KR102573827B1 - Manufacturing method of super water-repellent and oil-repellent fiber - Google Patents

Abstract

The present invention relates to a method for manufacturing super water-repellent and oil-repellent fibers, and a method for manufacturing super-water-repellent and oil-repellent fibers according to an embodiment of the present invention includes a plasma structuring process step of forming a three-dimensional structure on fibers; and a plasma deposition process step of vacuum depositing a material having a low surface energy on the structured fiber or a coating process step of wet or dry coating a material having a low surface energy on the structured fiber.

Description

Super water-repellent and oil-repellent fiber manufacturing method {MANUFACTURING METHOD OF SUPER WATER-REPELLENT AND OIL-REPELLENT FIBER}

The present invention relates to a method for producing super water-repellent and oil-repellent fibers.

Industrial protective clothing and chemical protective clothing are designed to protect individuals from the threat of chemicals, chemical agents, and biological agents in gaseous, liquid, and aerosol states. The outer shell of protective clothing primarily serves to protect against the threat of liquid chemical and biological agents. Therefore, by imparting super water repellent and oil repellent properties to the surface of the fiber, it is intended to delay the absorption of chemicals in liquid state into the inside of the protector, and ultimately to repel the chemicals remaining on the surface from the surface.

As an example of chemical and biological protection clothing and industrial protective clothing, a coating agent containing fluorine is coated on the surface of the fiber to realize super water repellent and oil repellent properties. Existing coating agents use a fluorine-based polymer having more than 8 perfluorocarbons (C8) as a main material. However, due to international and domestic restrictions on the use and production of persistent organic pollutants that are harmful to the environment and human body, the production and use of C8 perfluorinated compound coatings is not possible, and it is temporarily permitted in some fields for industrial safety and national safety. there is. Therefore, it is essential to develop a water-repellent and oil-repellent coating technology that can replace C8 or higher perfluorinated compounds.

As an example of CBRN protective clothing, the chemical agent used in recent CBRN terrorism has a high durability and does not easily evaporate and remains on the outer surface for a long time, so it is judged that primary protection through the outer shell is very important. Therefore, a technique to increase water and oil repellency by coating nanoparticles and C6 fluoropolymer for structuring the fiber surface has been proposed, but it is difficult to show oil repellency to chemical agents that have surface properties similar to those of oil.

In addition, in the existing technology, the water-repellent and oil-repellent performance of the fiber is deteriorated by repeated washing, which is because the coated nanoparticles and polymers are easily separated by mechanical friction. Therefore, it is necessary to design water-repellent and oil-repellent fibers that increase mechanical durability by precisely controlling the nanostructure of the fiber itself and designing the polymer not to be exposed to friction.

In order to solve the above problems, the present invention is to provide a method for producing super water-repellent and oil-repellent fibers and NBC protective clothing through three-dimensional surface structure control.

Specifically, according to the present invention, the three-dimensional nano / microstructure is directly controlled and formed on the surface of the fiber by a dry method, and a fluorine compound is deposited or a fluorine compound solution is coated by a dry method to obtain super water-repellent and oil-repellent fibers. want to manufacture Alternatively, after depositing a fluorine compound or coating a fluorine compound solution by a dry method, the eco-friendly coating material is not chemically denatured by a dry method on the surface of the fiber, and a three-dimensional structure is formed to produce super water-repellent and oil-repellent fibers.

An object of the present invention is to maximize water and oil repellency characteristics and washing durability characteristics by coating a structured and eco-friendly coating material on the surface of the fiber itself.

However, the problem to be solved by the present invention is not limited to the problems mentioned above, and other problems not mentioned will be clearly understood by those skilled in the art from the description below.

Super water-repellent and oil-repellent fiber manufacturing method according to an embodiment of the present invention includes a plasma structuring process step of forming a three-dimensional structure on the fiber; and a plasma deposition process step of vacuum depositing a material having a low surface energy on the structured fiber or a coating process step of wet or dry coating a material having a low surface energy on the structured fiber.

Super water-repellent and oil-repellent fiber manufacturing method according to an embodiment of the present invention includes a coating process step of wet or dry coating a material with low surface energy on a fiber; and a plasma structuring process step of forming a three-dimensional structure on the coated fiber.

According to one embodiment, the fiber may include at least one selected from the group consisting of cotton, nylon, polyester, rayon, PVDF, and PTFE.

According to one embodiment, the material having a low surface energy may include at least one selected from the group consisting of non-fluorine materials and C6 or less fluorine-based compounds.

