TWI655329B - Composite textile - Google Patents

Abstract

The present invention provides a composite textile. The composite textile comprises a textile substrate and a layer of thermal insulation material formed over the textile substrate. The layer of thermal insulation material comprises a nano composite powder. This nanocomposite powder is composed of a pyrrolidone-containing polymer and inorganic particles. The pyrrolidone-containing polymer is a polyvinylpyrrolidone, a derivative of polyvinylpyrrolidone or a combination thereof. The inorganic particles are metal oxides composed of a first metal M ^A , a doping metal M ^B and oxygen. The inorganic particles account for 62.5-99.9 wt% of the nano composite powder.

Description

Composite textile

The present invention relates to a composite textile, and more particularly to a composite textile capable of efficiently absorbing infrared rays and thereby generating heat.

For general textiles, there are several possible ways to achieve better warmth. For example, the density or thickness of the textile can be increased. However, such textiles have problems of poor air permeability and high weight, which will cause user discomfort.

In addition, fillers (eg, feathers of animals) may also be added to the final product of the textile (eg, apparel) to improve the warmth of the final product. However, since this filler will greatly increase the volume of the final product, it may cause inconvenience to the user's activities.

Therefore, there is still a need in the art to find a textile having excellent heat retention properties and being lightweight and thin.

One embodiment of the present invention discloses a composite textile comprising a textile substrate and a layer of thermal insulation material formed over the textile substrate. The layer of thermal insulation material comprises a nano composite powder. This nanocomposite powder is composed of a pyrrolidone-containing polymer and inorganic particles. The pyrrolidone-containing polymer is a polyvinylpyrrolidone, a derivative of polyvinylpyrrolidone or a combination thereof. The inorganic particles are metal oxides composed of a first metal M ^A , a doping metal M ^B and oxygen. This inorganic particle accounts for 62.5 to 99.9% by weight of the nano composite powder.

The above and other objects, features, and advantages of the present invention will become more apparent and understood.

100‧‧‧Composite textiles

100’‧‧‧Composite textiles

102‧‧‧Textile substrate

104‧‧‧Warm material layer

104a‧‧‧Nano composite powder

104b‧‧‧ polymer carrier

BRIEF DESCRIPTION OF THE DRAWINGS Figure 1 is a schematic cross-sectional view of a composite textile in accordance with some embodiments of the present invention.

2 is a schematic cross-sectional view of a composite textile in accordance with further embodiments of the present invention.

The above and other objects, features and advantages of the present invention will become more <RTIgt; However, it will be understood by those of ordinary skill in the art that the description In fact, in order to make the description clearer, the relative size ratio of various feature structures can be arbitrarily increased or decreased.

In the present specification, the terms "about" and "about" are usually expressed within 20%, preferably within 10%, and more preferably within 5% of a given value or range. The quantity given here is an approximate quantity, meaning that the meaning of "about" or "about" may be implied without specific explanation.

In accordance with some embodiments of the present invention, a composite textile is provided. The composite textile comprises a textile substrate and a layer of thermal insulation material formed over the textile substrate. The layer of thermal insulation material comprises a nano composite powder. The nano composite powder may be composed of a pyrrolidone-containing polymer and inorganic particles. The pyrrolidone-containing polymer may be a polyvinylpyrrolidone, a derivative of polyvinylpyrrolidone or a combination thereof. The inorganic particles are metal oxides composed of a first metal M ^A , a doping metal M ^B and oxygen. This inorganic particle accounts for 62.5 to 99.9% by weight of the nano composite powder.

The above-mentioned nanocomposite powder can efficiently absorb energy of light such as infrared rays, and after absorbing energy of light, can release absorbed energy as heat energy. Forming the layer of the heat retaining material including the nano composite powder on the textile substrate can greatly improve the warming effect of the textile without significantly increasing the volume or weight of the textile.

1 is a schematic cross-sectional view of a composite textile 100 in accordance with some embodiments of the present invention. Referring to FIG. 1 , in some embodiments, composite textile 100 includes a textile substrate 102 and a layer of thermal insulation material 104 formed over textile substrate 102 . In other embodiments, the layer of thermal insulation material 104 can be a film formed from nanocomposite powder 104a, while in such an embodiment, layer 40 of thermal insulation material is depicted in phantom as shown in FIG.

In some embodiments, the textile substrate 102 can comprise a polyethylene fiber textile, a polypropylene fiber textile, a polyamide fiber textile, a polyester fiber textile, a cellulose fiber textile, a cellulose acetate textile, an animal fiber textile, or a combination thereof. However, these materials are merely illustrative materials and are not intended to be limiting. In other embodiments, the textile substrate 102 can be any other suitable textile.

The nanocomposite powder 104a may be composed of inorganic particles and a polymer containing pyrrolidone. The nanocomposite powder 104a can efficiently absorb energy of light such as infrared rays, and after absorbing energy of light, can The way of heat releases the absorbed energy. The thermal energy released by the nanocomposite powder 104a is conducted to the textile substrate 102, thereby increasing the temperature of the final product of the composite textile 100. In this way, the warmth of the final product can be improved.

