.

  Recently, Mitsubishi Rayon Co., Ltd. in Japan developed Corebrid-B (trade name (registered trademark)) that absorbs sunlight with a core-sheath acrylic monofilament containing charcoal particles in the core and exhibits heat generation performance. Heat navigator (HEAT NAVI: trade name (registered trademark)) containing carbon-based inorganic substances so that Japan's Descente and Teijin Fibers jointly absorb sunlight and exhibit heat generation performance We have developed a special flat cross-section fiber that is applied mainly to outdoor clothing. However, such an existing technique requires a complex radiation process in which the light-absorbing particles are mixed into the fiber yarn when the fiber is emitted, so that the manufacturing cost is high, and the same heating effect can be obtained without increasing the surface area of the light-absorbing particles. Has the disadvantage that a large amount of light-absorbing particles must be put. That is, the conventional technology cannot obtain a heat storage and heat retention effect corresponding to an increase in manufacturing cost.

  The inventor of the present invention pays attention to the fact that carbon nanotubes having a large surface area and excellent light absorption rate can greatly contribute to the heat storage and heat retention effect of fibers and fabrics, and carbon nanotubes (CNTs) 0.1 to 15% by mass, dispersed Developed a heat storage woven fabric in which a coating liquid consisting of 0.01 to 5 mass% of an agent, 9.89 to 70 mass% of a resin binder, and 10 to 90 mass% of a solvent is coated on one or both sides of a textile fabric. -Patent application was filed under No. 117280 (filed on November 11, 2011).

  Carbon Nanotube (CNT) is a nano material in which a plate-like graphite sheet in which carbon atoms are combined in a hexagonal honeycomb shape is wound into a tube shape with a diameter of several nanometers to several hundred nanometers. It is. Carbon nanotubes exhibit unique electronic structures due to bonding morphology and unique electrical, mechanical and physicochemical properties due to nanometer diameters. For example, carbon nanotubes have a strength that is more than 100 times that of steel, despite a density about half that of aluminum. Moreover, since the size is small, it has a larger surface area per unit mass than a general carbon fiber, has a large energy absorption active area, and can produce a stable mixed material with a very large interaction within the mixed material. Due to the excellent physical properties of carbon nanotubes, industrial applications are actively progressing in various fields such as structural reinforcing materials, energy storage, fuel cells, and sensors. In particular, carbon nanotubes are known as materials that are extremely excellent in terms of light absorption. According to a paper published in 2008 (Zu-Po Yang et al., "Experimental Observation of an Extremely Dark Material Made by a Low-Density nanotube Array", NANO LETTERS, 2008 Vol. 8, No. 2, pp 446 -451), in the case of vertically grown carbon nanotube arrays, the total reflectivity is 0.045%, representing less than 3 times the reflectivity of the material with the lowest reflectivity published so far, It has been recorded as the black body with the lowest reflectivity of any known material.

  In consideration of the characteristics of carbon nanotubes as described above, the present inventors manufacture a coating solution containing carbon nanotubes having a large surface area and an excellent light absorption rate, and coat the surface of the feather with the coating solution. As a result, thermal storage feathers with excellent light-absorbing heat conversion effect were manufactured, and the technology for manufacturing nightwear such as futons and pillows as well as various winter clothing including jackets was developed. It was.

  The objective of this invention is providing the thermal storage feather excellent in the thermal storage heat retention effect.

  Another object of the present invention is to provide a heat storage feather having an excellent heat storage heat retention effect by containing carbon nanotubes.

  Still another object of the present invention is to provide a heat storage feather having an excellent heat storage heat retaining effect by including a multi-wall carbon nanotube among carbon nanotubes.

  Still another object of the present invention is to provide a heat storage feather having a low production cost and an excellent heat storage heat retention effect by including a multi-wall carbon nanotube among carbon nanotubes.

  Still another object of the present invention is to provide nightclothes such as futons and pillows including various types of cold protection clothing manufactured by using heat storage feathers having excellent heat storage and heat retention effects by containing multi-wall carbon nanotubes. .

  The above and other objects of the present invention can all be achieved by the present invention described in detail below.

  The carbon nanotube heat storage feather according to the present invention is characterized in that it is manufactured by a method of coating a feather used in cold clothing for cold protection with a coating liquid containing carbon nanotubes.

