KR20190094640A - Complex comprising nanoparticles composed of conductive polymers and fatty acids, Preparation method thereof, fiber containing the same and film containing the same - Google Patents

Abstract

The present invention relates to a complex comprising nanoparticles composed of conductive polymers and fatty acids, a preparation method thereof, a fiber containing the same, and a film containing the same. The present invention includes nanoparticles in which conductive polymers and fatty acids are made into a complex; and a polymer resin matrix, thereby providing a complex exhibiting excellent antimicrobial and heat storage properties.

Description

Complex comprising nanoparticles composed of conductive polymers and fatty acids, Preparation method, fiber containing the same and film containing the same}

The present invention relates to a composite comprising a nanoparticle made of a conductive polymer and a fatty acid, a method for preparing the same, a fiber including the same, and a film including the same.

Recently, as various sports activities are becoming popular, the demand for high-performance sports clothing products is continuously increasing. In particular, fiber products having a heating function are commercialized. Initially, thermal insulation materials aimed at thermal insulation to prevent the loss of heat generated by the body temperature were introduced, but recently, thermal heating materials, chemical reaction heating insulation materials, and solar thermal insulation materials (eg zirconium carbide (ZrC)) were fabricated inside the yarn. It is embedded in the surface of fabric or fabric, which absorbs near-infrared rays when it receives sunlight and heats it with heat energy and radiates heat to human body.

PCPDTBT is a material that has various effects (photothermal effect, photoacoustic, photocatalyst) by effectively absorbing sunlight and releasing energy. The conductive polymer is an organic semiconductor having a low band gap, and can absorb sunlight. When the conductive polymer is prepared in the form of nanoparticles, the conductive polymer effectively absorbs light energy and is released as heat. Therefore, it can be applied as a thermal fiber material in that it can effectively absorb sunlight and release it as heat.

However, particles having conventional functionality are limited to the thickness of the yarn with a micron size, and due to the functional particles, there is a limit in imparting functionality due to trimming problems during spinning. In addition, the treatment of the functional particles of the micron unit has a problem in durability because the particles degrade the air permeability and feel of the fibers and are simply attached to the surface. Therefore, there is a need for a method of using nanotechnology to exert a specific function without impairing the original function of the fiber and to improve durability through permanent bonding.

Republic of Korea Patent No. 10-1577403

It is an object of the present invention to provide a composite having a structure in which nanoparticles using a conductive polymer and a fatty acid are uniformly distributed in a polymer resin matrix, a method for preparing the same, a fiber including the same, and a film including the same.

The present invention, a polymer resin matrix; And

It comprises nanoparticles dispersed in the polymer resin matrix,

The nanoparticles provide a composite characterized in that the conductive polymer and fatty acid is a complex structure.

In addition, the present invention, the step of producing a nanoparticle by sonicating a solution mixed with a fatty acid and a conductive polymer; And

It provides a method for producing a composite comprising the step of preparing a composite by adding the prepared nanoparticles to the polymer resin solution.

In addition, the present invention provides a fiber comprising the composite according to the present invention.

The present invention also provides a film comprising the composite according to the present invention.

The composite according to the present invention has an advantage that the nanoparticles including the conductive polymer and the fatty acid and the polymer resin matrix are hydrogen-bonded and the nanoparticles are uniformly distributed in the polymer resin matrix to simultaneously satisfy the antimicrobial and thermal insulation properties.

Figure 1 (a) shows an embodiment of the conductive polymer and fatty acid, (b) is a schematic diagram of a method for producing nanoparticles according to one embodiment, (c) is in the nanoparticles according to one embodiment It is a schematic diagram of the binding form of the conductive polymer and fatty acid.
2 is an image of the nanoparticles taken by the field emission scanning electron microscope (a) and the transmission electron microscope (b) according to an embodiment.
3 is an image of a nanoparticle taken by a field emission scanning electron microscope according to an embodiment.
Figure 4 is an image taken with a scanning electron microscope (a) and transmission electron microscope (b) of a film including a composite according to an embodiment.
5 is an image taken with a field emission scanning electron microscope (FE-SEM) of a fiber including a composite according to an embodiment.
6 is an image taken with an optical microscope (OM) of a fiber including a composite according to an embodiment.
7 is a graph of a result of analyzing a film including a composite according to an embodiment by grazing angle X-ray diffraction, (a) is a 2D GIXD pattern graph, and (b) is a graph showing diffraction peaks of qtz and qrz. .
FIG. 8 is a graph of Fourier Transform-Infrared Spectroscopy (FT-IR) of a film including a composite. FIG.
9 is a UV absorption spectrum graph of the nanoparticles according to an embodiment, (a) is a graph of the nanoparticles prepared by mixing the conductive polymer and fatty acid in a molar ratio of 1:12, (b) is a conductive polymer and It is a graph of nanoparticles prepared while increasing the molar ratio of fatty acids from 1: 1 to 1:20 by 5 times.
10 is a graph showing a light stability test result for nanoparticles according to an embodiment.
11 is a graph showing the results of dynamic mechanical analysis of a film including a composite according to an embodiment.
12 is an image of an antimicrobial test result for a film including a composite according to an embodiment.
FIG. 13 is a graph of temperature change for 60 minutes and 60 minutes after light removal while irradiating light onto a film or fiber including a composite according to an embodiment.
FIG. 14 is a near infrared (NIR) image and data on temperature change during 60 minutes and 60 minutes after light removal while irradiating light onto a film or fiber including a composite according to an embodiment.