Inorganic particles absorb light energy and release heat energy, thus improving the warmth of the textile. In some embodiments, the inorganic particles may be a metal oxide composed of the first metal M ^A , the doping metal M ^{B ,} and oxygen, and the metal oxide may be represented by the following general formula (I): (M ^A ) (M ^B )O (I)

In the general formula (I), the first metal M ^A may be zinc, indium, or tin, and the doping metal M ^B may be tin, aluminum, gallium, iron, or antimony.

The above inorganic particles are formed by doping another oxide (for example, doping metal M ^B ) in an oxide of a single metal (for example, the first metal M ^A ). In other words, a first metal oxide of M ^A, M ^A first metal moiety is substituted doped metal M ^B. As a result, the energy level of the oxide of the first metal M ^A can be changed. When an inorganic particle is irradiated with light of a specific wavelength, the energy of the light is converted into the kinetic energy of a free carrier in the inorganic particle. These free carriers collide in the lattice of the inorganic particles, thereby releasing thermal energy. For example, in some embodiments, the inorganic particles can be gallium-doped zinc oxide, aluminum-doped zinc oxide, tin-doped zinc oxide, gallium-doped indium oxide, or tin-doped indium oxide. However, these materials are merely illustrative materials and are not intended to be limiting. In other embodiments, the inorganic particles may be any of the inorganic particles represented by the above formula (I).

If the content of the doping metal M ^B in the inorganic particles is too small, the concentration of the free carrier is too low. As a result, the inorganic particles cannot effectively absorb the light energy and release the heat energy. On the other hand, if the content of the doping metal M ^B in the inorganic particles is too large, the light energy cannot be efficiently absorbed and the thermal energy is released. Therefore, the content of the doping metal M ^B in the inorganic particles can be adjusted to a specific range so that the inorganic particles can efficiently absorb the light energy and release the heat energy. In some embodiments, the doping metal M ^B is 0.1 to 20 parts by weight based on 100 parts by weight of the first metal M ^A . In other embodiments, the doping metal M ^B is from 1 to 15 parts by weight based on 100 parts by weight of the first metal M ^A . In still other embodiments, the doping metal M ^B is 5 to 10 parts by weight based on 100 parts by weight of the first metal M ^A .

In some embodiments, the method of preparing inorganic particles can include the following steps.

Step 1: Mixing the nitrate or sulfate of the first metal M ^A with the chloride or sulfate of the doped metal M ^B and dissolving in water to obtain a mixed salt solution. In this mixed salt solution, the total concentration of the first metal M ^A and the doping metal M ^B is from 0.5 ml/L to 5.0 ml/L. Further, in the mixed salt solution, the doping metal M ^B is 0.1 to 20 parts by weight based on 100 parts by weight of the first metal M ^A .

Step 2: The mixed salt solution and the ammonium hydrogencarbonate solution disposed in the step 1 were separately added dropwise to water, and rapidly stirred to form a white precipitate. In step 2, the temperature is maintained at 40 ° C and the pH is controlled between 7.0 and 7.5. This white precipitate is the basic carbonate of the first metal M ^A uniformly doped with the doping metal M ^B .

Step 3: The above white precipitate was washed and separated and dried to give a white powder. The obtained white powder was sintered in an environment in which hydrogen gas and argon gas were mixed. The sintering temperature is from 400 ° C to 700 ° C, and the sintering time is from 30 to 60 minutes. The powder obtained after sintering is an inorganic particle doped with a first metal M ^A doped with a metal M ^B .

The pyrrolidone-containing polymer can form a complex with the inorganic particles (that is, the nanocomposite powder 104a). If a polymer containing no pyrrolidone is present, the inorganic particles are likely to aggregate, and the particle diameter of the inorganic particles is increased and the surface area of the inorganic particles is lowered. As a result, the efficiency of absorbing light energy and releasing heat energy is reduced. Therefore, by combining the pyrrolidone-containing polymer with the inorganic particles to form the nanocomposite powder 104a, aggregation of the inorganic particles can be avoided, and the problem of reduced absorption of light energy and release of thermal energy can be avoided.

In some embodiments, the pyrrolidone-containing polymer is polyvinylpyrrolidone (PVP), a derivative of polyvinylpyrrolidone, or a combination thereof. In some embodiments, the polyvinylpyrrolidone derivative comprises a polyvinylpyrrolidone having an isocyanate group at the end, a polyvinylpyrrolidone having a methoxy group at the end, a polyvinylpyrrolidone having an ethoxy group at the end, and a polyethylene having a carboxylic acid group at the end. Pyrrolidone or a combination thereof. However, these materials are merely illustrative materials and are not intended to be limiting. In other embodiments, the pyrrolidone-containing polymer can be any other suitable pyrrolidone-containing polymer.

When the content of the inorganic particles in the nanocomposite powder 104a is too small, the efficiency of absorbing light energy and releasing heat energy is lowered. On the other hand, if the content of the inorganic particles in the nanocomposite powder 104a is too large, the inorganic particles are likely to aggregate, and the particle diameter of the nanocomposite powder 104a is increased and the surface area is lowered. As a result, the efficiency of absorbing light energy and releasing heat energy is also reduced. Therefore, the content of the inorganic particles in the nanocomposite powder 104a can be adjusted to a specific range to avoid the influence of the efficiency of absorbing light energy and releasing heat energy. In some embodiments, the inorganic particles comprise from 62.5 to 99.9% by weight of the nanocomposite powder. In other embodiments, the inorganic particles comprise from 70.0 to 90.0% by weight of the nanocomposite powder. In still other embodiments, The inorganic particles account for 75.0-85.0% by weight of the nano composite powder.