According to an embodiment, the process gas of the plasma structuring process is a mixture of an etching gas and an inert gas, and the etching gas includes oxygen (O ₂ ), sulfur hexafluoride (SF ₆ ), and carbon tetrafluoride (CF ₄ ). It includes at least one selected from the group consisting of, and the inert gas is at least selected from the group consisting of nitrogen (N ₂ ), argon (Ar), helium (He), krypton (Kr), and xenon (Xe). may contain one.

According to an embodiment, the concentration of the process gas is 1 sccm to 1000 sccm, the vacuum pressure of the process gas is 10 ^-6 Torr to 10 ^-3 Torr, and the plasma discharge power of the plasma structuring process is 5 W to 500 sccm. It may be W.

According to one embodiment, the process gas of the plasma deposition process is sulfur hexafluoride (SF ₆ ), carbon tetrafluoride (CF ₄ ), ethylene tetrafluoride (C ₂ F ₄ ), ethane hexafluoride (C ₂ F ₆ ), It includes at least one selected from the group consisting of hexafluoropropylene (C ₃ F ₆ ), octafluorobutane (C ₃ F ₈ ), and octafluorocyclobutane (cC ₄ F ₈ ), and the process gas is , Hexamethyldisiloxane (Hexamethyldisiloxane, HDMSO), tetraethoxysilane (Tetraethoxysilane, TEOS), and trimethylchlorosilane (Trimethylchlorosilane, TMCS) may include at least one organic material selected from the group consisting of as a precursor.

According to an embodiment, the process gas may further include at least one selected from the group consisting of nitrogen (N ₂ ), argon (Ar), helium (He), krypton (Kr), and xenon (Xe). there is.

According to an embodiment, the plasma structuring process step and the plasma deposition process step may be performed in a continuous plasma process system.

According to one embodiment, the wet coating process step includes a padding-drying process, the pressure of the padding-drying process is 5 Pa or more, and the coating agent concentration of the padding-drying process is 15 wt% or less. it could be

According to one embodiment, the dry coating process step includes a polymer thin film chemical vapor deposition method coating, and the polymer thin film chemical vapor deposition method includes 1H, 2H, 2H, 2H-perfluorooctyl methacrylate (1H, 2H ,2H,2H-Perfluorooctyl methacrylate (PFOMA), 1H,1H,7H-dodecafluoroheptyl acrylate (DFHA) and pentafluorophenyl methacrylate (Pentafluorophenyl methacrylate) At least one selected from the group is used as a monomer, and the input concentration of the monomer may be 100 mTorr or less.

According to one embodiment, when the polymer thin film chemical vapor deposition method is coated, the temperature of the surface where the fiber is located may be 40 °C or higher.

According to one embodiment, the coating process step may include at least one selected from the group consisting of a padding-drying (P&D) process, a polymer thin film chemical vapor deposition (iCVD) process, and a spray process.

According to one embodiment, in the coating process step, the material having a low surface energy may be coated to a thickness of 1 μm or more.

According to an embodiment, the process gas of the plasma structuring process may include at least one reducing gas selected from the group consisting of hydrogen (H ₂ ) and carbon monoxide (CO).

According to one embodiment, the process gas is sulfur hexafluoride (SF ₆ ), carbon tetrafluoride (CF ₄ ), ethylene tetrafluoride (C ₂ F ₄ ), ethane hexafluoride (C ₂ F ₆ ), propylene hexafluoride ( It may further include _at least one fluorocarbon gas selected from the group consisting of C ₃ F ₆ ), octafluorobutane (C 3 F ₈ ), and octafluorocyclobutane (cC ₄ F ₈ ).

According to one embodiment, the flow rate of the process gas is 50 sccm or less, the plasma structuring process pressure is 10 ^-6 Torr to 10 ^-4 Torr, and the plasma discharge power of the plasma structuring process is 5 W to 500 W it could be

CBR protection coating according to an embodiment of the present invention is an outer shell; and a permselective separation membrane or a permeable adsorption layer and adsorbent fibers, and the outer shell may include super-water-repellent and oil-repellent fibers according to the method for producing super-water-repellent and oil-repellent fibers of claim 1 or 2.

The present invention is to provide a method for controlling a three-dimensional surface structure, a super water-repellent and oil-repellent fiber manufactured according to the method, and protective clothing using the same.

The water-repellent and oil-repellent protective clothing manufactured according to the present invention has air permeability, high mechanical and washing durability, and can be provided as a protective material that blocks various liquid chemicals and organic substances.

The material developed in the present invention can be provided as a chemical protection material that can repel liquid chemical agents such as VX, HD, and GD. This material can be used for impermeable, selectively permeable NBC protection clothing (eg, NBC protective clothing, NBC protective shoes, NBC protective gloves, etc.), and can be used for permeable NBC protection clothing.