As the invention allows for various changes and numerous embodiments, particular embodiments will be illustrated in the drawings and described in detail in the written description.

However, this is not intended to limit the present invention to specific embodiments, it should be understood to include all modifications, equivalents, and substitutes included in the spirit and scope of the present invention.

In the present invention, the terms "comprises" or "having" are intended to indicate that there is a feature, number, step, operation, component, part, or combination thereof described in the specification, and one or more other features. It is to be understood that the present invention does not exclude the possibility of the presence or the addition of numbers, steps, operations, components, components, or a combination thereof.

In addition, it is to be understood that the accompanying drawings in the present invention are shown to be enlarged or reduced for convenience of description.

The present invention relates to a composite comprising a nanoparticle made of a conductive polymer and a fatty acid, a method for preparing the same, a fiber including the same, and a film including the same.

Particles having conventional functionality are limited to the thickness of the yarn with a micron size, and due to the functional particles, there is a limit in imparting functionality due to a thread trimming problem. In addition, the treatment of the functional particles of the micron unit has a problem in durability because the particles deteriorate the breathability and feel of the fibers and are simply attached to the surface. Therefore, there is a need for a method of using nanotechnology to exert a specific function without impairing the original function of the fiber and to improve durability through permanent bonding.

Accordingly, the present invention is a composite of the nanoparticles containing a conductive polymer and fatty acid and a polymer resin matrix is hydrogen-bonded and the nanoparticles are uniformly distributed in the polymer resin matrix to simultaneously satisfy the antimicrobial and insulating properties, a method for preparing the same, and the like. To provide a fiber and a film comprising the same.

Hereinafter, the present invention will be described in more detail.

The present invention, in one embodiment,

Polymeric resin matrix; And

It comprises nanoparticles dispersed in the polymer resin matrix,

The nanoparticles provide a composite characterized in that the conductive polymer and fatty acid is a complex structure.

As shown in FIG. 1, the nanoparticles have a core-shell structure as a complexed structure of a fatty acid and a conductive polymer, the core may include a conductive polymer, and the shell may include a fatty acid. Specifically, an alkyl group of a fatty acid and an alkyl group of a conductive polymer (eg, an ethylhexyl group of PCPDTBT) may be bonded by hydrophobic attraction, and carboxylic acid of a fatty acid is formed on the surface of the nanoparticle due to emulsification in a polar medium to form a shell. can do.

As one example, the nanoparticles may have a molar ratio of 1: 5 to 20, with the content of the conductive polymer and the fatty acid. Specifically, the nanoparticles may have a content of the conductive polymer and the fatty acid in a 1: 8 to 18 molar ratio or 1:10 to 15 molar ratio. More specifically, the nanoparticles may have a content of 1:10 to 15 molar ratios of the conductive polymer and the fatty acid. By having such a ratio of the conductive polymer and fatty acid, it is possible to provide a composite having excellent antibacterial and exothermic properties.

As another example, the content of the nanoparticles may be 0.25 parts by weight to 2 parts by weight based on 100 parts by weight of the polymer resin. Specifically, the content of the nanoparticles may be 0.3 parts by weight to 1.5 or 0.5 to 1.3 parts by weight based on 100 parts by weight of the polymer resin. More specifically, the content of the nanoparticles may be 0.5 to 1.3 parts by weight based on 100 parts by weight of the polymer resin. When the nanoparticles are included in the content as described above, the composite of the present invention may simultaneously exhibit excellent exothermic properties having excellent antimicrobial properties.

Specifically, the nanoparticles may be elliptical, the size of the nanoparticles may be 200 to 350 nm based on the long axis, may be 80 to 150 nm based on the short axis. More specifically, the nanoparticles are elliptical, the size of the nanoparticles may be 250 to 320 nm based on the long axis, may be 100 to 150 nm based on the short axis.

For example, the nanoparticles may have a structure that is uniformly dispersed in the polymer resin matrix. Specifically, the nanoparticles in the polymer resin matrix may be bonded through hydrogen bonding. The surface of the nanoparticles may be linked to a carboxylic acid of a fatty acid and a secondary amine group of a polymer resin matrix through hydrogen bonding. Through the hydrogen bonds, nanoparticles may be uniformly distributed in the polymer resin matrix.

The polymer resin matrix may include one or more selected from the group consisting of polyurethane, nylon, urea, polyacrylonitrile, and polyvinyl alcohol. Specifically, the polymeric resin matrix may include one or more selected from the group consisting of polyurethane, nylon or urea. More specifically, the polymer resin matrix may include polyurethane or nylon. By including the polymer resin matrix as described above, by forming a hydrogen bond with the nanoparticles, the nanoparticles can be uniformly distributed in the polymer resin matrix.