In some embodiments, the pyrrolidone-containing polymer has a weight average molecular weight of from 3,000 to 1,500,000. In other embodiments, the pyrrolidone-containing polymer has a weight average molecular weight of 30,000 to 1,100,000. In still other embodiments, the pyrrolidone-containing polymer has a weight average molecular weight of from 300,000 to 700,000.

The method of preparing the nanocomposite powder 104a can be any suitable method. For example, in some embodiments, inorganic particles, pyrrolidone-containing polymers, and solvents can be combined to form a colloid mixture. Next, the colloidal mixture is dried by removing the solvent to obtain a nanocomposite powder 104a.

In order to obtain a colloidal mixture, the solubility of the pyrrolidone-containing polymer in a solvent should be good. Also, in order to be able to efficiently remove the solvent in the colloidal mixture, the solvent should have a lower boiling point. Under the above conditions, in some embodiments, suitable solvents may include dimethylacetamide (DMAc), dimethyl sulfoxide (DMSO). However, these solvents are merely exemplary solvents and are not intended to be limiting. In other embodiments, the solvent can be any other suitable solvent.

In some embodiments, the method of drying the colloidal mixture can include spray dry, reduced pressure distillation. However, these methods are merely exemplary methods and are not intended to be limiting. In other embodiments, the colloidal mixture can be dried by any other suitable method.

In some embodiments, the above colloidal mixture can be directly coated On the textile substrate 102. Next, the colloidal mixture is dried to obtain a composite textile 100. As shown in FIG. 1, the resulting composite textile 100 can have a textile substrate 102, and a layer of thermal insulation material 104 formed over the textile substrate 102. In such an embodiment, the composite textile 100 can be efficiently produced by a simple process. Therefore, the time and cost of production can be greatly reduced.

The colloidal mixture can be coated onto the textile substrate 102 by a suitable coating process. In some embodiments, the coating process may include a gravure printing, a screen-printing process, a roll coating process, a spray coating process, and a knife coating process ( Blade coating), other suitable deposition processes, or combinations thereof.

After the colloidal mixture is formed, if the colloidal mixture is left for a period of time (for example, 24 hours), the nanocomposite powder 104a in the colloidal mixture gradually aggregates and precipitates, resulting in an increase in the particle size of the nanocomposite powder 104a. . As a result, the efficiency of absorbing light energy and releasing heat energy will be reduced.

In still other embodiments, the above colloidal mixture (hereinafter also referred to as "first colloidal mixture") may be dried to obtain dried nanocomposite powder 104a. Thereafter, the dried nanocomposite powder 104a is dissolved in a suitable solvent as needed, and a colloidal mixture (hereinafter also referred to as "second colloidal mixture") is formed again. Next, the second colloidal mixture is applied to the textile substrate 102 and dried to obtain a composite textile 100. In such an embodiment, the dried nanocomposite powder 104a has the advantage of being small in size and stable in physicochemical properties. Therefore, the dried nanocomposite powder 104a can be used without being used immediately, and can be stored for a relatively long period of time under appropriate storage conditions (for example, from several days to several months), and is more suitable for the application. As a result, the process will be greatly improved. flexibility.

The particle size of the nanocomposite powder 104a can be substantially equal to the colloidal particle size in the colloidal mixture. For example, after drying the first colloidal mixture, the particle size of the obtained nanocomposite powder 104a may be substantially equal to the colloidal particle size in the first colloidal mixture. In other embodiments, after drying the second colloidal mixture, the particle size of the resulting nanocomposite powder 104a may be substantially equal to the colloidal particle size in the second colloidal mixture. Therefore, the particle diameter of the nanocomposite powder 104a can be known by measuring the colloidal particle diameter in the colloidal mixture.

When the particle diameter of the nanocomposite powder 104a is too large, the surface area of the nanocomposite powder 104a is lowered. As a result, the efficiency of absorbing light energy and releasing heat energy is reduced. On the other hand, in order to prepare the nanocomposite powder 104a having a small particle size, it may take a lot of time and cost. Therefore, the median particle diameter D50 of the nanocomposite powder 104a can be adjusted to a specific range. In some embodiments, the nanocomposite powder 104a has a median particle size D50 of 30-600 nm. In other embodiments, the nanocomposite powder 104a has a median particle size D50 of 35-200 nm. In still other embodiments, the nanocomposite powder 104a has a median particle diameter D50 of 40-100 nm.

Still referring to Fig. 1, the thickness of the heat retaining material layer 104 is T. If the thickness T of the heat retaining material layer 104 is too small, the efficiency of absorbing light energy and releasing heat energy is lowered. On the other hand, if the thickness T of the heat retaining material layer 104 is too large, a part of the nanocomposite powder 104a may peel off, which lowers the yield of the final product. Furthermore, if the thickness T of the heat retaining material layer 104 is too large, the breathability of the composite textile 100 may be lowered, which may cause discomfort to the user. Therefore, the thickness T of the heat retaining material layer 104 can be adjusted to a specific range. In some embodiments, the layer of thermal insulation material 104 The thickness T is 1-100 μm. In other embodiments, the thickness W of the layer of thermal insulation material 104 is between 5 and 80 microns. In still other embodiments, the thickness T of the layer of thermal insulation material 104 is 10-50 [mu]m. The thickness of the heat retaining material layer 104 can be measured using a TECLOCK thickness gauge (for example, manufacturer: Japan Dele; product model: SM-112).