Figure 1 is a flow chart showing a method for producing a three-dimensional structure super water-repellent and oil-repellent fibers through plasma structuring and plasma deposition according to an embodiment of the present invention.
Figure 2 is a flow chart showing a method for producing a three-dimensional structure super water-repellent and oil-repellent fibers through plasma structuring and wet coating according to an embodiment of the present invention.
3 is a flow chart showing a method for producing a three-dimensional super water-repellent and oil-repellent fiber through plasma structuring and dry coating according to an embodiment of the present invention.
Figure 4 is a flow chart showing a method for producing a three-dimensional structure super water-repellent and oil-repellent fibers through plasma structuring after a coating process according to an embodiment of the present invention.
5 is a SEM image of a fiber surface subjected to a plasma 3D structuring process for each fiber according to an embodiment of the present invention.
6 is an SEM image of a fiber surface according to plasma power in a plasma structuring process according to an embodiment of the present invention.
7 is a SEM image of a fiber surface subjected to a plasma deposition process according to an embodiment of the present invention.
8 is a plasma 3D structuring process and plasma deposition process continuous system according to an embodiment of the present invention.
9 is a SEM image of a fiber surface after a wet coating process after a plasma three-dimensional structuring process according to an embodiment of the present invention.
10 is a SEM image of a fiber surface after a dry coating process after a plasma three-dimensional structuring process according to an embodiment of the present invention.
11 is a water contact angle and slip angle measurement results of fibers according to an embodiment of the present invention.
12 is a result of oil repellency of fibers according to an embodiment of the present invention.
13 is a result of oil repellency according to friction of fibers according to an embodiment of the present invention.
14 is a result of measuring nerve agent permeability of protective clothing according to an embodiment of the present invention.

Hereinafter, embodiments will be described in detail with reference to the accompanying drawings. However, since various changes can be made to the embodiments, the scope of the patent application is not limited or limited by these embodiments. It should be understood that all changes, equivalents or substitutes to the embodiments are included within the scope of rights.

Terms used in the examples are used only for descriptive purposes and should not be construed as limiting. Singular expressions include plural expressions unless the context clearly dictates otherwise. In this specification, terms such as "include" or "have" are intended to designate that there is a feature, number, step, operation, component, part, or combination thereof described in the specification, but one or more other features It should be understood that the presence or addition of numbers, steps, operations, components, parts, or combinations thereof is not precluded.

Unless defined otherwise, all terms used herein, including technical or scientific terms, have the same meaning as commonly understood by a person of ordinary skill in the art to which the embodiment belongs. Terms such as those defined in commonly used dictionaries should be interpreted as having a meaning consistent with the meaning in the context of the related art, and unless explicitly defined in the present application, they should not be interpreted in an ideal or excessively formal meaning. don't

In addition, in the description with reference to the accompanying drawings, the same reference numerals are given to the same components regardless of reference numerals, and overlapping descriptions thereof will be omitted. In describing the embodiment, if it is determined that a detailed description of a related known technology may unnecessarily obscure the gist of the embodiment, the detailed description will be omitted. In addition, in describing the components of the embodiment, terms such as first, second, A, B, (a), and (b) may be used. These terms are only used to distinguish the component from other components, and the nature, order, or order of the corresponding component is not limited by the term. When an element is described as being “connected,” “coupled to,” or “connected” to another element, that element may be directly connected or connected to the other element, but there may be another element between the elements. It should be understood that may be "connected", "coupled" or "connected".

Components included in one embodiment and components having common functions will be described using the same names in other embodiments. Unless stated to the contrary, descriptions described in one embodiment may be applied to other embodiments, and detailed descriptions will be omitted to the extent of overlap.

Super water-repellent and oil-repellent fiber manufacturing method according to an embodiment of the present invention includes a plasma structuring process step of forming a three-dimensional structure on the fiber; and a plasma deposition process step of vacuum depositing a material having a low surface energy on the structured fiber or a coating process step of wet or dry coating a material having a low surface energy on the structured fiber.

The three-dimensional structure control, which creates a fiber surface with increased roughness by forming a micro/nano structure complex protrusion, can exert a synergistic effect with the deposition and coating process to maximize water and oil repellency and wash durability. In general, a surface having a contact angle of 150 ° or more between a liquid and a surface is defined as a super-repellent surface.

According to one embodiment, a process technology for coating a material having low surface energy while maintaining a three-dimensional surface structure may be included.

Figure 1 is a flow chart showing a method for producing a three-dimensional structure super water-repellent and oil-repellent fibers through plasma structuring and plasma deposition according to an embodiment of the present invention.

