KR102542019B1 - Nanofiber complex yarn for high strength wig raw yarn using electrospinning and manufacturing method thereof - Google Patents

Abstract

The present invention relates to a high-strength wig raw nanofiber composite yarn using an electrospinning method and a method for manufacturing the same, and more particularly, to a twist form using a conventional twisting machine after manufacturing a nanofiber yarn using an electrospinning method. Since it is possible to manufacture sheath-core type composite yarn by plying, ready-made equipment can be used as it is, which can reduce manufacturing cost, improve handling, mass production and uniformity, as well as nanofiber It relates to a high-strength wig raw nanofiber composite yarn using an electrospinning method capable of securing excellent stain resistance by coating the yarn with an antifouling coating composition and a manufacturing method thereof.

Description

Nanofiber complex yarn for high strength wig raw yarn using electrospinning and manufacturing method thereof}

The present invention relates to a high-strength wig raw nanofiber composite yarn using an electrospinning method and a method for manufacturing the same, and more particularly, to a twist form using a conventional twisting machine after manufacturing a nanofiber yarn using an electrospinning method. Since it is possible to manufacture sheath-core type composite yarn by plying, ready-made equipment can be used as it is, which can reduce manufacturing cost, improve handling, mass production and uniformity, as well as nanofiber It relates to a high-strength wig raw nanofiber composite yarn using an electrospinning method capable of securing excellent stain resistance by coating the yarn with an antifouling coating composition and a manufacturing method thereof.

In general, wig yarns are made of synthetic fiber materials such as PVC (polyvinylchlride), modacrylic (Modacryl), PET (polyethyleneterephthalate), PP (polypropylene), and the like. These synthetic fiber materials are continuously being developed to satisfy functional and aesthetic factors such as flame retardancy, heat resistance, curl formation, glossiness, and tactility.

Among them, PVC is a widely used wig yarn developed by a melt spinning method, and has good shape stability and good touch, but has a disadvantage in that it is heavy and has a poor sense of volume. In addition, modacrylic has the advantage of flame retardancy to form curls well and has a sense of volume, but creases easily and is lightweight, and acrylic fibers have a problem in that thermal stability is lowered due to a low glass transition temperature.

On the other hand, fibers whose main component is polyester represented by polyethylene terephthalate, which has excellent heat resistance, have excellent curl ability due to high glass transition temperature, good style stability, elasticity, good color and gloss, and easy setting after heat fixation. It is evaluated as a superior material than other fibers for wig yarn.

However, polyester-based resins have disadvantages such as poor texture due to high elastic modulus, difficulty in dyeing, occurrence of tangles due to static electricity, and rapid combustion after ignition. is in need of improvement.

As a method of improving the flame retardancy of these polyester fibers, there is a method of imparting flame retardancy by adding a reactive flame retardant together with a raw material during polyester polymerization or mixing a flame retardant additive with a polyester resin during molding. In this case, the flame retardant additive includes a halogen-containing compound, a mixture of metal oxides, a nitrogen-containing compound, and a phosphorus-containing compound. Among these, halogen-based flame retardants exhibit flame retardancy relatively easily, but problems such as toxicity and discoloration occur, and phosphorus-based flame retardants have problems such as poor processability due to low self-thermal stability and difficulty in increasing polymerization degree.

Therefore, due to the nature of artificial hair, there are problems such as cost increase, productivity decrease, or physical property decrease due to treatment at high temperature, increase in flame retardant content, or long flame retardant treatment time due to the requirement of high heat resistance.

In recent years, while harmless to the human body, research has been actively conducted to manufacture various wig yarns for improving workability, processability, heat resistance, flame retardancy, and physical properties of wig yarns to expand the scope of application. However, when the PET resin-based polyester resin wig yarn secures appropriate flame retardancy, there is a problem of poor mechanical properties and curling properties. In addition, in the case of polypropylene-based wig yarns, curling properties are excellent, but mechanical properties are poor, resulting in poor durability.