Similarly, if the amount of the nanocomposite powder 104a is too small, the efficiency of absorbing light energy and releasing heat energy is lowered. On the other hand, if the amount of the nanocomposite powder 104a is too large, a part of the nanocomposite powder 104a may peel off, and the yield of the final product may be lowered. Therefore, the amount of the nanocomposite powder 104a can be adjusted to a specific range. In some embodiments, the nanocomposite powder 104a is from 0.0001 to 100,000 parts by weight based on 100 parts by weight of the textile substrate 102. In other embodiments, the nanocomposite powder 104a is from 0.01 to 100 parts by weight based on 100 parts by weight of the textile substrate 102. In other embodiments, the nanocomposite powder 104a is from 0.1 to 50 parts by weight based on 100 parts by weight of the textile substrate 102. In still other embodiments, the nanocomposite powder 104a is from 1 to 10 parts by weight based on 100 parts by weight of the textile substrate 102.

In order to make the color of the composite textile 100 the same or similar to the color of the textile substrate 102, the thermal insulation material layer 104 may be a film having higher transparency. In other words, for visible light having a wavelength in the range of 400 to 700 nm, the higher the light transmittance of the heat retaining material layer 104, the better. In some embodiments, the light-shielding material layer 104 has a light transmittance of 70-83% in a range of wavelengths of 400-700 nm and a thickness T of the heat-insulating material layer 104 of 6 μm. In some embodiments, the visible light transmittance of the layer of thermal insulation material 104 may be an infrared/visible absorption spectrometer (eg, UV/VIS/NIR spectrometer; manufacturer: JASCO INTERNATIONAL CO., LTD.; product model: JASCO-V570 ) Perform the measurement. Furthermore, the layer of thermal insulation The value of the light transmittance of 104 is determined in accordance with the thickness T of the layer of thermal insulation material 104. Therefore, when the thickness T of the heat retaining material layer 104 is not 6 μm, the light transmittance of the heat retaining material layer 104 can be obtained by converting the thickness T. For example, assuming that the light transmittance of a certain heat retaining material layer 104 is X μm, the light transmittance when the thickness of the warming material layer 104 is 6 μm can be obtained by converting the following formula: Penetration rate = 1 - {[6(1-Y)] / X}.

In order to greatly improve the warming ability of the composite textile 100, the heat retaining material layer 104 may be a film having a high infrared absorbing ability. In other words, the higher the infrared absorbing ability of the heat retaining material layer 104, the better. More specifically, for infrared rays having a wavelength in the range of 1,000 to 2,500 nm, the higher the light absorptivity of the heat retaining material layer 104, the better. In some embodiments, the light-absorbing material layer 104 has a light absorptivity of 70-83% under the conditions of a wavelength of 1,000-2,500 nm and a thickness T of the heat retaining material layer 104 of 6 μm. In some embodiments, the infrared light absorption rate of the layer of thermal insulation material 104 may be an infrared/visible absorption spectrometer (eg, UV/VIS/NIR spectrometer; manufacturer: JASCO INTERNATIONAL CO., LTD.; product model: JASCO-V570 ) Perform the measurement. Furthermore, the value of the light absorption rate of the heat retaining material layer 104 is determined according to the thickness T of the heat retaining material layer 104. Therefore, when the thickness T of the heat retaining material layer 104 is not 6 μm, the light absorptivity of the heat retaining material layer 104 can be obtained by converting the thickness T. For example, if the light absorption rate of a certain heat retaining material layer 104 is A μm, the light absorptance when the thickness of the warming material layer 104 is 6 μm can be obtained by converting the following formula: light absorptivity = (6 × B / A).

Figure 2 is a schematic cross-sectional view of a composite textile 100' in accordance with further embodiments of the present invention. Please refer to Figure 2, composite textile 100' including textile A substrate 102, and a layer of thermal insulation material 104 formed over the textile substrate 102. Fig. 2 is similar to Fig. 1 except that the heat retaining material layer 104 includes the nanocomposite powder 104a and the polymer carrier 104b. The same elements in Fig. 2 and Fig. 1 are denoted by the same reference numerals. In order to simplify the description, the components similar to those of FIG. 1 and the steps of forming the same are not described herein again.

If the adhesion between the nanocomposite powder 104a and the textile substrate 102 is insufficient, a portion of the nanocomposite powder 104a is peeled off from the textile substrate 102. In some embodiments, the layer of thermal insulation material 104 is a film formed from nanocomposite powder 104a and polymeric carrier 104b, as depicted in FIG. In such an embodiment, the polymer carrier 104b functions as an adhesive and can further enhance the adhesion between the nanocomposite powder 104a and the textile substrate 102. Therefore, the problem of peeling of the above-described nanocomposite powder 104a can be improved or avoided.