According to FIG. 1, a method for manufacturing a three-dimensional super water-repellent and oil-repellent fiber according to an embodiment includes preparing a fiber, fabricating a three-dimensional structure on the surface of a fiber by a plasma three-dimensional structure process, and a three-dimensional plasma deposition process. A step of coating an environmentally friendly fluorine material on the structural fibers may be included.

Figure 2 is a flow chart showing a method for producing a three-dimensional structure super water-repellent and oil-repellent fibers through plasma structuring and wet coating according to an embodiment of the present invention.

According to FIG. 2, the method for manufacturing a three-dimensional super water-repellent and oil-repellent fiber according to an embodiment includes preparing a fiber, fabricating a three-dimensional structure on a fiber surface by a plasma three-dimensional structure process, coating agent padding wet process, drying and coating an environmentally friendly fluorine material on the three-dimensional structured fiber through a heat treatment process. Hydrophilizing the fiber during the plasma 3D structure process can increase the pick-up rate of the fluorine material through the padding process. The degree of hydrophilization can be controlled by the composition ratio of oxidizing gas, treatment time, and process power.

3 is a flow chart showing a method for producing a three-dimensional super water-repellent and oil-repellent fiber through plasma structuring and dry coating according to an embodiment of the present invention.

According to FIG. 3, a method for producing a three-dimensional structure super water-repellent and oil-repellent fiber according to an embodiment includes preparing a fiber, fabricating a three-dimensional structure on the surface of a fiber by a plasma three-dimensional structure process, and a dry process (iCVD). It may include the step of coating an environmentally friendly fluorine material through. During the plasma 3D structure process, the dry polymer coating yield can be increased through hydrophilization.

According to one embodiment, in the step of preparing the fiber, plasma may be treated to remove pre-treated chemicals from the fiber. In the case of existing fibers, chemicals may be pretreated to synthesize yarn or increase the efficiency of weaving, which can affect 3-dimensional structuring and water-repellent and oil-repellent coatings, so it can be removed through plasma pre-treatment.

Super water-repellent and oil-repellent fiber manufacturing method according to an embodiment of the present invention includes a coating process step of wet or dry coating a material with low surface energy on a fiber; and a plasma structuring process step of forming a three-dimensional structure on the coated fiber.

According to one embodiment, a process technology for controlling a plasma process may be included to adjust the surface structure without chemically modifying the super water repellent and oil repellent properties.

Figure 4 is a flow chart showing a method for producing a three-dimensional structure super water-repellent and oil-repellent fibers through plasma structuring after a coating process according to an embodiment of the present invention.

According to FIG. 4, the method for producing a three-dimensional super water-repellent and oil-repellent fiber according to an embodiment includes preparing a fiber, water- and oil-repellent coating on the fiber by a wet or dry coating process, and coating the fiber by a plasma three-dimensional structure process. A step of fabricating a three-dimensional structure may be included.

According to one embodiment, the fiber may include at least one selected from the group consisting of cotton, nylon, polyester, rayon, PVDF, and PTFE. However, it is not limited thereto, and any carbon material that can be fibrous can be used.

According to one embodiment, the cross section of the fiber yarn is at least one selected from the group consisting of flat, triangular, peanut, star, cross (+) and C-shaped cross-section yarns are used for structuring fibers. it may be The water-repellent and oil-repellent properties of fabric-type fibers can be adjusted depending on the type and weave density of weave, such as plain weave, twill weave, and double weave.

According to one embodiment, the material having a low surface energy may include at least one selected from the group consisting of non-fluorine materials and C6 or less fluorine-based compounds.

According to one embodiment, the non-fluorine material may include at least one selected from the group consisting of silicone polymers, siloxanes, propylated aromatics, sulfosuccinates, and polypropylene glycol ether (amine, sulfates), and C6 or less fluorine-based compounds are purple Perfluorohexane sulfonates, Perfluorobutane sulfonates, Fluorotelomer sulfonamide (6:2 FTSA), Fluorotelomer alcohols (4:2, 6 :2 FTOH)), Fluorotelomer carboxylic acid (6:2 FTCA), Perfluorobutyl methyl ether and Perfluorooctyl triethoxysilane. It may include at least one selected from the group.

According to an embodiment, the process gas of the plasma structuring process is a mixture of an etching gas and an inert gas, and the etching gas includes oxygen (O ₂ ), sulfur hexafluoride (SF ₆ ), and carbon tetrafluoride (CF ₄ ). It includes at least one selected from the group consisting of, and the inert gas is at least selected from the group consisting of nitrogen (N ₂ ), argon (Ar), helium (He), krypton (Kr), and xenon (Xe). may contain one.

5 is a SEM image of a fiber surface subjected to a plasma 3D structuring process for each fiber according to an embodiment of the present invention.