  The coating liquid is a carbon nanotube (CNT) 0.1 to 15% by mass, a dispersant 0.01 to 5% by mass, a resin binder 9.89 to 70% by mass and a solvent 10 to 90% by mass, and a solvent 10 to 90% by mass. It means a coating liquid (hereinafter “diluted coating liquid”) that is further diluted 1 to 20 times by further adding the solvent. An additive of 0.01 to 5 parts by mass can be further added to 100 parts by mass of the CNT coating solution.

  The additive may include an antistatic agent, an antibacterial agent, or a deodorant for preventing static electricity and deodorizing feathers.

  Further, 1 to 50 parts by mass of urethane or acrylic resin binder may be further mixed with respect to 100 parts by mass of the coating solution, and finally applied to the feather surface.

  The carbon nanotubes are preferably subjected to a surface modification step in order to improve adhesion and dispersibility with the resin binder.

  The carbon nanotube may be a single-wall carbon nanotube (SWNT), but a multi-wall carbon such as a double-wall carbon nanotube (DWNT), a thin multi-wall carbon nanotube (thin MWNT), a multi-wall carbon nanotube (MWNT), etc. Nanotubes can be preferably used.

  The method of coating the diluted coating solution on the down surface is most preferably a spray method. The diluted coating solution sprayed on the feather surface is preferably 0.01 kg to 1 kg per kg of down.

  Hereinafter, specific contents of the present invention will be described in detail with reference to the accompanying drawings.

  The carbon nanotube heat storage feather of the present invention provides a heat storage down with excellent heat storage and heat retention effect by containing carbon nanotubes in the feather, and by including multi-wall carbon nanotubes among carbon nanotubes, the production cost is reduced. Although it is low, it has the effect of the invention that heat storage feathers that are excellent in heat storage heat retention effect can be manufactured, and various cold protection clothing can be manufactured therefrom.

It is a graph for showing the thermal storage property before washing of the carbon nanotube thermal storage feather by Examples 1-2 of the present invention, and comparative example 1. It is a graph for showing the thermal storage property after washing of the carbon nanotube thermal storage feather by Examples 1-2 and comparative example 1 of the present invention. It is a graph for showing the thermal storage property before washing of the carbon nanotube thermal storage feather by comparative examples 2-5 of the present invention. It is a graph for showing the thermal storage property after washing of the carbon nanotube thermal storage feather by comparative examples 2-5 of the present invention.

  The present invention relates to a heat storage and heat insulation down, and relates to a heat storage and heat insulation feather having a heat storage and heat insulation effect by coating a carbon nanotube composition liquid on the surface of the down and a cold protection clothing using the same.

  The carbon nanotube heat storage feather according to the present invention is manufactured by coating a feather used for down clothing for cold protection with a coating liquid containing carbon nanotubes.

  The coating liquid is a CNT coating liquid comprising 0.1 to 15% by mass of carbon nanotubes (CNT), 0.01 to 5% by mass of a dispersant, 9.89 to 70% by mass of a resin binder, and 10 to 90% by mass of a solvent. In addition, it means a coating liquid (hereinafter, “diluted coating liquid”) diluted 1 to 20 times by further adding the solvent.

  The carbon nanotube may be a single-wall carbon nanotube (SWNT), but a multi-wall carbon nanotube such as a double-wall carbon nanotube (DWNT), a thin multi-wall carbon nanotube (thin MWNT), a multi-wall carbon nanotube (MWNT), etc. Can be preferably used.

  Single wall carbon nanotubes (SWNT) can be used to produce the carbon nanotube coating liquid of the present invention, but single wall carbon nanotubes are expensive. In the present invention, as a result of testing with multi-walled carbon nanotubes in order to solve such problems of single-walled carbon nanotubes, it has been found that they have an excellent heat storage and heat retention effect. And since a multi-wall carbon nanotube is low in price unlike a single-wall carbon nanotube, a thermal storage fabric can be manufactured at low cost. In the present invention, both double-walled carbon nanotubes (DWNT) and thin multi-walled carbon nanotubes (thin MWNT) exhibit an excellent heat storage effect and are low in price, and therefore can be used. Carbon nanotubes are composed in the coating solution in the range of 0.1 to 15% by mass. However, if the content is 0.1% by mass or less, it is difficult to expect a sufficient heat storage and insulation effect. Carbon nanotubes are used, which increases the cost.

  The carbon nanotubes are preferably subjected to a surface modification step in order to improve adhesion and dispersibility with the resin binder. As a conventional method for modifying the surface of carbon nanotubes, there are liquid or gaseous acid treatment, ozone water treatment, plasma treatment and the like. These usual methods for modifying the surface of carbon nanotubes can be easily carried out by a person having ordinary knowledge in the technical field to which the present invention belongs.