In order to avoid the peeling of the above-mentioned nanocomposite powder 104a, the adhesion of the polymer carrier 104b to the textile substrate 102 may be superior to the adhesion of the nanocomposite powder 104a to the textile substrate 102. Further, if the compatibility between the polymer carrier 104b and the nanocomposite powder 104a is not good, the polymer carrier 104b and the nanocomposite powder 104a may be delaminated. That is, the nanocomposite powder 104a may be concentrated on the top or bottom of the polymer carrier 104b without being uniformly dispersed in the polymer carrier 104b. When the polymer carrier 104b and the nanocomposite powder 104a are layered, the adhesion between the nanocomposite powder 104a and the textile substrate 102 cannot be effectively enhanced. As a result, peeling of the nanocomposite powder 104a cannot be avoided. Therefore, a material having good adhesion to the textile substrate 102 and good compatibility with the nanocomposite powder 104a can be selected as the polymer carrier. 104b.

In some embodiments, the polymeric carrier 104b can comprise polyurethane, polyacrylonitrile, polyvinylidene fluoride, polyacrylate, polypropylene, polyamide, polyester, thermoplastic polyester elastomer, or combinations thereof. However, these materials are merely illustrative materials and are not intended to be limiting. In other embodiments, the polymeric carrier 104b can be any other suitable polymeric medium. By adding the polymer carrier 104b, the heat retaining material layer 104 including the nanocomposite powder 104a and the polymer carrier 104b can be prepared by a spinning process. As a result, the film formability of the nanocomposite powder 104a can be greatly improved.

The method for preparing the composite textile 100' as depicted in Figure 2 can be any suitable method. For example, in some embodiments, inorganic particles, pyrrolidone-containing polymers, and solvents can be combined to form a colloidal mixture. Next, this colloidal mixture was added to the polymer carrier 104b, and a nonwoven fabric film was formed by electrospinning. Next, the nonwoven fabric film is bonded to the textile substrate 102 to obtain a composite textile 100'. As described above, in such an embodiment, the time and cost of production can be greatly reduced.

In other embodiments, the dried nanocomposite powder 104a can be dissolved in a suitable solvent to form a colloidal mixture. Next, this colloidal mixture was further added to the polymer carrier 104b, and a nonwoven fabric film was formed by electrospinning. Next, the nonwoven fabric film is bonded to the textile substrate 102 to obtain a composite textile 100'. As described above, in such an embodiment, the flexibility of the process can be greatly improved.

If the ratio of the polymer carrier 104b to the nanocomposite powder 104a is too low, the nanocomposite powder 104a and the textile substrate 102 cannot be reinforced. Adhesion between. Further, if the ratio of the polymer carrier 104b to the nanocomposite powder 104a is too low, the surface roughness of the heat retaining material layer 104 is increased, and the surface tension and mechanical strength of the heat retaining material layer 104 are lowered. As a result, the material layer 104 will be damaged or peeled off. On the other hand, if the ratio of the polymer carrier 104b to the nanocomposite powder 104a is too high, the efficiency of absorbing light energy and releasing heat energy is lowered. Therefore, the ratio of the polymer carrier 104b to the nanocomposite powder 104a can be adjusted to a specific range. In some embodiments, in the heat retaining material layer 104, the polymer carrier 104b is 0.1 to 60 parts by weight based on 100 parts by weight of the nanocomposite powder 104a. In still other embodiments, the polymer carrier 104b is 1 to 40 parts by weight based on 100 parts by weight of the nano composite powder 104a in the heat retaining material layer 104. In other embodiments, the polymer carrier 104b is 5 to 20 parts by weight based on 100 parts by weight of the nanocomposite powder 104a in the heat retaining material layer 104.

The composite textiles of the present invention and methods of making the composite textiles are described below by way of specific examples.

In the present specification, a method of preparing inorganic particles will be described by taking gallium-doped zinc oxide (hereinafter referred to as "GZO") and aluminum-doped zinc oxide (hereinafter referred to as "AZO") as an example.

[Preparation Example 1] Preparation of GZO (weight ratio: Ga/Zn = 5.0/100.0):

10 g of zinc nitrate was mixed with 0.33 g of gallium chloride and dissolved in water to obtain a mixed salt solution. Next, 50 ml of the above mixed salt solution and 50 ml of an ammonium hydrogencarbonate solution were respectively added dropwise to water, and rapidly stirred to form a white precipitate. In this step, the temperature was maintained at 40 ° C and the pH was controlled at 7.0-7.5. Connect The white precipitate was washed and separated and dried to obtain a white powder. The obtained white powder was sintered in an environment in which hydrogen gas and argon gas (the partial pressure of hydrogen was the same as the partial pressure of argon gas) were mixed. The sintering temperature was 50 ° C and the sintering time was 60 minutes. The powder obtained after sintering is GZO inorganic particles (weight ratio: Ga/Zn = 5.0/100.0).

[Preparation Example 2] Preparation of AZO (weight ratio: Al/Zn = 0.4/100.0):

10 g of zinc nitrate was mixed with 0.7 g of aluminum chloride and dissolved in water to obtain a mixed salt solution. Except for this, the same procedure as in Preparation Example 1 was carried out to prepare AZO inorganic particles (weight ratio: Al/Zn = 0.4/100.0).

