KR101611380B1 - Carbon nanotube coating solution for improving thermokeeping, carbon nanotube thermokeeping product, and clothes including the carbon nanotube thermokeeping product - Google Patents

Abstract

The present invention discloses a carbon nanotube insulating functional composition, a carbon nanotube insulating functional product, and a garment manufactured using the carbon nanotube insulating functional product. The carbon nanotube insulating function functional composition of the present invention is coated on a substrate to improve the warming ability of the substrate, and includes carbon nanotubes (CNT), a metal additive, and a solvent. INDUSTRIAL APPLICABILITY According to the present invention, the heat generating function and the heat reflecting function can be combined to maximize the warming effect.

Description

[TECHNICAL FIELD] The present invention relates to a carbon nanotube insulating functional material, a carbon nanotube insulating functional material, a carbon nanotube insulating functional material, a carbon nanotube insulating functional material, and a carbon nanotube thermocouping product, product}

The present invention relates to a carbon nanotube insulating functional composition, a carbon nanotube insulating functional product, and a garment manufactured using the carbon nanotube insulating functional product, and is applicable to a field requiring heat insulation.

Carbon nanotubes have high thermal conductivity and excellent absorption of light energy at all wavelengths. It is possible to manufacture a light emitting functional product by utilizing the ability to convert absorbed light energy into thermal energy.

Korean Patent Laid-Open Publication No. 2002-0059047 discloses a heat-generating heat insulating coating fabric having a multilayer structure.

In recent years, Mitsubishi Leon of Japan has developed a fiber in which core-sheathed acrylic staple fibers containing charcoal particles are absorbed by sunlight to exhibit heat-generating performance. Japan's DeSant and Deijin fibers absorb solar light We have developed a special flat section fiber containing a carbon-based inorganic material that exhibits heat generation performance.

However, since the products have a function of absorbing sunlight, it is inevitably deteriorated in the nighttime or cloudy weather without sunlight.

Especially, various advantageous effects such as a fiber fabric for clothes, a home textile fabric such as a curtain, a sofa, etc., can be obtained in addition to a light heating effect and a reduction in heating cost if they have a warming effect.

It is an object of the present invention to provide a carbon nanotube insulating functional composition, a carbon nanotube insulating functional product and a garment manufactured using the carbon nanotube insulating functional product, which are excellent in a heat reflecting effect as well as a light exothermic functional effect.

In order to achieve the above object, the carbon nanotube insulating functional composition of the present invention is coated on a substrate to improve the warming ability of the substrate, and includes carbon nanotubes (CNT), a metal additive, and a solvent.

The metal additive is preferably selected from the group consisting of aluminum (Al), zinc (Zn), titanium (Ti), copper (Cu), magnesium (Mg), silver (Ag), gold (Au) At least one selected.

Wherein the metal additive is an aluminum paste containing an aluminum (Al) metal, and the aluminum paste is at least one selected from the group consisting of mineral spirits, water, and ethyl acetate (EA); And an aluminum metal contained in the solvent and having a flake or power shape with a particle diameter of 1 to 35 占 퐉,

The solid content of the aluminum paste may be 10 wt% to 80 wt% of the aluminum paste. In this case, the metal additive may further include a lubricant, and the lubricant may include stearic acid. The aluminum metal may have a plate-like shape having a diameter of 4 to 15 占 퐉.

The carbon nanotube insulating functional composition of the present invention may further comprise a resin binder, wherein the resin binder is selected from the group consisting of urethane resin, acrylic resin, urethane-acrylic copolymer, polyimide, polyamide, polyether resin, polyolefin resin and melamine resin Resin, or a mixture of two or more thereof. In this case, 0.1 to 15 wt% of the carbon nanotubes, 0.01 to 15 wt% of a dispersant, 0.1 to 50 wt% of a metal additive, 1 to 50 wt% of a resin binder, and 10 to 98 wt% of a solvent may be included.

It further includes an additive selected from the group consisting of a dispersant, a slip agent, a flow improver, a thickener, an anti-settling agent, a defoaming agent, an antistatic agent, a water repellent agent, an air permeability agent, .