  The carbon nanotube coating solution should uniformly and finely disperse the carbon nanotubes in order to improve the light absorption area. For this purpose, a dispersant, that is, a surfactant is added. As the dispersant used in the present invention, a commercially available normal surfactant can be used, and representative examples include SDS, SDBS, SDSA, DTAD, CTAB, NaDDBS, Cholic Acid, and Tween (registered trademark). 85, Brij (registered trademark) 78, Brij 700, Triton (registered trademark) X, PVP, EC (Ethyl Cellulose), Nafion (registered trademark), HPC (Hydroxy Propyl Cellulose), CMC (Carboxy Methyl Cellulose), HEC (Hydroxy Ethyl) Cellulose) and Pluronic (PEO-PPO Copolymer (registered trademark)). These can be used alone or in the form of a mixture of two or more.

  The dispersant is used in the coating liquid in the range of 0.01 to 5% by mass. However, when the content is 0.01% by mass or less, sufficient dispersibility is not exhibited. An agent is used, which is not preferable.

  A resin binder is used for the coating liquid in order to ensure bonding with fibers and fastness to washing. The resin binder includes a thermosetting binder and a UV curable binder, and includes a urethane resin, an acrylic resin, a urethane-acrylic copolymer, a polyimide, a polyamide, a polyether resin, a polyolefin resin, and a melamine resin. One selected from the above or a mixture of two or more of these can be preferably used. The resin binder is used in the coating solution at 9.89 to 70% by mass, and the type and amount of the resin binder are easily implemented by those skilled in the art within the above range in consideration of the relationship with other components. Can do.

  The carbon nanotubes, the dispersant and the resin binder are mixed in a solvent to form a coating solution. Examples of the solvent used include water, methanol, ethanol, ethyl acetate, acetone, methyl ethyl ketone (MEK), toluene, dimethylformamide (DMF) and the like alone or a mixture thereof. However, it is not necessarily limited to these solvents. The solvent is the remaining part excluding the carbon nanotube, the dispersant and the resin binder, and is used at 10 to 90% by mass.

  Of course, various additives may be added to the coating liquid in addition to the carbon nanotubes, the dispersant, and the resin binder in order to provide the stability of the solution and the specific functions required. Additives added include slip agents, fluidity improvers, thickeners, antistatic agents, antibacterial agents, deodorants, water repellents, air / water vapor / sweat permeants, friction coefficient improvers, UV stabilizers, etc. These may be used alone or in combination of two or more. Of course, the additives are not necessarily limited, and other additives can be appropriately used depending on the required usage. An additive of 0.01 to 5 parts by mass can be further added to 100 parts by mass of the coating liquid.

  The diluted coating solution may be applied directly to the feather surface, or may be further mixed with a urethane or acrylic resin binder and finally applied to the feather surface. By mixing the urethane resin binder, the CNT particles are not dropped off during the washing process and are fixed to the feathers. It is preferable to further mix 1 to 50 parts by mass of urethane or acrylic resin binder with respect to 100 parts by mass of the coating liquid.

  The method of coating the diluted coating liquid on the surface of the feathers is most preferably a spray method. In the present invention, the diluted coating liquid sprayed onto the feathers is a diluted coating liquid obtained by diluting a CNT coating liquid containing 0.1 to 15% by mass of carbon nanotubes (CNT) 1 to 20 times with a solvent, Use 0.01 kg to 1 kg per kg of feathers. When the diluted coating solution is used at 0.01 kg or less per 1 kg of feathers, it is difficult to expect a good heat storage effect, and when it is 1 kg or more, use of an unnecessary coating solution causes an increase in cost.

  As described above, the CNT-coated feather coated with the CNT coating liquid dries the coating liquid applied in a room temperature or a heated chamber. The coating method and the drying process after coating, that is, the temperature of the chamber, the drying time in the chamber, and the like can be changed according to the type and specification of the feathers, and such changes are in the technical field to which the present invention belongs. And can be easily implemented by those having ordinary knowledge.

  The heat storage and insulation feathers manufactured as described above are used as nightwear items such as futons and pillows, including down jacket clothing, to manufacture various products. Manufacture of clothing and nightwear using the heat storage and keeping feathers of the present invention can be easily performed by a person having ordinary knowledge in the technical field to which the present invention belongs.