[Example 1-1] Preparation of GZO/PVP nano composite powder:

100 g of GZO (weight ratio: Ga/Zn = 5.0/100.0), 5 g of polyvinylpyrrolidone (PVP; Mw = 58,000) and 400 g of dimethylacetamide (DMAc) were mixed and stirred to form a first Colloidal mixture. The first median particle size D50 of the colloid was determined. The stability of the colloidal mixture was observed at room temperature to maintain stable dispersion for at least 24 hours. The colloidal mixture was spray dried to obtain a GZO/PVP nano composite powder. After 14 days of storage, the obtained GZO/PVP nanocomposite powder was dissolved in dimethylacetamide to form a second colloidal mixture. The second median particle size D50 of the colloid was determined.

[Example 1-2] Preparation of GZO/PVP nano composite powder:

100 g of GZO (weight ratio: Ga/Zn = 5.0/100.0), 5 g of PVP (Mw = 10,000) and 400 g of DMAc were mixed and stirred uniformly to form a first colloidal mixture. The first median particle size D50 of the colloid was determined. The stability of the colloidal mixture was observed at room temperature to maintain stable dispersion for at least 24 hours. Mixing colloids The spray was dried to obtain a GZO/PVP nano composite powder. After 14 days of storage, the obtained GZO/PVP nanocomposite powder was dissolved in dimethylacetamide to form a second colloidal mixture. The second median particle size D50 of the colloid was determined.

[Example 1-3] Preparation of GZO/PVP nano composite powder:

100 g of GZO (weight ratio: Ga/Zn = 1.5/100.0), 5 g of PVP (Mw = 1,280,000) and 400 g of DMAc were mixed and stirred uniformly to form a first colloidal mixture. The first median particle size D50 of the colloid was determined. The stability of the colloidal mixture was observed at room temperature to maintain stable dispersion for at least 24 hours. The colloidal mixture was spray dried to obtain a GZO/PVP nano composite powder. After 14 days of storage, the obtained GZO/PVP nanocomposite powder was dissolved in dimethylacetamide to form a second colloidal mixture. The second median particle size D50 of the colloid was determined.

[Comparative Example 1] Preparation of GZO/PEI nano composite powder:

100 g of GZO (weight ratio: Ga/Zn = 1.5/100.0), 5 g of polyethylenimine (PEI; Mw = 10,000) and 400 g of DMAc were mixed and stirred uniformly to form a first colloidal mixture. The first median particle size D50 of the colloid was determined. The stability of the colloidal mixture was observed at room temperature, and only the solution state was maintained for 6 hours. Over 6 hours, a precipitate formed. Further, since PEI is a liquid polymer, GZO/PEI nano composite powder cannot be obtained.

[Measurement of median particle size D50]

The particle size of the colloid was measured using a laser particle size analyzer (manufacturer: Malvern; product model: Zetasizer Nano ZS), and a particle size distribution map was drawn. The median diameter D50 was determined from the particle size distribution map.

The experimental results of Examples 1-1, 1-2, 1-3 and Comparative Example 1 are shown in Table 1. Referring to Table 1, the colloidal mixture of Example 1-1, Example 1-2 and Example 1-3 can maintain stable dispersion for at least 24 hours. In contrast, the colloidal mixture of Comparative Example 1 was only able to maintain stable dispersion for about 6 hours. From this, it is understood that the colloidal mixture formed of the pyrrolidone-containing polymer and the inorganic particles has better stability than the pyrrolidone-free polymer. Therefore, it is advantageous to prepare a nano composite powder.

Further, the first median diameter D50 of Example 1-1, Example 1-2, and Example 1-3 was smaller than the first median diameter D50 of Comparative Example 1. From this, it is understood that the efficiency of releasing heat energy of Example 1-1, Example 1-2, and Example 1-3 is superior to that of Comparative Example 1.

In Example 1-1, Example 1-2, and Example 1-3, a nano composite powder was obtained. In contrast, in Comparative Example 1, the nanocomposite powder could not be obtained. Further, in Example 1-1, Example 1-2, and Example 1-3, the second median diameter D50 is very close to the first median diameter D50. From this, it was found that in Example 1-1, Example 1-2, and Example 1-3, the properties of the nanocomposite powder did not largely change even after storage for a while.

[Example 2]

200 g of AZO (weight ratio: Al/Zn = 0.4/100.0), 6 g of PVP (Mw = 58,000) and 800 g of dimethylarylene (DMSO) were mixed and stirred to form a colloidal mixture. The median particle diameter D50 of the colloid was measured to be 102.8 nm. The colloidal mixture was coated on a polyester fiber cloth by gravure printing and dried to obtain a composite textile. The AZO nano composite powder was measured to be 0.15 parts by weight based on 100 parts by weight of the textile substrate. Next, the composite textile was subjected to an illumination temperature rise test such as TN-037 and an infrared absorption rate test (test wavelength of 1,000-2,500 nm).

[Comparative Example 2]

200 g of AZO was replaced with 200 g of zinc oxide ZnO. Except for this, other process steps are the same as those of Embodiment 2, and will not be described in detail herein.