In another aspect of the present invention, there is provided a carbon nanotube insulating functional product comprising a substrate made of fiber or glass or polymer, and a coating layer comprising a carbon nanotube (CNT) and a metal additive on the surface of the substrate.

The fibers may be at least one selected from vegetable fibers, animal fibers, regenerated fibers, semi-synthetic fibers, synthetic fibers, woven fabrics, knitted fabrics, nonwoven fabrics and felt.

Another aspect of the present invention provides a garment manufactured using the carbon nanotube insulating functional product.

In this case, it is preferable that a metal is distributed in an upper portion of the coating layer in contact with human skin and distributed in a concentration of 80 wt% or more.

According to the present invention, it is possible to obtain a carbon nanotube insulating functional composition, a carbon nanotube insulating functional product, and a garment manufactured using the carbon nanotube insulating functional product, which are excellent in heat reflection and light exothermic functions. Therefore, heat exiting from the inner skin or the like is reflected, and light exiting from the outside is saved, so that a heat generating function for generating heat can be performed at the same time.

Therefore, in the presence of sunlight, it receives light from the sun to emit heat to increase the internal temperature, and to reflect the heat from the inside, resulting in a warming function.

Fig. 1 is a graph showing the evaluation of the light generating functional properties of the carbon nanotube insulating functional product according to the example, the comparative example 1, and the comparative example 2. Fig.
Fig. 2 is a photograph of thermal reflection property evaluation of the product of Comparative Example 1. Fig.
3 is a photograph showing the thermal reflection property of the carbon nanotube insulating function product according to the embodiment

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will now be described in more detail with reference to the accompanying drawings.

A carbon nanotube insulating functional composition according to a preferred embodiment of the present invention includes a carbon nanotube (CNT), a metal additive, and a solvent.

The carbon nanotubes may be single wall carbon nanotubes (SWNTs), double wall carbon nanotubes (DWNTs), thin wall carbon nanotubes (thin MWNTs), and multiwall carbon nanotubes (MWNTs).

The carbon nanotubes may be dispersed in a solvent by a dispersant.

The dispersant functions to uniformly and finely disperse the carbon nanotubes to improve the light absorption area. As the dispersant used in the present invention, commercially available surfactants can be used. Representative examples of the dispersing agent include sodium dodecyl sulfate (SDS), sodium dodecylbenzene sulfonate (SDBS), SDSA (sodium dodecanesulfonic acid), DTAD (triad (dodecyldinethylammonioacetoxy) diethyltriaminetrichloride), cetyltrimethylammonium (CTAB), sodium dodecylbenzene sulfonate (NaDDBS), cholic acid, polyoxyethylene lenesorbitan trioleate (trade name: Tween 85), polyoxyethylene sorbitan trioleate polyethylene glycol octadecyl ether (polyethylene glycol octadecyl ether) (trade name: Sigma-Aldrich Co., Brij 78, Brij 700), polyethylene glycol tert-octylphenyl ether (polyethylene glycol tert -octylphenyl ether) (trade name: Triton X), polyvinyl (PVP), Ethyl Cellulose (EC), Nafion, HPC (Hydroxy Propyl Cellulose), CMC (Carboxy Methyl Cellulose), HEC (Hydroxy Ethyl Cellulose) uronic (PEO-PPO Copolymer), etc. These may be used singly or in the form of a mixture of two or more kinds.

The dispersing agent is 5 to 500 parts by weight based on 100 parts by weight of the carbon nanotubes. When the content of the dispersant is within the above range, a coating composition having excellent dispersibility can be obtained.

The metal additive is at least one selected from the group consisting of aluminum (Al), zinc (Zn), titanium (Ti), copper (Cu), magnesium (Mg), silver (Ag), gold (Au) Lt; / RTI > The metal additive is mixed with the carbon nanotubes and functions to reflect heat introduced from the outside. This is because the function of reflecting radiant heat is excellent in metals such as gold, silver and aluminum.

Accordingly, if the carbon nanotubes and the metal additives are added to the coating composition in an appropriate amount, it is possible to maximize the effect that the carbon nanotubes are exposed to the sun, for example, For example, at night, which is not exposed to sunlight, the effect of heat reflection of the metal additive is maximized, and the warming effect can be obtained.

In this case, the metal additive may include an aluminum (Al) metal. The aluminum metal can maximize heat reflection.