  The sewing feathers used in the present invention usually use the specifications of 90/10 to 80/20 which are already commercially available, but this contains 80 to 90% feathers and 10 to 20% other components. means. Other components are composed of small feathers, damaged feathers, down fibers, feather fibers, and the like. Feathers are mainly used for down, but include goose hair and other usable hair.

  The invention is further embodied by the following examples, which are for purposes of illustration of the invention and are not to be construed as limiting or limiting the protection scope of the invention.

Production of CNT coating solution:
In manufacturing the CNT coating liquid according to the present invention, the surface of MWNT is oxidized using a mixed solution of nitric acid and sulfuric acid (3: 1) to manufacture MWNT with improved dispersion performance. 5% by mass of the above-treated MWNT, 5% by mass of a dispersant (trade name: Triton X100), 0.2% by mass of an antifoaming agent (trade name: Surfynol (registered trademark) 104H) and 39.8% by mass of distilled water Then, ultrasonic waves were applied for 1 hour at an output of 140 W (70%) to disperse the CNTs. The dispersion was mixed with 50% by mass of an acrylic binder and stirred with a stirrer for 30 minutes to produce a coating solution.

Example 1
Production of heat storage feathers:
The CNT coating solution prepared above is diluted with 100% by mass of distilled water to prepare a diluted coating solution. 2 kg of the diluted coating solution is sprayed for 10 seconds onto 10 kg of 90/10 standard feathers flowing in the air in a chamber at 120 ° C. After spraying the coating liquid, the feathers are further flowed for 2 minutes, and then the humidity in the chamber is removed, and further drying is performed for 3 minutes while maintaining the chamber temperature at 120 ° C.

Measurement of heat storage performance:
6 g of the feathers manufactured as described above are put into a 15 cm × 15 cm polyester fabric bag to prepare a heat storage performance test sample. While irradiating at a distance of 30 cm using an infrared lamp at room temperature, the temperature change of the sample surface was observed using a thermal image camera. The infrared lamp was turned on to measure the temperature over time, the lamp was turned off and the temperature over time was measured and shown in Table 1, and the temperature change after washing is shown in Table 2. Numerical values for Table 1 are shown in the graph of FIG. 1, and numerical values for Table 2 are shown in the graph of FIG. FIG. 1 is a graph for showing heat storage properties before washing of untreated feathers not coated with a diluted coating solution and carbon nanotube heat storage feathers according to Examples 1 and 2 of the present invention, and FIG. It is a graph for showing the heat storage property after washing of the untreated feather which is not coated, and the carbon nanotube heat storage feather by Examples 1-2 of the present invention.

  As a result of measurement, the examples of the present invention had a temperature rise effect of 3 ° C. or more at maximum, and there was no change in the heat storage performance even after washing.

(Example 2)
The same procedure as in Example 1 was performed except that 1 kg of the diluted coating solution was sprayed onto 10 kg of feathers. As a result of measuring the heat storage performance, the examples of the present invention had a temperature rise effect of 2 ° C. or more at maximum, and there was no change in the heat storage performance even after washing. Further, it was found that the heat storage performance was decreased in proportion to the decrease in the coating amount as compared with Example 1.

(Comparative Example 1)
The same method as in Example 1 was performed except that the CNT coating liquid was not sprayed.

(Comparative Examples 2 to 5)
Production of CNT coating solution:
In manufacturing the CNT coating liquid according to the present invention, the surface of MWNT is oxidized using a mixed solution of nitric acid and sulfuric acid (3: 1) to manufacture MWNT with improved dispersion performance. The acid-treated MWNT 5% by mass, a dispersant (trade name: Triton X100) 5% by mass, an antifoaming agent (trade name: Surfynol 104H) 0.2% by mass and distilled water 89.8% by mass were mixed, and 140 W (70 %) Was applied for 1 hour to disperse CNTs. In this comparative example, no acrylic binder was added to the dispersion.

(Comparative Example 2)
The same method as in Example 1 was performed except that the CNT coating liquid was not sprayed.

(Comparative Example 3)
Production of heat storage feathers:
The CNT coating solution prepared above is diluted with 100% by mass of distilled water to prepare a diluted coating solution. 2 kg of the diluted coating solution is sprayed for 10 seconds onto 10 kg of 90/10 standard feathers flowing in the air in a chamber at 120 ° C. After spraying the coating liquid, the feathers are further flowed for 2 minutes, and then the humidity in the chamber is removed and further drying is performed for 3 minutes while maintaining the chamber temperature at 120 ° C.

Measurement of heat storage performance:
The heat storage performance was measured by the same method as in the example.