The conductive polymer may be at least one selected from the group consisting of polythiophene polymer, polypyrrole polymer, polyfluorene polymer, polyacetylene polymer, polythiodiazole polymer, and polyaniline polymer. Specifically, the conductive polymer is (poly (cylcopentadithiophene-alt-benzothiadiazole), (poly (acenaphthothienopyrazine-alt-benzodithiophene)), Poly (2,5-bis (2-hexyldecyl) -3- (5-methylthiophen-2-yl pyrrolo [3,4-c] pyrrole-1,4 (2H, 5H) -dione), poly [9,9-bis (4- (2-ethylhexyl) phenyl) fluorene- alt-co -6,7- bis (4- (hexyloxy) phenyl) -4,9-di- (thiophen-2-yl) thiadiazolo-quinoxaline], poly {3- (5- (9-hexyl-9-octyl-9H-fluoren-2- yl) thiophen-2-yl) -2,5-bis (2-hexyldecyl) -6- (thiophen-2-yl) pyrrolo (3,4-c) pyrrole-1,4 (2H, 5H) -dione} , Poly [9,9-bis (4- (2-ethylhexyl) phenyl) -fluorene-alt-co-6,7-bis (4- (hexyloxy) phenyl) -4,9-di- (thiophen-2- yl) thiadiazolo-quinoxaline] and poly (9,9-dihexylfluorene-alt-2,1,3-benzothiadiazole), which may be at least one selected from the group consisting of: poly (cylcopentadithiophene-alt-benzothiadiazole) , (poly (acenaphthothienopyrazine-alt-benzodithiophene)), Poly (2,5-bis (2-hexyldecyl) -3- (5-methylthiophen-2-yl) pyrrolo [3,4-c] pyrrole-1,4 ( 2H, 5H) -dione) and poly [9 , 9-bis (4- (2-ethylhexyl) phenyl) fluorene- alt-co -6,7-bis (4- (hexyloxy) phenyl) -4,9-di- (thiophen-2-yl) thiadiazolo-quinoxaline ]. By including the conductive polymer as described above has a characteristic of absorbing light energy having a wavelength of 500 ~ 1000nm which is the main component of sunlight and converting the energy into thermal energy, the composite according to the present invention can exhibit excellent insulating properties.

The fatty acid may include an alkyl group having 5 to 15 carbon atoms. Specifically, the fatty acid may be a saturated fatty acid including an alkyl group having 5 to 15 carbon atoms. More specifically, the fatty acid may be a saturated fatty acid including an alkyl group having 8 to 13 carbon atoms. For example, the fatty acid may be octanoic acid. By including the fatty acid as described above, the nanoparticles are uniformly distributed in the polymer matrix, and the composite including the same may exhibit excellent antimicrobial properties.

In addition, the present invention comprises the steps of producing a nanoparticle by sonicating a solution mixed with a fatty acid and a conductive polymer; And

It provides a method for producing a composite comprising the step of preparing a composite by adding the prepared nanoparticles to the polymer resin solution.

As one example, the step of preparing the nanoparticles may be performed by irradiating the ultrasound of 10 to 100 kHz for 1 minute to 10 minutes. Specifically, preparing the nanoparticles may be performed by irradiating 20 to 60 kHz ultrasonic waves for 1 minute to 5 minutes. Through this, the conductive polymer and the fatty acid may be uniformly mixed.

Specifically, the fatty acid may be mixed in a molar ratio of 5 to 20 with respect to 1 mole of the conductive polymer in the step of preparing the nanoparticles. More specifically, the fatty acid may be mixed in an amount of 8 to 18 or 10 to 15 moles per 1 mole of the conductive polymer in the step of preparing the nanoparticles. When mixed in the above ratio it can be produced a composite having excellent antimicrobial and exothermic properties at the same time. The conductive polymer and the fatty acid may be independently prepared by using any one or more of chloroform, tetrahydrofuran, toluene, xylene, hexane, and chlorobenzene as a solvent. Specifically, in the preparation of each conductive polymer solution and fatty acid solution, the solvent may independently use chloroform, toluene or hexane.

In addition, when mixing the conductive polymer and fatty acid, one or more of dimethyl formamide (DMF) or dimethyl sulfoxide (DMSO) and N-methyl-2-pyrrolidone (NMP) may be used. Specifically, dimethyl formamide (DMF) or dimethyl sulfoxide (DMSO) may be used as a solvent in the preparation of the complex. More specifically, when the conductive polymer solution and the fatty acid solution are mixed, dimethyl formamide (DMF) or dimethyl sulfoxide (DMSO) may be used as a solvent.

By using the solvent as described above, it is possible to produce nanoparticles in which the conductive polymer and the fatty acid form a core-shell. Specifically, the nanoparticles may be prepared by combining the polar end groups of the conductive polymer and the fatty acid at the interface of the chloroform solution and the dimethyl formamide solution.

As another example, before the ultrasonic irradiation in the step of preparing the nanoparticles, the solution mixed with the conductive polymer and fatty acid may be stirred for 30 minutes to 2 hours at room temperature (20 to 25 ℃). Specifically, the solution containing the conductive polymer and the fatty acid may be stirred at 25 ° C. for 30 to 60 minutes. In the case of stirring as described above, the conductive polymer and the fatty acid may sufficiently react to help form the nanoparticles.

In the preparing of the nanoparticles, the nanoparticles may be prepared by stirring the ultrasonic wave at a temperature of 50 ° C. to 100 ° C. for 2 hours to 4 hours before adding the nanoparticles to the polymer resin solution. Specifically, the nanoparticles may be prepared by evaporating the solvent by stirring for 2 hours to 3 hours at a temperature of 70 ℃ to 90 ℃.

As one example, the nanoparticles prepared in the step of preparing the composite may be mixed at 0.25 parts by weight to 2 parts by weight based on 100 parts by weight of the polymer resin. Specifically, the prepared nanoparticles may be mixed in an amount of 0.3 parts by weight to 1.5 or 0.5 to 1.3 parts by weight based on 100 parts by weight of the polymer resin. More specifically, the prepared nanoparticles may be mixed at 0.5 to 1.3 parts by weight based on 100 parts by weight of the polymer resin. When the nanoparticles are mixed in the same amount as described above, the composite prepared in the present invention may simultaneously exhibit excellent exothermic properties having excellent antimicrobial properties.