The experimental results of Example 2 and Comparative Example 2 are shown in Table 2. In Table 2, the higher the A value, the better the ability of the composite textile to absorb light energy. Furthermore, the higher the T value, the better the ability of the composite textile to release thermal energy. As shown in Table 2, Example 2 was superior to Comparative Example 2 in terms of the ability to absorb light energy and the ability to release heat energy. In other words, aluminum-doped zinc oxide has better ability to absorb light energy and release heat energy than undoped zinc oxide.

[Example 3]

Mix 200 g of GZO (weight ratio: Ga/Zn = 5.0/100.0), 20 g of PVP (Mw = 58,000) and 800 g of DMAc and mix well to form a colloidal mixture. Things. The colloidal median particle diameter D50 was measured to be 127.6 nm. The colloidal mixture was coated on a nylon fiber cloth by gravure printing and dried to obtain a composite textile. The GZO nanocomposite powder was found to be 1.5 parts by weight based on 100 parts by weight of the textile substrate. Next, the composite textile was subjected to an illumination temperature rise test such as the TN-037 specification and an infrared absorption rate test as described above.

[Comparative Example 3]

The NN-037 specification illumination temperature rise test and infrared absorption rate test were carried out using a nylon fiber cloth.

The experimental results of Example 3 and Comparative Example 3 are shown in Table 3. As shown in Table 3, Example 3 was superior to Comparative Example 3 in terms of the ability to absorb light energy and the ability to release heat energy. In other words, composite textiles including nano composite powders have better ability to absorb light energy and release heat energy than textiles that do not include nano composite powder.

[Embodiment 4]

200 g of GZO (weight ratio: Ga/Zn = 5.0/100.0), 20 g of PVP (Mw = 58,000) and 800 g of DMAc were mixed and stirred uniformly to form a colloidal mixture. The colloidal median particle diameter D50 was measured to be 127.6 nm. This colloidal mixture was added to a polyurethane (PU), coated on a nylon fiber cloth by gravure printing, and dried to obtain a composite powder textile. The GZO nanocomposite powder was found to be 1.5 parts by weight based on 100 parts by weight of the textile substrate. Then, on this The composite textile is subjected to an illumination temperature rise test such as the TN-037 specification and an infrared absorption rate test as described above.

The experimental results of Example 4 and Comparative Example 3 are shown in Table 4. As shown in Table 4, Example 4 was superior to Comparative Example 3 in terms of the ability to absorb light energy and the ability to release heat energy. In other words, the composite textile including the polymer carrier (i.e., PU) and the nano composite powder has better ability to absorb light energy and release heat energy than textiles not including the nano composite powder.

[Embodiment 5]

100 g of GZO (weight ratio: Ga/Zn = 1.5/100.0), 5 g of PVP (Mw = 1,280,000) and 400 g of DMAc were mixed and stirred uniformly to form a colloidal mixture. The median particle diameter D50 of the colloid was measured to be 62.0 nm. The colloidal mixture was added to polyacrylonitrile (PAN), and the non-woven fabric film of the electrospinning process was applied to a nylon fiber cloth to obtain a composite powder textile. The GZO nanocomposite powder was found to be 1.0 part by weight based on 100 parts by weight of the textile substrate. Next, the composite textile was subjected to an illumination temperature rise test such as the TN-037 specification and an infrared absorption rate test as described above.

The experimental results of Example 5 and Comparative Example 3 are shown in Table 5. Compared to textiles that do not include nanocomposite powders, composite textiles comprising both polymeric carriers (i.e., PAN) and nanocomposite powders have better ability to absorb light energy and release heat energy.

[Embodiment 6]

100 g of GZO (weight ratio: Ga/Zn = 1.5/100.0), 5 g of PVP (Mw = 1,280,000) and 400 g of DMAc were mixed and stirred uniformly to form a colloidal mixture. The median particle diameter D50 of the colloid was measured to be 62.0 nm. The colloidal mixture was added to polyvinylidene fluoride (PVDF), and the non-woven fabric film of the electrospinning process was applied to a nylon fiber cloth to obtain a composite powder textile. The GZO nanocomposite powder was found to be 1.0 part by weight based on 100 parts by weight of the textile substrate. Next, the composite textile was subjected to an illumination temperature rise test such as the TN-037 specification and an infrared absorption rate test as described above.

The experimental results of Example 6 and Comparative Example 3 are shown in Table 6. Compared to textiles that do not include nanocomposite powders, composite textiles comprising both polymeric carriers (i.e., PVDF) and nanocomposite powders have better ability to absorb light energy and release heat energy.

[Comparative Example 4]

Mix 100 g of GZO (weight ratio: Ga/Zn = 1.5/100.0), 5 g of PEI (Mw = 1,800) and 400 g of DMAc and mix well to form a colloidal mixture. Things. The median particle diameter D50 of the colloid was measured to be 310.8 nm. This colloidal mixture was added to PVDF and subjected to an electrospinning process. As a result, the colloidal mixture containing PVDF could not be formed into a nonwoven film by electrospinning.