Referring to FIG. 5, it can be confirmed that a three-dimensional structure was formed on the surface of the fiber strands without roughness using Ar/O ₂ plasma. The plasma structuring process is applicable to various fibers, and depending on the characteristics of the fibers, the size of the three-dimensional structure may be different even under the same process conditions.

According to an embodiment, the concentration of the process gas is 1 sccm to 1000 sccm, the vacuum pressure of the process gas is 10 ^-6 Torr to 10 ^-3 Torr, and the plasma discharge power of the plasma structuring process is 5 W to 500 sccm. It may be W.

According to an embodiment, the size and shape of the 3D surface structure can be adjusted from several tens of nanometers to several tens of micrometers by controlling the type of plasma processing gas, the concentration of the processing gas, the vacuum pressure, the plasma power, and the processing time.

According to one embodiment, when the concentration of the process gas exceeds 1000 sccm, a problem of not being structured may occur, and when the concentration is less than 1 sccm, a problem of slowing down the process may occur.

According to an embodiment, when the vacuum pressure of the process gas exceeds 10 ⁻³ Torr, a problem of not being structured may occur, and when it is less than 10 ⁻⁶ Torr, a problem of slowing down the process may occur.

According to an embodiment, the width and depth of the surface structure may be adjusted according to the plasma discharge power and time of the process gas. When the plasma discharge power exceeds 500 W, it may be difficult to control the desired surface structure, and when the plasma discharge power is less than 5 W, the surface structure may not be generated.

6 is an SEM image of a fiber surface according to plasma power in a plasma structuring process according to an embodiment of the present invention.

Referring to FIG. 6, the surface structure of the PTFE surface, which had been smooth, began to be created through plasma treatment at 5 W, and when confirmed by increasing to 90 W, it was confirmed that the depth and width of the surface structure increased.

According to one embodiment, the process gas of the plasma deposition process is sulfur hexafluoride (SF ₆ ), carbon tetrafluoride (CF ₄ ), ethylene tetrafluoride (C ₂ F ₄ ), ethane hexafluoride (C ₂ F ₆ ), It includes at least one selected from the group consisting of hexafluoropropylene (C ₃ F ₆ ), octafluorobutane (C ₃ F ₈ ), and octafluorocyclobutane (cC ₄ F ₈ ), and the process gas is , Hexamethyldisiloxane (Hexamethyldisiloxane, HDMSO), tetraethoxysilane (tetraethoxysilane, TEOS), and trimethylchlorosilane (trimethylchlorosilane, TMCS) may include at least one organic material selected from the group consisting of as a precursor.

According to an embodiment, the plasma deposition method is plasma enhanced chemical vapor deposition (PECVD), and a polymer having low surface energy may be deposited. According to an embodiment, an environmentally friendly fluorine compound or a non-fluorine compound of C6 or less may be deposited by discharging the fluorine-based gas and the silicon-based organic precursor.

According to an embodiment, the process gas may further include at least one selected from the group consisting of nitrogen (N ₂ ), argon (Ar), helium (He), krypton (Kr), and xenon (Xe). there is.

According to an embodiment, the inert gas may be added to assist discharge of fluorine gas during deposition. According to an embodiment, the chemical properties and structure of the deposited material are controlled according to the mixing ratio of the inert gas, process gas and precursor, process pressure, discharge power, and treatment time.

According to one embodiment, the PECVD discharge power may be 5 W to 500 W, and the characteristics of the surface polymer, polymerization structure, and surface deposition structure may be adjusted according to the discharge power and time.

7 is a SEM image of a fiber surface subjected to a plasma deposition process according to an embodiment of the present invention.

Referring to FIG. 7, it can be confirmed that the fluorine material can be coated on the three-dimensional structure in a dry process, and as the deposition conditions change from 50 W to 200 W, the surface of the sharp structure is deposited thickly. It can be confirmed that it becomes blunt like a mushroom protrusion.

According to an embodiment, the plasma structuring process step and the plasma deposition process step may be performed in a continuous plasma process system.

8 is a plasma 3D structuring process and plasma deposition process continuous system according to an embodiment of the present invention.

Referring to FIG. 8 , it can be seen that the plasma 3D structuring process 110 and the plasma deposition process 120 are continuously performed on the fabric through the roll-to-roll process 100 .

According to one embodiment, the wet coating process step includes a padding-drying process, the pressure of the padding-drying process is 5 Pa or more, and the coating agent concentration of the padding-drying process is 15 wt% or less. it could be

According to one embodiment, the coating may be performed while maintaining a three-dimensional structure by adjusting process conditions using a padding-drying process. The padding-drying wet process is a process of immersing fibers in a coating solution and then weaving the fibers with pressure, so that the coating agent permeates between the surface structures of the fibers to form a coating.