Republic of Korea Patent Publication No. 10-2011-0108974 (2011.10.06. Publication)

It is an object of the present invention to manufacture nanofiber yarns using the electrospinning method, and then use an existing twisting machine to ply yarn to form a sheath-core type composite yarn, so that ready-made equipment can be used as it is. Using the electrospinning method, which can reduce manufacturing cost, improve handling, mass productivity, and uniformity, and secure excellent stain resistance by coating nanofiber yarns with an antifouling coating composition. It is to provide a high-strength wig fiber nanofiber composite yarn and a manufacturing method thereof.

Method for manufacturing nanofiber composite yarn for high-strength wig source using electrospinning according to an embodiment of the present invention is (a) dissolving a polymer resin in a solvent to form a spinning solution, and then spinning the spinning solution by electrospinning to polymer nano forming a fibrous web; (b) forming a polymer membrane by laminating the nanofiber web; (c) forming nanofiber yarns by slitting the polymer membrane; (d) coating an antifouling coating composition on the surface of the nanofiber yarn and then drying to form an antifouling coating layer; (e) forming a nanofiber composite yarn by plying and twisting the nanofiber yarn on which the antifouling coating layer is formed; characterized in that it comprises a.

In step (a), the polymer resin includes at least one selected from a thermoplastic polymer resin and a thermosetting polymer resin.

In step (c), the nanofiber yarn has an average diameter of 10 to 300 nm.

In the step (e), the screening includes 15 to 35 wt% of the flame retardant, 0.01 to 3.0 wt% of the heat stabilizer, 0.1 to 2.0 wt% of the process stabilizer, 3 to 10 wt% of the strength reinforcing agent, and the remainder of the polyester resin.

The strength enhancer includes at least one selected from talc, alumina, calcium carbonate, magnesium carbonate, magnesia, calcium silicate, glass fiber, titanium oxide, and antimony oxide, and the strength enhancer has an average diameter of 0.1 to 5 μm.

In the step (e), a tension of 10 to 50 g is applied to the nanofiber yarn, and no force is applied to the screening to perform plying and twisting.

High-strength wig yarn nanofiber composite yarn using the electrospinning method according to an embodiment of the present invention is a high-strength wig yarn nanofiber composite yarn using the electrospinning method, screening; Nanofiber yarns plied in a twist form along the outer circumferential surface of the screening; and an antifouling coating layer formed to cover the surface of the nanofiber yarn, wherein the screening includes 15 to 35 wt% of a flame retardant, 0.01 to 3.0 wt% of a heat stabilizer, 0.1 to 2.0 wt% of a process stabilizer, and 3 to 10 wt% of a strength reinforcing agent. And a remaining polyester resin, and the nanofiber yarn includes at least one selected from a thermoplastic polymer resin and a thermosetting polymer resin.

The nanofiber yarn has an average diameter of 5 to 300 nm.

The strength enhancer includes at least one selected from talc, alumina, calcium carbonate, magnesium carbonate, magnesia, calcium silicate, glass fiber, titanium oxide, and antimony oxide, and the strength enhancer has an average diameter of 0.1 to 5 μm.

The antifouling coating layer includes a urethane oligomer containing 20 to 45% by weight of a binder resin, 5 to 15% by weight of an antifouling agent, 0.5 to 3.0% by weight of a slip agent and the remaining fluorine component, and the antifouling coating layer has a thickness of 50 to 1,000 nm has a thickness of

High-strength wig raw nanofiber composite yarn using electrospinning and its manufacturing method according to the present invention is a sheath-core type by manufacturing nanofiber yarn using electrospinning and then plying the yarn in a twist form using a conventional twisting machine Since it is possible to manufacture a composite yarn of, ready-made equipment can be used as it is, so manufacturing costs can be reduced, and handling, mass productivity, and uniformity can be improved.