  The infrared lamp was turned on and the temperature over time was measured. The lamp was turned off and the temperature over time was measured and shown in Table 3. Table 4 shows the temperature change after washing. Numerical values for Table 3 are shown in the graph of FIG. 3, and numerical values for Table 4 are shown in the graph of FIG. FIG. 3 is a graph for illustrating heat storage properties before washing of carbon nanotube heat storage feathers according to Comparative Examples 2 to 5 of the present invention, and FIG. 4 is a graph after washing of carbon nanotube heat storage feathers according to Comparative Examples 2 to 5 of the present invention. It is a graph showing heat storage property.

(Comparative Example 4)
The same as in Comparative Example 3 except that the CNT coating solution prepared above was diluted with 200% by weight distilled water to prepare a diluted coating solution, and 2 kg of the diluted coating solution was sprayed onto 10 kg of feathers. The method was carried out. The infrared lamp was turned on and the temperature over time was measured. The lamp was turned off and the temperature over time was measured and shown in Table 3. Table 4 shows the temperature change after washing.

(Comparative Example 5)
Comparative Example 3 except that the CNT coating solution prepared above was diluted with 200% by weight of distilled water to prepare a diluted coating solution and sprayed 0.8 kg of the diluted coating solution onto 10 kg of feathers. The same method was used. The infrared lamp was turned on and the temperature over time was measured. The lamp was turned off and the temperature over time was measured and shown in Table 3. Table 4 shows the temperature change after washing.

  According to Comparative Examples 3 to 5, there was a temperature increase effect of 1 to 4 ° C. or more depending on the coating amount, but a decrease in heat storage performance after washing was observed by not adding a resin binder to the CNT coating liquid.

  From the data of Tables 1 to 4 and the graphs of FIGS. 1 to 4, it can be seen that the heat storage and keeping feathers of the present invention have excellent heat storage properties and have excellent wash fastness when a resin binder is added. In the comparative example, the heat storage effect after washing is reduced from that before washing because the CNT particles fall off from the feathers due to the addition of no resin binder. That is, it can be seen that a resin binder is necessary to improve washing durability and maintain heat storage performance.

  The protection scope of the present invention is embodied by the following appended claims, and all simple variations and modifications of the present invention should be construed as belonging to the protection scope of the present invention.

Claims (12)

  A carbon nanotube heat storage feather manufactured by coating a feather used for down clothing or nightwear with a coating solution containing carbon nanotubes.   The coating solution is a CNT coating solution comprising 0.1 to 15% by mass of carbon nanotubes (CNT), 0.01 to 5% by mass of a dispersant, 9.89 to 70% by mass of a resin binder, and 10 to 90% by mass of a solvent. The carbon nanotube heat storage feather according to claim 1, wherein the heat storage feather is a carbon nanotube heat storage feather.   The surface of the carbon nanotube is modified by liquid acid treatment, gaseous acid treatment, ozone water treatment, or plasma treatment in order to improve adhesion and dispersibility with a resin binder. 2. The carbon nanotube thermal storage feather according to 2.   Furthermore, 1-50 mass parts of urethane or an acrylic resin binder is mixed with respect to 100 mass parts of said coating liquids, The carbon nanotube thermal storage feather of Claim 2 characterized by the above-mentioned.   The carbon nanotube heat storage feather according to claim 2, wherein the coating liquid is mixed with at least one additive selected from an antistatic agent, an antibacterial agent, a deodorant, and a water repellent.   The carbon nanotube heat storage feather according to claim 2, wherein the coating liquid is coated by a spray method.   The carbon nanotube thermal storage feather according to claim 2, wherein the carbon nanotube is a multi-wall carbon nanotube (MWNT).   The carbon nanotube thermal storage feather according to claim 1, wherein the feather is a down or goose hair.   A clothing or night product manufactured using the carbon nanotube thermal storage feather according to any one of claims 1 to 7.   The carbon nanotube thermal storage feather according to claim 2, wherein the CNT coating liquid is a coating liquid ('diluted coating liquid') further diluted 1.1 to 20 times by further adding the solvent. .   The surface of the carbon nanotube is modified by liquid acid treatment, gaseous acid treatment, ozone water treatment, or plasma treatment in order to improve adhesion and dispersibility with a resin binder. 10. The carbon nanotube thermal storage feather according to 10.   The carbon nanotube heat storage feather according to claim 10 or 11, wherein 1 to 50 parts by mass of a urethane or acrylic resin binder is further mixed with 100 parts by mass of the coating liquid.