The metal additive may be a metal paste. In this case, the metal paste may be an aluminum paste containing the aluminum metal. The aluminum paste may include an aluminum metal having a flake or power shape having a particle diameter of 1 to 35 μm and a fatty acid derivative having 0.2 to 10 wt% of the aluminum metal.

In this case, the solid content of the aluminum paste is preferably 10 to 80 wt% of the entire aluminum paste.

The aluminum paste may be an aluminum pigment. The aluminum pigment may include a pigment solvent, an aluminum metal, and a pigment component. The pigment solvent may be at least one selected from the group consisting of mineral sprites, water, and ethyl acetate. A lubricant may be added to prevent cold pressing during the production of the aluminum paste.

The metal paste may be divided into a leafing type and a nonleafing type. In this case, more preferably, the metal paste has a ripping type shape.

The ripping type floats on the surface of the coating layer without wetting the metal in the coating layer due to the surface tension. For example, when the metal paste is an aluminum pigment, it may be formed when stearic acid is used as a lubricant in the production of an aluminum pigment.

The logic ping type means wetted to the coating layer so that the metal is arranged to spread evenly. For example, when the metal is aluminum, a strong polar substance or a lubricating oil (for example, oleic acid) is added to the lipid pigment, and the metal is completely wetted and spread evenly on the coating layer.

Therefore, in the case of the above-mentioned ripping type during coating, it is possible to bias the metals closer to one side of the substrate, for example, human skin, so that the heat from the human body can be reflected back toward the skin , The amount of the metal is relatively small in a portion close to the outside, relatively small heat is reflected from the outside, and at the same time, the carbon nanotube absorbs light and emits heat.

The aluminum metal preferably has a plate-like shape having a diameter of 4 to 15 占 퐉.

More preferably, in the ripping type, the metal has a plate-like shape, and more preferably has a diameter of 4 to 15 탆. This is because the frequency of the body temperature is 4 to 15 占 퐉 and the effect of reflecting heat from the body temperature is the best in the diameter. This is because the wavelength of the sun is 0.2 to 7 占 퐉, and the metal having the diameter of 4 to 15 占 퐉 relatively has a relatively small effect of reflecting heat from the sun.

The carbon nanotube insulating functional composition may further include a resin binder. The resin binder includes a thermosetting binder and a UV curable binder. Specific examples of the resin binder include a urethane resin, an acrylic resin, a urethane-acrylic copolymer, a polyimide, a polyamide, a polyether resin, a polyolefin resin and a melamine resin Or a mixture of two or more thereof may be used.

The resin binder is 0.1 to 900 parts by weight based on 1 part by weight of the carbon nanotubes. The kind and amount of the resin binder can be easily practiced by those skilled in the art within the range in consideration of the relationship with other components.

The solvent is selected from the group consisting of water, methanol, ethanol, ethyl acetate, acetone, methyl ethyl ketone (MEK), toluene and N, N-dimethylformamide (DMF). However, it is not necessarily limited to these solvents. The solvent is used in an amount of 70 to 99% by weight when the solid content of the coating composition is 1-30% by weight.

The content of the solvent is 10 to 998 parts by weight based on 1 part by weight of the carbon nanotubes. When the content of the solvent is within the above range, a uniform composition of the coating composition can be obtained and the coating operation using the coating composition is easy.

Wherein the carbon nanotube insulating functional composition comprises 0.1 to 15 wt% of carbon nanotubes (CNT), 0.01 to 15 wt% of a dispersant, 0.1 to 15 wt% of a metal additive, 1 to 50 wt% of a resin binder, 10 To 90% by weight.

In this case, the weight ratio of the carbon nanotubes is more preferably 1 wt% to 2 wt% with respect to the total composition. This is to keep the light emitting effect deteriorated due to the addition of the metal additive excellent. When the weight ratio of the carbon nanotubes is more than 2 wt%, the light emitting effect is not increased any more and the manufacturing cost is increased.

In this case, in the case of aluminum as the metal additive, the weight ratio of aluminum is preferably 1 part by weight to 10 parts by weight relative to 1 part by weight of the carbon nanotubes.