In addition, the high-strength wig raw nanofiber composite yarn using the electrospinning method according to the present invention and its manufacturing method use a polyester resin as a main component as a core part, and nanofibers plied in a twist form along the outer circumferential surface of the yarn By using the yarn as the sheath portion, not only can it have excellent mechanical properties and curling properties, but also it is possible to secure excellent stain resistance by coating the surface of the nanofiber yarn with an antifouling coating composition.

As a result, the nanofiber composite yarn for high-strength wig yarn using the electrospinning method according to the present invention and its manufacturing method show strength of 3.20 to 3.90 g / de and elongation of 68 to 75% when the fineness is 50 denier (de).

1 is a schematic diagram showing a nanofiber composite yarn for high-strength wig yarn using an electrospinning method according to an embodiment of the present invention.
2 is an enlarged cross-sectional view of a cut surface of the nanofiber yarn of FIG. 1;
Figure 3 is a process flow chart showing a method for manufacturing a high-strength wig yarn nanofiber composite yarn using an electrospinning method according to an embodiment of the present invention.

Hereinafter, a preferred embodiment of the present invention will be described in detail, but it is intended to be described in detail to the extent that a person skilled in the art can easily practice the invention. It does not mean that the technical idea and scope are limited.

Figure 1 is a schematic diagram showing a high-strength wig raw nanofiber composite yarn using the electrospinning method according to an embodiment of the present invention, Figure 2 is a cross-sectional view showing an enlarged cut surface of the nanofiber yarn of Figure 1.

As shown in FIGS. 1 and 2, the nanofiber composite yarn 100 for high-strength wig yarn using the electrospinning method according to an embodiment of the present invention includes screening 120, nanofiber yarn 140 and antifouling coating layer 160 includes

Screening 120 is used as a core portion located at the inner center of the high-strength wig yarn nanofiber composite yarn 100. Such screening 120 may include a polyester resin as a main component to improve mechanical properties and curling properties.

More specifically, the screening 120 includes 15 to 35% by weight of a flame retardant, 0.01 to 3.0% by weight of a heat stabilizer, 0.1 to 2.0% by weight of a process stabilizer, 3 to 10% by weight of a strength reinforcing agent and the balance polyester resin.

The flame retardant may be a flame retardant generally used in the manufacture of wig yarn, preferably one or a mixture of two selected from phosphorus-based flame retardants and polymeric bromine-based flame retardants, more preferably polymeric bromine-based flame retardants. It is good to use

In the present invention, the flame retardant is preferably added in a content ratio of 15 to 35% by weight of the total weight of the screening 120, more preferably 20 to 30% by weight. If the amount of the flame retardant added is less than 15% by weight of the total weight of the screening 120, sufficient flame retardancy may not be secured, and if the amount exceeds 35% by weight, mechanical properties may deteriorate.

The polymeric bromine-based flame retardant may use a polymeric bromine-based flame retardant having a bromine content of 40 to 80% by weight, preferably 55 to 75% by weight, and more preferably 58 to 70% by weight. At this time, the polymeric brominated flame retardant has a weight average molecular weight (Mw) of 10,000 to 120,000, preferably Mw 30,000 to 95,000, and more preferably Mw 55,000 to 95,000, self-extinguishing property of wig yarn, melt dripping inhibition, fiber It is advantageous in terms of formability and good heat resistance deformation temperature of wig yarn. If the polymeric brominated flame retardant has a Mw of less than 10,000, self-extinguishing properties may be obtained, but an anti-dripping function may not be exhibited during ignition.

Specifically, the polymeric bromine flame retardant may use at least one selected from polystyrene bromo flame retardants, polybromoepoxy flame retardants, polybromophenoxy flame retardants, polybromocarbonate flame retardants and polybromoacrylate flame retardants, preferably Preferably, a polybromoepoxy or polybromophenoxy flame retardant composed of a polymer of brominated bisphenol A diglycidyl ether and brominated bisphenol A is preferably used.