According to one embodiment, the pressure of the padding-drying process may apply a pressure of 5 Pa or more so that the coating agent may be coated between the three-dimensional surface structures. When the process pressure is less than 5 Pa, the coating agent may not permeate between the three-dimensional structures formed by the plasma structuring process.

According to one embodiment, when the concentration of the coating agent exceeds 15wt%, the three-dimensional structure formed by the plasma structuring process may not be maintained.

According to one embodiment, the padded fibers may need to be dried and heat treated. This may be performed for drying of the wet-processed fiber and heat treatment for imparting oil repellency to the fluoropolymer coating agent.

9 is a SEM image of a fiber surface after a wet coating process after a plasma three-dimensional structuring process according to an embodiment of the present invention. Figure 9 (a) is a SEM image of the fiber surface after the coating process, Figure 9 (b) is a SEM image of the fiber surface before the coating process.

Referring to FIG. 9, it can be confirmed that the fluorine material is evenly coated between the three-dimensional structures, and the three-dimensional structure is maintained even after coating.

According to one embodiment, the dry coating process step includes a polymer thin film chemical vapor deposition method coating, and the polymer thin film chemical vapor deposition method includes 1H, 2H, 2H, 2H-perfluorooctyl methacrylate (1H, 2H ,2H,2H-Perfluorooctyl methacrylate (PFOMA), 1H,1H,7H-dodecafluoroheptyl acrylate (DFHA) and pentafluorophenyl methacrylate (Pentafluorophenyl methacrylate) At least one selected from the group is used as a monomer, and the input concentration of the monomer may be 100 mTorr or less.

According to one embodiment, the coating may be performed while maintaining the three-dimensional structure by adjusting process conditions using polymer thin film deposition (iCVD). According to one embodiment, the iCVD coating process may be a mixture of a monomer and an initiator and vapor deposition at a filament temperature or higher. As the monomer, a monomer that polymerizes linearly may be selected, and a perfluorinated monomer having 6 carbon atoms or less may be used.

According to one embodiment, the concentration of the monomer may be preferably 100 mTorr or less. When the monomer concentration exceeds 100 mTorr, there may be a problem of not maintaining a three-dimensional structure.

According to one embodiment, when the polymer thin film chemical vapor deposition method is coated, the temperature of the surface where the fiber is located may be 40 °C or higher.

According to one embodiment, when the temperature of the surface where the fiber is located is less than 40 ° C., it may be difficult to thinly coat the polymer on the surface while maintaining the three-dimensional structure. The smaller the difference between the temperature of the surface and the temperature of the filament where the reaction occurs, the slower the rate at which the polymer is deposited, and the less roughness deposited on the surface, so that it can be thinly coated in the three-dimensional surface structure. According to one embodiment, the polymer deposited by iCVD may have a thickness of 10 nm to 100 nm.

10 is a SEM image of a fiber surface after a dry coating process after a plasma three-dimensional structuring process according to an embodiment of the present invention. 10 (a) is a SEM image of the surface of a fiber subjected to a dry coating process on an existing fiber, and FIG. 10 (b) is an SEM image of a surface of a fiber subjected to a dry coating process after a three-dimensional structuring process.

Referring to FIG. 10, it can be seen that there is a difference in structure between the fiber coated by growing on the fiber surface through the dry process on the existing fiber and the fiber subjected to the dry process after the three-dimensional structure process. When dry coating is performed on a surface with increased roughness, the roughness of the material to be deposited increases, thereby increasing super water/oil repellent properties.

According to one embodiment, the coating process step may include at least one selected from the group consisting of a padding-drying (P&D) process, a polymer thin film chemical vapor deposition (iCVD) process, and a spray process.

According to one embodiment, in the wet and dry coating process, a polymer solution may be wet coated or a chemical substance exhibiting water and oil repellent properties may be coated on the fiber surface by directly growing the polymer on the fiber surface in a dry process.

According to one embodiment, in the coating process step, the material having a low surface energy may be coated to a thickness of 1 μm or more.

According to one embodiment, in order to proceed with surface structuring after coating the chemical material, a material having low surface energy may be coated to a thickness of 1 μm or more. When the coating is less than 1 μm thin, problems may occur in forming a three-dimensional structure exhibiting oil and water repellency during the surface structuring process.

According to an embodiment, the process gas of the plasma structuring process may include at least one reducing gas selected from the group consisting of hydrogen (H ₂ ) and carbon monoxide (CO).

According to an embodiment, since the plasma 3D structure process maintains the chemical properties of the coated fluoropolymer and prevents oxidation through the plasma process, reducing gas may be added to the existing process gas.