From the results of Comparative Example 4, it was found that the nonwoven fabric using PEI could not be made into a nonwoven fabric film by electrospinning. In contrast, a non-woven film can be produced by electrospinning (electrospinning) using a colloidal mixture of PVP (i.e., Example 6). Process flexibility is improved due to the wide range of coating methods available. Further, the diameter of the fiber prepared by the conventional spinning method is not easily less than 1 μm. In contrast, electrospinning not only reduces the fiber diameter to the nanometer scale, but also produces fibers having a high specific surface area, high hygroscopicity, and high strength equivalent energy. In addition, the electrospinning process is simpler than the conventional spinning method, and does not require the production of solid fibers from liquids by chemical reaction or high temperature, and is particularly suitable for the production of macromolecular fibers or composite molecular fibers. Further, electrospinning can also be used to extract fibers from the melt, so that the final product obtained does not contain a solvent. Furthermore, electrospinning has the advantages of low cost, many spinnable materials, and controllable process, and has become one of the main ways to efficiently prepare nanofiber materials.

In summary, in some embodiments, a composite textile and a method of making the same are provided. The composite textile and the preparation method thereof have at least the following advantages:

(1) The composite textile includes a specific nano composite powder, and the nano composite powder can efficiently absorb energy of light such as infrared rays, and after absorbing energy of light, can release absorbed energy by heat energy. . Therefore, it is possible to greatly improve the spinning without significantly increasing the volume or weight of the textile. The warmth of the fabric.

(2) The colloidal mixture including the nanocomposite powder is directly coated on a textile substrate, and the composite textile 100 can be efficiently produced. Therefore, the time and cost of production can be greatly reduced.

(3) The dried nanocomposite powder can be stored for a long period of time (for example, from several days to several months) as needed. Therefore, the flexibility of the process can be greatly improved.

(4) The layer of the heat retaining material further comprises a polymer carrier, whereby the adhesion between the nanocomposite powder and the textile substrate can be further enhanced. Therefore, the problem of peeling of the nano composite powder can be improved or avoided.

(5) The layer of the heat retaining material is a film having high transparency, and therefore, the color of the composite textile can be the same as or similar to the color of the textile substrate.

While the invention has been described above in terms of several preferred embodiments, it is not intended to limit the scope of the present invention, and any one of ordinary skill in the art can make any changes without departing from the spirit and scope of the invention. And the scope of the present invention is defined by the scope of the appended claims.

Claims (15)

A composite textile comprising: a textile substrate; and a layer of thermal insulation material formed on the textile substrate, wherein the thermal insulation material layer comprises a nano composite powder, and the nano composite powder is composed of the following components The composition comprises: a pyrrolidone-containing polymer, wherein the pyrrolidone-containing polymer is polyvinylpyrrolidone, a derivative of polyvinylpyrrolidone or a combination thereof; and an inorganic particle, wherein the inorganic particle is composed of a first metal M ^A , a metal oxide composed of a doped metal M ^B and oxygen; wherein the inorganic particles account for 62.5-99.9 wt% of the nano composite powder. The composite textile of claim 1, wherein the metal oxide is represented by the following general formula (I): (M ^A )(M ^B )O (I) wherein the first metal M ^A is zinc, Indium, or tin; the doping metal M ^B is tin, aluminum, gallium, iron, or antimony. The composite textile according to claim 2, wherein the inorganic particles have a doping metal M ^B of 0.1 to 20 parts by weight based on 100 parts by weight of the first metal M ^A . The composite textile according to claim 1, wherein the nano composite powder has a median diameter D50 of 30 to 600 nm. The composite textile according to claim 1, wherein the pyrrolidone-containing polymer has a weight average molecular weight of 3,000 to 1,500,000. The composite textile according to claim 1, wherein the composite Derivatives of vinylpyrrolidone include polyvinylpyrrolidone having an isocyanate group at the end, polyvinylpyrrolidone having a methoxy group at the end, polyvinylpyrrolidone having an ethoxy group at the end, polyvinylpyrrolidone having a carboxylic acid group at the end, or a combination thereof. The composite textile of claim 1, wherein the warming material layer further comprises a polymer carrier. The composite textile according to claim 7, wherein the polymer carrier comprises polyurethane, polyacrylonitrile, polyvinylidene fluoride, polyacrylate, polypropylene, polyamide, polyester, thermoplastic polyester elastomer. Or a combination of the above. The composite textile according to claim 7, wherein the polymer carrier is 0.1 to 60 parts by weight based on 100 parts by weight of the nano composite powder in the heat retaining material layer. The composite textile according to claim 1, wherein the nano composite powder is 0.0001 to 100 parts by weight based on 100 parts by weight of the textile substrate. The composite textile of claim 1, wherein the layer of thermal insulation material is a film. The composite textile of claim 11, wherein the film has a thickness of from 1 to 100 μm. The composite textile according to claim 11, wherein the film has a light transmittance of 70 to 83% in a range of a wavelength of 400 to 700 nm and a film thickness of the film of 6 μm. The composite textile according to claim 11, wherein the film has a light absorptivity of 70 to 83% in a range of from 1,000 to 2,500 nm and a film thickness of the film of 6 μm. The composite textile of claim 1, wherein the textile substrate comprises a polyethylene fiber textile, a polypropylene fiber textile, a polyamide fiber textile, a polyester fiber textile, a cellulose fiber textile, an acetate fiber textile, an animal. Fiber textile or a combination of the above.