The polymeric brominated flame retardant has a melting temperature of 200 ~ 230 ℃, and the melt spinning temperature of the polyester resin is in the range of about 270 ~ 330 ℃, so the melting temperature of the polyester resin is higher than the melting temperature of the flame retardant by about 70 ~ 100 ℃, so the extruder Since it is kneaded while receiving a large shear force inside the cylinder, thermal decomposition is likely to occur. When thermal decomposition occurs, a three-dimensional cross-linked material is formed and gelation occurs. When operated for a long time, these substances clog the fine nozzle holes, resulting in a state in which spinning is impossible. Fine substances that have passed through the nozzle holes accumulate around the nozzle holes, eventually acting as an obstacle to the flow of polymer, causing filament and warp yarn, resulting in trimming. This causes a decrease in productivity and non-uniformity of the fineness of the wig yarn produced.

Heat stabilizers and process stabilizers minimize the generation of radicals, which are products of thermal decomposition of the resin, improve compatibility between polyester resins and flame retardants, and prevent flame retardants from sticking to metal surfaces such as cylinders, screws and nozzles of melt extruders. added In this case, Iganox 1010 may be used as a heat stabilizer, and Structol TR 065 may be used as a process stabilizer, but is not limited thereto. These heat stabilizers and process stabilizers can obtain significant improvement effects when polybromoepoxy flame retardants or polybromophenoxy flame retardants are used.

The heat stabilizer is preferably added in a content ratio of 0.01 to 3.0% by weight of the total weight of the screening 120, and the process stabilizer is preferably added in a content ratio of 0.1 to 2.0% by weight of the total weight of the screening 120.

A strength enhancer is added to reinforce the strength of the screening 120. The strength reinforcing agent includes at least one selected from among talc, alumina, calcium carbonate, magnesium carbonate, magnesia, calcium silicate, glass fiber, titanium oxide, and antimony oxide.

The strength reinforcing agent is preferably added in a content ratio of 3 to 10% by weight of the total weight of the screening 120, and is more preferably added in a content ratio of 5 to 7% by weight. If the added amount of the strength reinforcing agent is less than 3% by weight of the total weight of the screening 120, the strength reinforcing effect cannot be properly exerted, and if it is added in excess of 10% by weight, there is a high risk of deterioration in physical properties such as heat resistance.

It is preferable that these strength enhancers have an average diameter of 0.1 to 5 μm. When the average diameter of the strength reinforcing agent is less than 0.1 μm, the particle size is refined and the dispersibility of the particles is not uniform, which can cause uneven strength. When the average diameter of the strength reinforcing agent exceeds 5 μm, physical properties such as heat resistance may be lowered

Polyester resins include polyethylene terephthalate (PET) resin, polybutylene terephthalate (PBT) resin, polypropylene terephthalate (PPT) resin, polynaphthalene terephthalate (PEN) resin and polycyclohexanedimethanol terephthalate. (PCT) One or more selected resins may be used. Among these, it is preferable to use a PET resin as the polyester resin, more preferably a difference in intrinsic viscosity of 0.15 to 0.25, most preferably a difference in intrinsic viscosity (IV) of 0.17 to 0.22 by mixing high and low viscosity PET resins. good to use At this time, if the intrinsic viscosity difference is less than 0.15 or exceeds 0.25, it may be difficult to manufacture the nanofiber composite yarn 100 for wig origin having curling properties and mechanical properties to be obtained.

In addition, the polyester resin may further include polycyclohexylene dimethylene terephthalate (PCT) in addition to high-viscosity and low-viscosity PET resins in order to improve the feel and appearance of the nanofiber composite yarn 100 for wig raw materials. The content of PCT may include 1 to 10 parts by weight, more preferably 5 to 10 parts by weight, and most preferably 6 to 9 parts by weight, based on 100 parts by weight of the high-viscosity PET resin. At this time, if the PCT resin content is less than 1 part by weight based on 100 parts by weight of the high-viscosity PET resin, the amount of addition is too small to see the effect of improving the appearance quality of the nanofiber composite yarn 100 for wig origin. When added in excess, the PET resin content is relatively low, which may cause a problem in that the physical properties of the nanofiber composite yarn 100 for wig origin are lowered.