In preparing the complex, any one or more of dimethyl formamide (DMF), dimethyl sulfoxide (DMSO), and N-methyl-2-pyrrolidone (NMP) may be used as a solvent. Specifically, dimethyl formamide (DMF) or dimethyl sulfoxide (DMSO) may be used as a solvent in the preparation of the complex. By using the solvent, the fatty acid constituting the shell of the nanoparticles and the polymer resin matrix can be bonded.

In addition, the present invention provides a fiber comprising the composite according to the present invention.

Specifically, the fiber according to the present invention is a polymer resin matrix; And nanoparticles dispersed in the polymer resin matrix,

The nanoparticles may include a complex characterized in that the conductive polymer and the fatty acid is a complex structure.

As one example, the fiber according to the present invention may be produced by electrospinning, and accordingly, the diameter of the fiber may be variously determined according to the diameter of the hole of the spinning machine emitting the fiber. Specifically, the average diameter of the fibers may be 0.05 to 500 ㎛. More specifically, the average diameter of the fibers may be 0.05 to 10 μm, 1 to 300 μm, 200 to 300 μm or 50 to 250 μm.

As another example, the fiber according to the present invention may include a nanoparticle in which a conductive polymer and a fatty acid are complexed, thereby providing a fiber having excellent antibacterial and heat insulating properties.

The present invention also provides a film comprising the composite according to the present invention.

Specifically, the fiber according to the present invention is a polymer resin matrix; And nanoparticles dispersed in the polymer resin matrix,

The nanoparticles may include a complex characterized in that the conductive polymer and the fatty acid is a complex structure.

As one example, the film according to the present invention may be produced through a sputtering method. Specifically, the average thickness of the film may be 50 to 180 μm, and more specifically, the average thickness of the film may be 100 to 150 μm.

As another example, the film according to the present invention includes nanoparticles in which a conductive polymer and a fatty acid are complexed, thereby providing a fiber having excellent antibacterial and heat insulating properties.

Hereinafter, the present invention will be described in more detail with reference to Examples and Experimental Examples.

However, the following Examples and Experimental Examples are only illustrative of the present invention, and the content of the present invention is not limited to the following Examples and Experimental Examples.

Example  One

The octanoic acid solution was prepared by adding 74 mg of octanoic acid to 10 ml of chloroform. Stir the mixed solution of 0.22 ml of the prepared octanoic acid solution in 20 ml of N, N-dimethyl formamide (DMF) while stirring at 1500 rpm was stirred for 15 minutes. Then chloroform 10 ㎖ poly [2,6 - (4,4 -bis- (2-ethylhexyl) -4 H -cyclopenta [2,1-b; 3,4-b '] - dithiophene) - alt -4 5 ml of a solution of PCPDTBT dissolved in 1 mg of, 7- (2,1,3-benzothiadiazole]] (PCPDTBT) was added dropwise to the mixed solution and stirred for 1 hour, wherein the molar ratio of PCPDTBT and octanoic acid was 1:12. The concentration of PCPDTBT was 0.94 μM and the concentration of octanoic acid was 11.29 μM The stirred solution was sonicated in a bath-type ultrasonic cleaner at 40 kHz for 5 minutes at room temperature and stirred at 1500 rpm. Nanoparticle solution was prepared by completely evaporating chloroform by heating at 80 ° C. for 3 hours.

The nanoparticle solution prepared in the polyurethane solution in which 15% by weight of polyurethane was dissolved in dimethyl formamide (DMF) was mixed to include 1.0% by weight of nanoparticles relative to the polyurethane. Then, a solution containing polyurethane and nanoparticles was poured into a petri dish and dried in a vacuum oven at 25 ° C. for 48 hours to prepare a composite, and the composite was prepared into a film having a diameter of 5 cm.

Example  2

In the same manner as in Example 1, except that the nanoparticle solution prepared in the polyurethane solution in which 15% by weight of polyurethane was dissolved in dimethyl formamide (DMF) was mixed to contain 0.5% by weight of nanoparticles. To prepare a composite, a film having a diameter of 5 cm was prepared from the composite.

Example  3

In the same manner as in Example 1, except that the nanoparticle solution prepared in the polyurethane solution in which 15% by weight of polyurethane was dissolved in dimethyl formamide (DMF) was mixed to include 0.25% by weight of nanoparticles. To prepare a composite, a film having a diameter of 5 cm was prepared from the composite.

Example  4

A composite was prepared in the same manner as in Example 1, except that the prepared composite was manufactured in the form of a fiber having a diameter of 200 to 300 μm to prepare a fiber from the composite.

Comparative example  One

Silver nanoparticles were synthesized by adding silver trifluoroacetate dispersed in water to dimethyl formamide (DMF) and reducing the silver particles at 100 ° C for 5 min. Was stirred at 1500 rpm. At this time, 1.0 parts by weight of silver (Ag) was mixed with respect to 100 parts by weight of polyurethane. The stirred solution was poured into a petri dish and dried in a vacuum oven at 25 ° C. for 48 hours to prepare a polyurethane composite including silver nanoparticles, and a film having an average diameter of 5 cm was prepared from the composite.

Comparative example  2

Commercially available polyurethane beads (Estane® S TPU, Lubrizol Co., USA) were dissolved in dimethyl formamide (DMF) solvent and the dissolved polyurethane solution was poured into a petri dish and dried in a vacuum oven at 25 ° C. for 48 hours. Drying produced a film having an average diameter of 5 cm.