This is because when the weight ratio of aluminum is less than 1 part by weight, the heat reflecting function is lowered. When the weight ratio of aluminum is more than 10 parts by weight, the light emitting function is lowered.

According to the present invention, the effect of heat reflection is maximized by adding a metal additive, and the content of the metal additive and the carbon nanotube is controlled to maintain excellent light heating effect. Particularly, if the content of carbon nanotubes is increased to a certain amount or more, there is an adverse effect that the light emitting effect is not excellently increased but the cost is increased.

Various additives may be added to the coating composition to impart the stability of the solution or the specific function required. Additives to be added include additives such as slip agents, flow improvers, thickeners, antistatic agents, antimicrobial agents, deodorants, water repellents, air / water vapor / perspiration agents, friction coefficient improvers, antistatic agents, antistatic agents, antimicrobial agents, deodorants, / Sweat transfer agent, a friction coefficient improver, and an ultraviolet stabilizer. These may be used singly or in combination of two or more. Of course, the additive is not necessarily limited to the above additives, and other additives may be suitably used depending on the intended use. The content of the additive is 10 to 1000 parts by weight based on 100 parts by weight of the carbon nanotubes.

Meanwhile, the carbon nanotube insulating functional product according to another embodiment of the present invention includes a substrate and a coating layer.

The substrate may be a fiber, a transparent substrate, or glass. The fibers can be used in a variety of outdoor clothes requiring heat insulation, leisure goods such as sporting goods, mountain climbing, fishing, etc., uniforms, sofas for curtains and sofas for interior decorations. Thus, the fibers usable in the present invention include natural fibers and synthetic fibers.

In addition, the fibers of the present invention include vegetable fibers such as cotton and hemp, animal fibers such as monospores, regenerated fibers such as rayon, and semi-synthetic fibers such as acetate.

One kind of the fibers includes woven fabrics, knitted fabrics, nonwoven fabrics, and felt. A fabric is a fabric made by crossing a vertical inclination and a horizontal inclination at right angles. A knitted fabric refers to a fabric made up of a single yarn or a plurality of strands made up of loops (nose, loop) connected to each other.

Examples of the transparent substrate include glass, and polymers such as PET, PC, PI, PEN, and COC.

The coating layer comprises a carbon nanotube (CNT) and a metal additive on the surface of the substrate. In this case, the carbon nanotubes and the metal additive are the same as the carbon nanotubes and the metal additive described in the above-mentioned carbon nanotube insulating functional composition, and therefore, detailed description thereof will be omitted.

Examples of the method of coating the coating composition on one of the substrates include gravure, offset, kiss bar, knife, Meyer bar, roll coating, dipping, padding and spraying.

As a method of coating the above coating composition on a substrate, a general wet coating method such as spray coating, gravure coating, slot die coating, dip coating, bar coating, roll to roll coating and the like can be used.

When the coating composition is coated on the fiber, the coating product is cured by transferring the coated product at a constant rate in the chamber or at room temperature. The coating method or the curing process after the coating, that is, the temperature of the chamber, the transfer speed of the fibers in the chamber, and the like can be changed according to the type and the specification of the fibers. Such changes can be made by those skilled in the art The present invention can be easily carried out by a person skilled in the art.

The fibers can be used as garments. In this case, the fibers wrap the human skin. Accordingly, when there is light, the fabric absorbs light and exothermically functions to increase the body temperature of a person.

In addition, the heat generated from the skin functions to maintain the body temperature by being reflected from the clothes.

The coating layer may be coated on the substrate in a leafing type. Alternatively, the coating layer may be coated on the substrate in a non-leafing type.

The ripping type floats on the surface of the coating layer without wetting the metal in the coating layer due to the surface tension. For example, when the metal additive is an aluminum pigment, it may be formed when stearic acid is used as a lubricant, for example, in the production of an aluminum pigment.

The logic ping type means wetted to the coating layer so that the metal is arranged to spread evenly. For example, when the metal is aluminum, a strong polar substance or a lubricating oil (for example, oleic acid) is added to the lipid pigment, and the metal is completely wetted and spread evenly on the coating layer.