The nanofiber yarn 140 is used as a sheath part surrounding the core part of the nanofiber composite yarn 100 for wig origin. To this end, the nanofiber yarn 140 is plied along the outer circumferential surface of the screening 120 in a twisted form. The nanofiber yarn 140 is formed by an electrospinning method in which a spinning solution formed by dissolving a polymer resin in a solvent is electrospun using an electrospinning device, so that the diameter size can be miniaturized. Accordingly, the nanofiber yarn 140 has an average diameter of 5 to 300 nm.

The nanofiber yarn 140 includes at least one selected from a thermoplastic polymer resin and a thermosetting polymer resin. More preferably, the nanofiber yarn 140 is PVdF (polyvinylidene fluoride), nylon (nylon), nitrocellulose (PU (polyurethane), PC (polycarbonate), PS (polystryene), PAN (polyacrylonitrile), PEI ( polyethyleneimine), PPI(polypropyleneimine), PMMA(Polymethylmethacrylate), PVC(polyvinylcholride), PVAc(polyvinylacetate), PVC(poly vinyl chloride), PVA(poly vinyl alcohol) and PVP(poly vinyl pyrrolidone). can be formed

The antifouling coating layer 160 is formed to cover the surface of the nanofiber yarn 140 . The antifouling coating layer 160 may be formed to cover and seal the entire surface of the nanofiber yarn 140 . In addition, the antifouling coating layer 160 may be formed to locally cover a portion of the surface of the nanofiber yarn 140.

The antifouling coating layer 160 includes a urethane oligomer containing 20 to 45% by weight of a binder resin, 5 to 15% by weight of an antifouling agent, 0.5 to 3.0% by weight of a slip agent, and the remaining fluorine component.

As the binder resin, at least one selected from polyimide, polyethersulfone, polycarbonate, polypropylene, polyethylene, polyethylene terephthalate (PET), and the like may be used.

When the binder resin is less than 20% by weight of the total weight of the antifouling coating layer 160, it may be difficult to secure dispersibility, and when it is added in excess of 45% by weight, the content of the antifouling agent is relatively reduced, There may be difficulties in securing the function.

The antifouling agent is used to prevent adhesion of contaminants and to facilitate removal of adhered contaminants. As the antifouling agent, fluorine-containing alkyl compounds, fluorine-containing alkanols, fluorine-containing silane coupling agents, and fluorine-containing silicon compounds may be used.

The antifouling agent is preferably added in a content ratio of 5 to 15% by weight of the total weight of the antifouling coating layer 160 . It is more preferably added in a content ratio of 8 to 12% by weight. If the amount of the antifouling agent added is less than 5% by weight of the total weight of the antifouling coating layer 160, the antifouling function cannot be implemented, and if it exceeds 15% by weight, durability may be deteriorated.

Slip agent is an organic or inorganic particle in which fine particles are uniformly distributed. It is applied uniformly to a coating film to form fine projections to show a high water contact angle, and to improve surface properties such as slip, abrasion resistance, and scratch resistance. used As such a slip agent, copolymers of olefin-based, silicone-based, fluorine-based and fluorine-containing olefins, urethane, and acrylic may be used.

The slip agent is preferably added in a content ratio of 0.5 to 3.0% by weight of the total weight of the antifouling coating layer 160. It is more preferably added in a content ratio of 1.0 to 2.5% by weight.

If the amount of the slip agent added is less than 0.5% by weight of the total weight of the antifouling coating layer 160, the slip properties, abrasion resistance, and scratch resistance are not improved, and if it exceeds 3.0% by weight, the viscosity increases and the fluidity decreases, so that the interparticle material There is a problem that aggregation occurs and dispersibility is lowered.