Comparative example  3

The polyurethane solution and the octanoic acid solution were stirred at 1500 rpm. At this time, octanoic acid compared to 100 parts by weight of polyurethane to prepare a mixed solution by mixing 1.0 parts by weight. The mixed solution was poured into Petri dishes and dried in a vacuum oven at 25 ° C. for 48 hours to prepare a polyurethane composite including octanoic acid, and a film having a diameter of 5 cm was prepared from the composite.

Comparative example  4

The polyurethane solution and the 0.1 mg / ml conductive polymer (PCPDTBT) solution were stirred at 1500 rpm. At this time, the conductive polymer was mixed with 1.0 parts by weight based on 100 parts by weight of polyurethane. The stirred solution was poured into a petri dish and dried in a vacuum oven at 25 ° C. for 48 hours to prepare a polyurethane composite including a conductive polymer. A film having an average diameter of 5 cm was prepared from the composite.

Experimental Example  One

In order to confirm the shape of the nanoparticles and the composite including the same according to the present invention, the scanning electron microscope (Scanning Electron Microscope, SEM), the transmission electron microscope (Transmission Electron Microscope, TEM) for the composite prepared in Examples and Comparative Examples ), A field emission scanning electron microscope (Field Emission Scanning Electron Microscope, FE-SEM) and an optical microscope (Optical Microscope, OM) was photographed, the results are shown in FIGS.

2 is an image of the nanoparticles prepared in Example 1 taken with a field emission scanning electron microscope (a) and a transmission electron microscope (b). Referring to (a) of FIG. 2, in the case of the nanoparticles prepared in Example 1, dimethyl formamide is used as a solvent, the nanoparticles are in an elliptic form, and the average size of the nanoparticles is 298.5 ± 56.9 nm based on the long axis and shortened. Based on this, it was confirmed that the 119.5 ± 22.9 nm. In addition, looking at (b) of Figure 2, it was confirmed that the conductive polymer (conjugated polymer) having a high electron density appears as dark fine particles.

In addition, Figure 3 is an image taken with a field emission scanning electron microscope of the nanoparticles prepared by changing the ratio of the conductive polymer and fatty acid in a five-fold ratio of 1: 1 to 1:20 using acetic acid as a solvent. The nanoparticles of FIG. 3 are nanoparticles prepared using acetic acid as a solvent. It was confirmed that the nanoparticles showed similar shapes and sizes regardless of magnification.

4 is an image taken with a scanning electron microscope (a) and a transmission electron microscope (b) of the film containing the composite prepared in Example 1. Looking at Figure 4 (a), it was confirmed that the film prepared in Example 1 is uniformly distributed nanoparticles on the surface of the polyurethane resin, having a smaller size than when photographing the nanoparticles alone It was. In addition, looking at (b) of Figure 4, it was confirmed that the nano-particles appearing as dark particles in the polyurethane matrix uniformly distributed in the cross-sectional transmission electron microscope image of the film prepared in Example 1.

FIG. 5 is an image of the fiber prepared in Example 4 taken with a field emission scanning electron microscope (FE-SEM). FIG. In FIG. 5, (a) is an image of one fiber (scal bar = 100 μm), (b) is a cross-sectional image (scale bar = 1 μm) of the cut fiber side, and (c) to (f) are It is an image of the fiber surface, in which the scale bar represents 1 μm in (c) and (d) and the scale bar represents 2 μm in (e) and (f). Looking at Figure 5, it was confirmed that the fiber containing the composite according to the present invention has an average diameter of 200 to 300㎛.

6 is an image taken with an optical microscope (OM) of the fiber prepared in Example 4, (a) is an optical image measured without an optical filter, (b) is an optical image at 650nm light irradiation, (c) Fluorescence image at 650 nm light irradiation. Looking at Figure 6, the average diameter of the fiber is about 150㎛, it was confirmed that the light is emitted during light irradiation. In FIG. 6, the scale bar represents 200 μm.

Through this, it can be seen that the composite according to the present invention has a structure in which nanoparticles in which the conductive polymer and the fatty acid are complexed on the polymer matrix are uniformly distributed.

Experimental Example  2

Fourier Transform-Infrared spectroscopy (FT) of the composites prepared in Examples and Comparative Examples to confirm the nanoparticles and the binding properties between the components including the same according to the present invention -IR) and Grazing-Incidence X-ray Diffraction (GIXD) were measured, and the measured results are shown in FIGS. 7 and 8.

7 is a graph of a result of analyzing the film including the composite prepared in Example 1 by grazing angle X-ray diffraction, (a) is a 2D GIXD pattern graph, (b) is a graph showing the diffraction peak of qtz and qrz to be. Referring to FIG. 7, in Example 1, the nanoparticles prepared with a conductive polymer and a fatty acid molar ratio of 1:12 have a carboxylic acid structure on the surface thereof, and dried by applying a nanoparticle solution on a silicon substrate, followed by drying. Analyzing by diffraction, referring to FIG. 7, the q value showed a slightly blurry diffusion ring in the range of 1.2 to 1.7 Å ⁻¹ , showing an arbitrarily dispersed assembly structure. On the other hand, in Figure 7 (a), the diffraction spots derived from the close conjugated backbone with lateral packing of the alkyl chains are clearly seen in the red dotted box. In particular, the d spacing of the (2h1) diffraction at a q value of 1.25 is about 5.0 Hz, which is indicated by the side packing of the conjugate backbone plane. In addition, the 2D GIXD pattern and the pattern cut out of the out-of-plane direction clearly showed (0h0) diffraction and confirmed to the fifth-order diffraction peak. The d-spacing and coherence length (eg, apparent crystallite size), calculated by the peak width of the (010) diffraction, was 36.6 kHz and about 76 nm, respectively. This d-spacing corresponds to the bilayer thickness with the conductive polymer (PCPDTBT) chain self-assembled in the fatty acid bilayer. The coherent length of 76 nm indicates that the elliptical nanoparticles have 20 overlapping layers of these fatty acid bilayers. In general, the emulsification process of assembling conjugated polymers with surfactants produces spherical particulates by packing between side chain alkyl groups by hydrophobic interactions and minimizing surface tension overwhelming π-π interactions between conjugated main chains. Here, the molecular assembly in the long axis is active by the contribution of hydrogen bonds by the carboxylic acid through an emulsion process using octanoic acid to generate an ellipsoid.