According to one embodiment, the process gas is sulfur hexafluoride (SF ₆ ), carbon tetrafluoride (CF ₄ ), ethylene tetrafluoride (C ₂ F ₄ ), ethane hexafluoride (C ₂ F ₆ ), propylene hexafluoride ( It may further include _at least one fluorocarbon gas selected from the group consisting of C ₃ F ₆ ), octafluorobutane (C 3 F ₈ ), and octafluorocyclobutane (cC ₄ F ₈ ).

According to one embodiment, the flow rate of the process gas is 50 sccm or less, the plasma structuring process pressure is 10 ^-6 Torr to 10 ^-4 Torr, and the plasma discharge power of the plasma structuring process is 5 W to 500 W it could be

According to one embodiment, the flow rate of the process gas may be preferably 50 sccm or less. When the gas flow rate exceeds 50 sccm, problems may occur in forming the three-dimensional structure.

According to an embodiment, the aspect ratio of the structure may be adjusted according to the plasma structuring process pressure. When the process pressure exceeds 10 ⁻⁴ Torr, a problem of not being structured may occur, and when the process pressure is less than 10 ⁻⁶ Torr, a problem of slowing down may occur. If it is not within the above range, the coating material may be denatured or the structure may not be formed, resulting in deterioration in oil and water repellency properties.

According to an embodiment, the width and depth of the surface structure may be adjusted according to the plasma discharge power and time, and the degree of denaturation of the coating material may be affected. When the plasma discharge power exceeds 500 W, it may be difficult to control the desired surface structure, and when the plasma discharge power is less than 5 W, the surface structure may not be generated.

11 is a water contact angle and slip angle measurement results of fibers according to an embodiment of the present invention.

Referring to FIG. 11, it can be seen that the contact angle for water increases as the three-dimensional structuring and coating (LIS+PECVD) through plasma is applied to the existing fiber, which indicates that the water repellency performance is increased. In addition, when three-dimensional structuring was performed (LIS+C6), the slip angle was measured to be 5° or less, and it could be confirmed that super water repellency was exhibited.

12 is a result of oil repellency of fibers according to an embodiment of the present invention.

Referring to FIG. 12, n-dodecane is a material having a low surface energy of 25.3 N/m and is a material used for the 5th class oil repellency test of fabrics in KS and ISO standards. It was confirmed that the oil repellency increased through structuring (LIS + C6), and 3-dimensional super water-repellent and oil-repellent fibers can be produced through structuring and dry coating (LIS + iCVD).

13 is a result of oil repellency according to friction of fibers according to an embodiment of the present invention.

Referring to FIG. 13, it is intended to standardize surface properties according to washing of fibers. The main cause of the decrease in durability due to washing is physical friction, and the friction is the result of measuring the repellency with n-dodecane as a test solution after 250 times of Martindale using the standardized Martindale test method. The fiber subjected to 3D structuring (LIS+C6) can confirm the contact angle close to 100° even after 250 rubbing, which indicates that the 3D structuring helps to maintain oil repellency after rubbing.

CBR protection coating according to an embodiment of the present invention is an outer shell; and a permselective separation membrane or a permeable adsorption layer and adsorbent fibers, and the outer shell may include super-water-repellent and oil-repellent fibers according to the method for producing super-water-repellent and oil-repellent fibers of claim 1 or 2.

14 is a result of measuring nerve agent permeability of protective clothing according to an embodiment of the present invention.

Referring to FIG. 14, when compared to conventional water and oil repellents including C8 and C6, the amount of nerve agent passing through is reduced by up to 20% in the case of three-dimensional structuring and coating (LIS-P&D). You can check.

Although the embodiments have been described as above, those skilled in the art may apply various technical modifications and variations based on the above. For example, the described techniques may be performed in an order different from the method described, and/or components of the described system, structure, device, circuit, etc. may be combined or combined in a different form than the method described, or other components may be used. Or even if it is replaced or substituted by equivalents, appropriate results can be achieved.

Therefore, other implementations, other embodiments, and equivalents of the claims are within the scope of the following claims.