According to the present invention, when the coating material is coated on the base material by the ripping type and the metal side is directed toward the skin side of the person, the body temperature reflection effect is further improved, the body temperature maintaining effect is improved, and the metal is minimized in the opposite direction The function of reflecting light is minimized, and carbon nanotube absorbs light, maximizing heat generation and heat storage effect. In this case, it is preferable that the upper part of the coating layer is directed to the skin by allowing the metal to be contained in the upper part of the coating layer by 80% or more.

The metal on the coating layer preferably has a plate-like shape having a diameter of 4 to 15 占 퐉. This is because the frequency of the body temperature is usually about 4 to 15 mu m and the effect of the metal reflecting heat from the body temperature is the best at a diameter of 4 to 15 mu m. This is because the wavelength of the sun is 0.2 to 7 占 퐉, and the metal having the diameter of 4 to 15 占 퐉 relatively has a relatively small effect of reflecting heat from the sun.

In this case, it is more preferable that the metal on the coating layer has a plate-like shape and has a diameter of 4 to 6 占 퐉.

According to another embodiment of the present invention, the carbon nanotube insulating functional product can be manufactured by mixing an adhesive and a carbon nanotube coating composition during bonding of the fiber and the fiber by bonding. The kind and amount of the adhesive used in this case can be easily carried out by a person having ordinary skill in the art to which the present invention belongs.

The fiber and garment according to the present invention are excellent in thermal insulation effect and excellent in light absorption and heat generation effect in the sun. It can be seen that the fibers and clothes coated with the carbon nanotube coating composition of the present invention maintain their performance even after washing.

The present invention will be further illustrated by the following examples, which should not be construed to limit or limit the scope of protection of the present invention.

Example: Preparation of carbon nanotube insulating functional product

In preparing the carbon nanotube insulating functional coating composition according to the present invention, 1 g of aluminum paste and 1 g of toluene are mixed and wetted to prepare a metal additive. 10 g of 1 wt% of dispersed MWNT, 12 g of urethane resin and 60 g of DMF are mixed in advance to prepare a carbon nanotube solution. The carbon nanotube solution and the metal additive were mixed together with 16 g of DMF and agitated at a speed of 600 to 800 rpm for 30 minutes with a stirrer.

Preparation of Carbon Nanotube Insulating Functional Product: The coating composition obtained by the above procedure was coated on the backside of a 100% polyethylene fabric by a knife edge coating method with a knife at a distance of 0.05 mm between the knife and the fabric surface, And cured for 30 minutes.

Comparative Example 1: Production of carbon nanotube product

In the carbon nanotube product of the comparative example, the same carbon nanotube solution as the example is prepared. The carbon nanotube solution was mixed with 16 g of DMF and stirred at a speed of 600 to 800 rpm for 30 minutes using a stirrer. In this case, the metal additives were not further mixed.

Production of the product: The same procedure as in the production of the heat reflecting product of the Example was carried out.

Comparative Example 2: A coating solution consisting of only a binder and a solvent in which carbon nanotubes and metal additives were removed was coated.

≪ Evaluation Example 1 >: Evaluation of light generating functional property

1) Photothermal functional properties of the carbon nanotube insulating functional product according to the example, comparative example 1 and comparative example 2

The light exothermic functional effects of the carbon nanotube insulating functional products according to the above Examples and Comparative Examples 1 and 2 were evaluated according to the following methods.

The temperature was measured using a thermocouple while irradiating the coated surface with light at room temperature by using an infrared lamp disposed at a distance of about 60 cm from the PET film coated with the heat-sensitive functional coating composition. The temperature of the PET film before application of the coating composition and the temperature of the film after application and drying of the coating composition were measured and the temperature difference (? T) was calculated and shown in Table 1 below.

division ΔT (° C.) Example 5.7 Comparative Example 1 5.7 Comparative Example 2 0

Referring to Table 1, it can be seen that the warming product including the carbon nanotube coating composition obtained by mixing the carbon nanotubes and the metal additives of the examples has excellent light heating functional effect.

2) Photothermal functional properties of carbon nanotube insulating functional products

In the above Examples and Comparative Examples 1 and 2, the infrared lamp was turned on and the temperature was measured with time. The lamp was then turned off and the temperature was measured over time, which is shown in Figure 1, respectively. Referring to FIG. 1, in comparison with Comparative Example 2, it can be seen that the product containing carbon nanotubes (Example, Comparative Example 1) is excellent in the light exothermic functional effect.