FIG. 8 is a graph of Fourier Transform-Infrared spectroscopy (FT-IR) of a film including a composite of Examples and Comparative Examples. Referring to Figure 8, the polyurethane film is a hydrogen-bonding peak appeared in the secondary amine (-NH) at about 3315 cm ^-1, it was confirmed the non-hydrogen-bonded carbonyl group at 1730cm ^-1, Urethane unit at 1700 cm ^-1 Hydrogen-bonded carbonyl group was confirmed at, and the carbonyl group was identified at the urea unit at 1664 cm ⁻¹ . The yellow boxed portion of FIG. 8 confirms the presence of partial hydrogen bonds and by-product urea between our coal units. Example 1 The film was confirmed a hydrogen-bonded carbonyl group, a secondary amine at 3315cm ^-1 in 1700 cm ^-1 of the, resulting poly we can seen that the hydrogen bonding enhanced between the carboxyl group and the carbon nanoparticles surface have.

Experimental Example  3

In order to confirm the mechanical and optical properties of the composite according to the present invention, UV-Vis absorbance, light stability and dynamic mechanical analysis experiments were performed on the composites of Examples and Comparative Examples. To FIG. 11.

9 is a UV absorption spectrum graph of the nanoparticles prepared in Examples and Comparative Examples, (a) is a graph of the nanoparticles prepared by mixing the conductive polymer and fatty acid in a molar ratio of 1:12, (b) is It is a graph of the nanoparticles prepared while increasing the molar ratio of the conductive polymer and fatty acid from 5-fold by 1: 1 to 1:20. Specifically, in the case of (a) of FIG. 9, the nanoparticles are manufactured by using dimethyl formamide (DMF) as a solvent to form a composite with polyurethane, and measured by UV on dimethyl formamide (DMF). In the case of the nanoparticles are prepared using acetic acid (Acetic acid) as a solvent to make a composite with nylon, and measured the UV on acetic acid. Looking at Figure 9, it was confirmed that the nanoparticles including the conductive polymer (PCPDTBT) combined with fatty acids exhibit improved optical properties. Specifically, when PCPDTBT was dissolved in chloroform as a single chain, it showed a maximum absorption at 718 nm, reflecting the intramolecular delocalization of the conjugated backbone. On the other hand, the nanoparticles of Example 1 exhibited maximum absorption at 799 nm and this change indicates that the alkyl chain of octanoic acid and the conjugated backbone of the conductive polymer are bonded to each other. In addition, as shown in Figure 9 (b) it was confirmed that the wavelength absorption rate increases as the proportion of fatty acids in the nanoparticles increases.

FIG. 10 is a graph showing results of light stability experiments on nanoparticles in Example 1. FIG. Referring to FIG. 10, the maximum absorption at 799 nm was observed under white light, and the maximum absorption amount of the nanoparticles was measured by irradiating white light by blocking ultraviolet irradiation generated by a solar simulator. It was confirmed that the light absorption rate is better. Specifically, after irradiating light for 3 hours under white light and visible / near infrared light excluding ultraviolet light, the absorption maximum was decreased to 87.0% and 94.5% of the initial intensity, respectively. Although not shown in the graph, nanoparticles prepared by diluting a conductive polymer (PCPDTBT) in methanol in excess and precipitating in chloroform solution were reduced to 73.4% and 83.0% of initial strength, respectively, under the same conditions. These results indicate that the conductive polymer combined with the fatty acid can be protected from active species in the surrounding medium such as active radicals or ions generated upon irradiation with light, and thus can be used as a fiber material.

11 is a graph showing the results of dynamic mechanical analysis of the films prepared in Comparative Example 4 and Example 1. FIG. Referring to Figure 10, in order to confirm the mechanical properties of the polyurethane containing nanoparticles, the tensile storage of the polyurethane film of Comparative Example 2 and the film comprising the composite of Example 1 in the temperature range of -80 ℃ to 150 ℃ Modulus of elasticity (E ') and heat transfer of the loss tangent were measured by dynamic mechanical analysis. In the plot of the loss tangent, the two films showed the same β relaxation corresponding to soft segment relaxation in polyurethane at -38 ° C. The storage modulus values of the two films were about GPa more than β relaxation, markedly reduced to several tens of MPa than β relaxation, and reached almost zero at 150 ° C., which is typical of thermoplastic elastomers. Surprisingly, the difference in storage modulus value between the film of Comparative Example 4 and the film of Example 1 was less than 5 MPa in the temperature range of 0 to 150 ° C., and the polyurethane film containing nanoparticles had a slight change in mechanical properties after including the nanoparticles. Only a decrease was observed. Through this, it can be seen that even showing the nanoparticles exhibit excellent mechanical properties of the polyurethane film.