100: roll-to-roll process
110: Plasma 3D structuring process
120: plasma deposition process

Claims (18)

Plasma structuring process step of forming a three-dimensional structure on the fiber; and
A plasma deposition process step of vacuum depositing a material having a low surface energy on the structured fiber or a coating process step of wet or dry coating a material having a low surface energy on the structured fiber;
The wet coating process step includes a padding-drying process,
The pressure of the padding-drying process is 5 Pa or more,
The coating agent concentration of the padding-drying process is 15 wt% or less,
The dry coating process step includes polymer thin film chemical vapor deposition coating,
The polymer thin film chemical vapor deposition method, 1H,2H,2H,2H-perfluorooctyl methacrylate (1H,2H,2H,2H-Perfluorooctyl methacrylate, PFOMA), 1H,1H,7H-dodecafluoroheptyl acrylic At least one selected from the group consisting of 1H, 1H, 7H-Dodecafluoroheptyl acrylate (DFHA) and pentafluorophenyl methacrylate is used as a monomer,
The monomer input concentration is 100 mTorr or less,
When the polymer thin film chemical vapor deposition method coating, the temperature of the surface where the fiber is located is 40 ℃ or more,
The process gas of the plasma structuring process is a mixture of an etching gas and an inert gas,
The etching gas includes at least one selected from the group consisting of oxygen (O ₂ ), sulfur hexafluoride (SF ₆ ) and carbon tetrafluoride (CF ₄ ),
The inert gas includes at least one selected from the group consisting of nitrogen (N ₂ ), argon (Ar), helium (He), krypton (Kr), and xenon (Xe),
The concentration of the process gas is 1 sccm to 1000 sccm,
The vacuum pressure of the process gas is 10 ^-6 Torr to 10 ^-3 Torr,
The plasma discharge power of the plasma structuring process is 5 W to 500 W,
Method for producing super water-repellent and oil-repellent fibers.
A coating process step of wet or dry coating a material with low surface energy on fibers; and
Including; plasma structuring process step of forming a three-dimensional structure on the coated fiber,
The coating process step is to coat the material having a low surface energy to a thickness of 1 μm or more,
The process gas of the plasma structuring process includes at least one reducing gas selected from the group consisting of hydrogen (H ₂ ) and carbon monoxide (CO),
The flow rate of the process gas is 50 sccm or less,
The plasma structuring process pressure is 10 ^-6 Torr to 10 ^-4 Torr,
The plasma discharge power of the plasma structuring process is 5 W to 500 W,
Method for producing super water-repellent and oil-repellent fibers.
According to claim 1 or 2,
The fiber comprises at least one selected from the group consisting of cotton, nylon, polyester, rayon, PVDF and PTFE,
Method for producing super water-repellent and oil-repellent fibers.
According to claim 1 or 2,
The material having a low surface energy includes at least one selected from the group consisting of non-fluorine materials and C6 or less fluorine-based compounds,
Method for producing super water-repellent and oil-repellent fibers.
delete delete According to claim 1,
The process gas of the plasma deposition process is sulfur hexafluoride (SF ₆ ), carbon tetrafluoride (CF ₄ ), ethylene tetrafluoride (C ₂ F ₄ ), ethane hexafluoride (C ₂ F ₆ ), propylene hexafluoride (C ₃ F ₆ ), octafluorobutane (C ₃ F ₈ ) and octafluorocyclobutane (cC ₄ F ₈ ) It includes at least one selected from the group consisting of,
The process gas of the plasma deposition process is a precursor of at least one organic material selected from the group consisting of hexamethyldisiloxane (HDMSO), tetraethoxysilane (TEOS), and trimethylchlorosilane (TMCS). which includes,
Method for producing super water-repellent and oil-repellent fibers.
According to claim 7,
The process gas of the plasma deposition process further includes at least one selected from the group consisting of nitrogen (N ₂ ), argon (Ar), helium (He), krypton (Kr), and xenon (Xe),
Method for producing super water-repellent and oil-repellent fibers.
According to claim 1,
The plasma structuring process step and the plasma deposition process step,
Which proceeds in a continuous plasma process system,
Method for producing super water-repellent and oil-repellent fibers.
delete delete delete According to claim 2,
The coating process step includes at least one selected from the group consisting of a padding-drying (P&D) process, a polymer thin film chemical vapor deposition (iCVD) process, and a spray process,
Method for producing super water-repellent and oil-repellent fibers.
delete delete According to claim 2,
The process gas includes sulfur hexafluoride (SF ₆ ), carbon tetrafluoride (CF ₄ ), ethylene tetrafluoride (C ₂ F ₄ ), ethane hexafluoride (C ₂ F ₆ ), propylene hexafluoride (C ₃ F ₆ ), Further comprising at least one fluorocarbon gas selected from the group consisting of octafluorobutane (C ₃ F ₈ ) and octafluorocyclobutane (cC ₄ F ₈ ),
Method for producing super water-repellent and oil-repellent fibers.
delete coat; and
Including a permselective separation membrane or a permeable adsorption layer and adsorption fibers,
The outer shell comprises the first water-repellent and oil-repellent fibers according to the method of manufacturing super-water-repellent and oil-repellent fibers of claim 1 or 2,
NBC protective clothing.

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