≪ Evaluation Example 2 >: Measurement of warming property

In the above-mentioned Examples and Comparative Example 1 products, the infrared ray lamp (FLIR) was turned on while the hand was put on the product to compare the effect of body temperature reflection. In the case of an infrared lamp, the warmer the better, the more reddish it appears. Fig. 2 shows a case where a hand is put on the product of Comparative Example 1, and Fig. 3 shows a case where a hand is put on the product of the embodiment.

As shown in FIG. 2 and FIG. 3, it can be seen that a darker red color appears in the embodiment than in the case of Comparative Example 1. Accordingly, it can be seen that the case of the embodiment is excellent in the warming effect.

Table 2 shows the results of the evaluation by the external organization (FITI test institute).

division Heat retention rate (%) Example 28.7 Comparative Example 1 23.3 Comparative Example 2 24.1

As shown in Table 2, in the case of the embodiment, 5.4% in comparison with the comparative example 1 and 4.6% higher than that in the comparative example 2 were measured and the heat retention rate was 23.2% and 19.1% Respectively.

This is because, in general, when the carbon nanotubes alone are coated without metal additives, the heat reflecting effect is not generated and the heat retention rate is not high. In contrast, in the case of the embodiment, the heat reflecting effect is excellent and the thermal retention ratio is excellent.

The scope of protection of the present invention will be defined by the claims appended hereto, and all mere modifications or alterations of the present invention should be construed as falling within the scope of the present invention.

Claims (14)

delete delete Which is coated on a substrate to simultaneously improve the light emitting ability and heat reflecting ability of the substrate,
A carbon nanotube (CNT), a metal additive, and a solvent,
The metal additive is an aluminum paste containing an aluminum (Al) metal,
The aluminum paste comprises:
At least one solvent selected from mineral spirits, water and ethyl acetate (EA); And
And an aluminum metal contained in the solvent and having a flake or power shape with a particle diameter of 1 to 35 占 퐉,
Wherein the solid content of the aluminum paste has 10 wt% to 80 wt% of the aluminum paste. The method of claim 3,
Wherein the metal additive further comprises a lubricant,
Wherein the lubricant comprises stearic acid. ≪ RTI ID = 0.0 > 21. < / RTI > The method of claim 3,
Wherein the aluminum metal has a plate-like shape having a diameter of 4 to 15 占 퐉. The method of claim 3,
Further comprising a resin binder,
The resin binder may be selected from the group consisting of a urethane resin, an acrylic resin, a urethane-acrylic copolymer, a polyimide, a polyamide, a polyether resin, a polyolefin resin and a melamine resin or a mixture of two or more thereof Wherein the carbon nanotube-retaining functional composition is a carbon nanotube-retaining functional composition. The method according to claim 6,
Wherein the carbon nanotube insulating functional composition comprises 0.1 to 15 wt% of the carbon nanotubes, 0.01 to 15 wt% of a dispersant, 0.1 to 15 wt% of a metal additive, 1 to 50 wt% of a resin binder, and 10 to 98 wt% of a solvent. The method of claim 3,
An additive selected from the group consisting of a dispersant, a slip agent, a flow improver, a thickener, an anti-settling agent, a defoamer, an antistatic agent, a water repellent agent, an air permeability agent, Wherein the carbon nanotube insulating function functional composition is a carbon nanotube. A substrate made of fiber or glass or polymer; And
A carbon nanotube (CNT) on the surface of the substrate, and a coating layer containing a metal additive,
Wherein the coating layer is formed by applying the carbon nanotube insulating function functional composition of any one of claims 3 to 8 on the substrate and curing the carbon nanotube insulating functional material composition. 10. The method of claim 9,
Wherein the fiber is at least one selected from a vegetable fiber, an animal fiber, a regenerated fiber, a semisynthetic fiber, a synthetic fiber, a woven fabric, a knitted fabric, a nonwoven fabric and a felt. . delete delete A garment manufactured using the carbon nanotube insulating functional product of claim 9. 14. The method of claim 13,
Wherein a metal is distributed in an amount of 80 wt% or more distributed on the upper side of the coating layer in contact with human skin.

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