Experimental Example  4

In order to confirm the antimicrobial and photothermal properties of the composite according to the present invention, the following experiment was performed.

(1) antibacterial

Evaluation experiments were carried out using a polyurethane film including the conductive polymer nanoparticles of the present invention, a film containing silver particles, and a film not treated as a comparative example, and the results are shown in FIG. 12 and Table 1. .

Experimental Method

-Test strain used: Strain 1-Staphylococcus aureus ATCC 6538P

                 Strain 2-Escherichia coli ATCC 8739

Standard coating film: Stomacher 400 POLY-BAG

-Test condition: Test bacteria after 35 hours incubation at 35 ± 1 ℃, RH 90 ± 5%

-Sample surface area: Requestor presentation condition

-Antibacterial activity value (S): log (M _b / M _c ), reduction rate (%): [(M _b -M _c ) / M _b ] × 100

-Growth value (F): log (M _b / M _a ) (more than 1.5)

-M _a : Average number of viable cells immediately after inoculation of test bacteria of standard sample (3 samples)

-M _b : Average number of viable cells after incubation for 24 hours with standard sample (3 samples)

-M _c : Mean number of viable cells after incubation for a certain time (24 hours) of antimicrobial processed samples (3 samples)

12 is an image of an antimicrobial test result for a film including a composite of Examples and Comparative Examples. The upper image (corresponding to a-0 to a-7) is experimental data of test strain 1, and the lower image (corresponding to b-0 to b-7) is experimental data of test strain 2. Looking at Table 1, the film containing the composite according to the present invention showed as excellent antimicrobial activity as a polyurethane film containing conventional antimicrobial silver nanoparticles. Specifically, the conventional polyurethane film showed the lowest antimicrobial activity, and the antimicrobial activity value was 0.1 and the reduction rate was 27.3%. The film in which 1 wt% silver nanoparticles were dispersed compared to polyurethane was incubated at 35 ° C. for 24 hours, and the antimicrobial activity was 6 and the reduction rate was 99.9% in S.aureus and E. coli. In the film including the composite of the present invention, the polyurethane film containing 0.5 wt% and 1.0 wt% of the nanoparticles showed the same antimicrobial activity value and bacterial concentration reduction rate as the polyurethane film including the silver nanoparticles. On the other hand, the polyurethane film containing 0.25% by weight of the nanoparticles had an antimicrobial activity of 0.7 and a bacterial concentration reduction rate of 80.8%. Through this, the composite according to the present invention can exhibit excellent antimicrobial properties, including nanoparticles exhibiting the same antimicrobial properties even when using less than silver nanoparticles.

(2) photothermal evaluation experiment

Evaluation of the polyurethane film containing the nanoparticles of the present invention as an example, using a polyurethane film containing silver particles, a film that is not treated as a comparative example was carried out, the results are shown in Figure 13, Figure 14 and Table 2.

Experimental Method

 Laboratory temperature: (25 ± 1) ℃

 Samples were stabilized to equal temperature in the dark.

 The solar simulator induces photo-heating after irradiating light at 20cm away from the sample, and measures the temperature of the film in the film state every 10 minutes for 60 minutes, and checks whether the temperature persists for 60 minutes after turning off the light irradiation. The temperature was measured using an IR thermometer.

(b-1) (b-2) (b-3) (b-4) (b-5) (b-6) (b-7) (b-8) 0 min 25.6 ℃ 25.5 ℃ 25.6 ℃ 25.3 ℃ 25.5 ℃ 25.3 ℃ 25.6 ℃ 25.5 ℃ 10 min 31.3 ℃ 31.7 ℃ 32.2 ℃ 42.8 ℃ 34.7 ℃ 36.5 ℃ 38.3 ℃ 27.1 ℃ 20 min 31.7 ℃ 31.8 ℃ 34.2 ℃ 46.7 ℃ 35.2 ℃ 37.0 ℃ 40.0 ℃ 29.5 ℃ 30 min 31.8 ℃ 31.9 ℃ 34.5 ℃ 47.0 ℃ 35.7 ℃ 38.4 ℃ 40.8 ℃ 30.5 ℃ 40 min 31.7 ℃ 31.9 ℃ 34.5 ℃ 48.9 ℃ 36.3 ℃ 38.5 ℃ 40.8 ℃  31.7 ℃ 50 min 31.9 ℃ 32.0 ℃ 34.6 ℃ 49.2 ℃ 36.4 ℃ 38.7 ° C 42.3 ℃ 34.1 ℃ 60 min 32.0 ℃ 32.3 ℃ 34.7 ℃ 50.0 ℃ 36.8 ℃ 39.2 ℃ 44.2 ℃ 34.2 ℃ 70 min 30.0 ℃ 30.2 ℃ 30.2 ℃ 31.6 ℃ 30.7 ℃ 29.8 ℃ 31.6 ℃ 27.0 ℃ 80 min 29.5 ℃ 29.7 ℃ 29.8 ℃ 30.9 ℃ 29.5 ℃ 29.3 ℃ 31.3 ℃ 26.5 ℃ 90 min 29.1 ℃ 29.3 ℃ 29.3 ℃ 30.1 ℃ 29.3 ℃ 29.1 ℃ 31.2 ℃ 26.5 ℃ 100 min 28.9 ℃ 29.0 ℃ 29.2 ℃ 30.1 ℃ 28.9 ℃ 29.0 ℃ 30.7 ℃ 26.4 ℃ 110 min 28.7 ℃ 28.7 ℃ 29.0 ℃ 29.7 ℃ 28.9 ℃ 29.0 ℃ 30.7 ℃ 26.5 ℃ 120 min 28.2 ℃ 28.2 ℃ 28.6 ℃ 28.7 ℃ 28.1 ℃ 28.8 ℃ 30.7 ℃ 26.5 ℃

Referring to Figure 13, (a-1) is a pure polyurethane film of Comparative Example 2, (a-2) is a polyurethane film containing 1% by weight of octanoic acid of Comparative Example 3, (a-3) is a Comparative Example Polyurethane film containing 1% by weight of silver nanoparticles of 1, (a-4) is a polyurethane film containing 1% by weight of conductive polymer of Comparative Example 4, (a-5) is 0.25 of the nanoparticles of Example 3 Polyurethane film comprising a weight%, (a-6) is a polyurethane film containing 0.5% by weight of nanoparticles of Example 2, (a-7) is a poly containing 1% by weight of nanoparticles of Example 1 The urethane film, (a-8), is a graph of temperature change for 60 minutes during light irradiation and 60 minutes after light removal of a polyurethane fiber including 1 wt% of the nanoparticles of Example 4. Looking at Figure 13, the polyurethane fiber of Example 4 has a lower temperature change rate than the film because of the small area. On the other hand, the film was only mixed with polyurethane without nanoparticles of 1% by weight of conductive polymer showed the highest temperature change rate. In addition, it was confirmed that the film or fiber including the composite according to the present invention has a heat storage effect even after removing light including nanoparticles, as can be seen from the 1 hour data after light removal.

14 and Table 2 (b-1) is a pure polyurethane film of Comparative Example 2, (b-2) is a polyurethane film containing 1% by weight of octanoic acid of Comparative Example 3, (b-3) is a comparison Polyurethane film containing 1% by weight of silver nanoparticles of Example 1, (b-4) is a polyurethane film containing 1% by weight of the conductive polymer of Comparative Example 4, (b-5) is a nanoparticle of Example 3 Polyurethane film comprising 0.25% by weight, (b-6) is a polyurethane film containing 0.5% by weight of nanoparticles of Example 2, (b-7) comprises 1% by weight of nanoparticles of Example 1 Polyurethane film, (b-8), is a near infrared (NIR) image and data on temperature change during 60 minutes of light irradiation and then 60 minutes after light removal of a polyurethane fiber comprising 1% by weight of nanoparticles of Example 4 .

14 and Table 2, when the white light from the solar simulator is exposed for 1 hour, the polyurethane film, a composite comprising the nanoparticles according to the present invention is a pure polyurethane film and silver nanoparticles regardless of the content of nanoparticles The temperature increased more than the polyurethane film containing 1 weight. After 1 hour of irradiation, the median temperature of the film exposed to light was 32.0 ° C, 32.3 ° C, 34.7 ° C, 50.0 ° C, 36.8 ° C, 39.2 ° C, 44.2 ° C, and (b-1) to (b-8), respectively. 34.2 ° C. Therefore, it can be seen that the composite (polyurethane film) according to the present invention emits more thermal energy after light absorption than the comparative example. In addition, it was confirmed that the polyurethane film of Example 1, which has the highest content of nanoparticles, stored 30.7 ° C. even after 60 minutes of light irradiation, thus storing a lot of thermal energy.

Claims (13)

Polymeric resin matrix; And
It comprises nanoparticles dispersed in the polymer resin matrix,
The nanoparticles are complex, characterized in that the conductive polymer and the fatty acid complex structure. The method of claim 1,
The nanoparticles have a core-shell structure as a complexed structure of a fatty acid and a conductive polymer,
Wherein said core comprises a conductive polymer and said shell comprises a fatty acid. The method of claim 1,
The nanoparticles are a composite, characterized in that the content of the conductive polymer and fatty acid in a molar ratio of 1: 5 to 20. The method of claim 1,
Nanoparticles content is 0.25 to 2 parts by weight based on 100 parts by weight of the polymer resin composite. The method of claim 1,
The polymer resin matrix is a composite comprising at least one member selected from the group consisting of polyurethane, nylon, urea, polyacrylonitrile, and polyvinyl alcohol. The method of claim 1,
The conductive polymer is at least one composite selected from the group consisting of polythiophene-based polymer, polypyrrole-based polymer, polyfluorene-based polymer, polyacetylene-based polymer, polythiodiazole-based polymer, and polyaniline-based polymer. The method of claim 1,
The fatty acid is a complex containing an alkyl group having 5 to 15 carbon atoms. Preparing nanoparticles by sonicating a solution mixed with a fatty acid and a conductive polymer; And
Method of producing a composite comprising the step of preparing a composite by adding the prepared nanoparticles to the polymer resin solution. The method of claim 8,
Step of preparing the nanoparticles is a method for producing a composite is carried out by irradiating for 10 minutes to 10 to 100kHz ultrasonic waves. The method of claim 8,
Fatty acid relative to 1 mole of the conductive polymer in the step of preparing the nanoparticles is a method for producing a composite, characterized in that for mixing in a molar ratio of 5 to 20. The method of claim 8,
Nanoparticles prepared in the step of preparing the composite is a method for producing a composite, characterized in that mixed by 0.25 parts by weight to 2 parts by weight based on 100 parts by weight of the polymer resin. Fiber comprising the composite according to claim 1. Film comprising the composite according to claim 1.

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