Urethane oligomer containing a fluorine component is used to improve adhesion and enhance durability of a coating film, specifically containing a polyurethane component composed of a dicarboxylic acid component, a glycol component, and a diisocyanate component, and an OH group and a COOH group. It is prepared by copolymerizing a polyester component to

Each component of the urethane oligomer containing a fluorine component is generally used in the field and is not particularly limited, but specifically, when a copolymer of a urethane component and an ester component in a weight ratio of 1: 1 is used, adhesion and durability are improved. found to be the most desirable.

The urethane oligomer containing such a fluorine component is preferably added in an amount of 20 to 60% by weight of the total weight of the antifouling coating layer 160 . When the amount of the urethane oligomer containing fluorine is less than 20% by weight of the total weight of the antifouling coating layer 160, durability cannot be realized, and when it is added in excess of 60% by weight, the antifouling function is deteriorated.

The antifouling coating layer 160 preferably has a thickness of 50 to 1,000 nm, and a thickness of 300 to 500 nm may be presented as a more preferable range. When the thickness of the antifouling coating layer 160 is too thin, less than 50 nm, it is difficult to exhibit the antifouling function properly, and when the thickness of the antifouling coating layer 160 is formed too thick, exceeding 1,000 nm, there is a problem of reducing strength.

In addition, the antifouling coating layer 160 may further include one or more of 0.1 to 2.0 wt % of polytrimethyltriphenyl cyclosiloxane and 0.1 to 1.5 wt % of 4-hydroxymethylcyclohexylmethyl acrylate.

Polytrimethyltriphenyl cyclosiloxane is added to the antifouling coating layer 160 to improve strength without reducing elongation. If the amount of the polytrimethyltriphenyl cyclosiloxane added is less than 0.1% by weight of the total weight of the antifouling coating layer 160, the amount of the added amount is insignificant and it is difficult to exhibit the strength improvement effect properly, and if it exceeds 2.0% by weight and is excessively added, the strength is improved. Although the effect is insignificant, there is a risk of a rapid decrease in elongation.

4-hydroxymethylcyclohexylmethylacrylate is added to the antifouling coating layer 160 to improve wettability. When the amount of 4-hydroxymethylcyclohexylmethylacrylate added is less than 0.1% by weight of the total weight of the antifouling coating layer 160, the amount of 4-hydroxymethylcyclohexylmethylacrylate added is insignificant, and it may be difficult to secure slip properties, and excessive addition exceeds 1.5% by weight. If it does, there is a problem of lowering the strength.

As described above, the nanofiber composite yarn for high-strength wig yarn using the electrospinning method according to the embodiment of the present invention is used to prepare nanofiber yarn using the electrospinning method, and then the yarn is plied in a twist form using a conventional twisting machine. Since it is possible to manufacture the sheath-core type composite yarn, it is possible to use ready-made equipment as it is, thereby reducing manufacturing cost and improving handling, mass productivity and uniformity.

In addition, the nanofiber composite yarn for high-strength wig yarn using the electrospinning method according to an embodiment of the invention uses a polyester resin as a main component as a core part, and along the outer circumferential surface of the screening nanofiber yarns plied in a twist form as a sheath By using it as a part, not only can it have excellent mechanical properties and curling properties, but also it is possible to secure excellent stain resistance by coating the surface of the nanofiber yarn with an antifouling coating composition.

Hereinafter, a method for manufacturing nanofiber composite yarns for high-strength wig yarns using an electrospinning method according to an embodiment of the present invention will be described with reference to the accompanying drawings.

3 is a process flow chart showing a method for manufacturing nanofiber composite yarns for high-strength wig raw materials using an electrospinning method according to an embodiment of the present invention.

As shown in FIG. 3, the manufacturing method of high-strength wig yarn nanofiber composite yarn using the electrospinning method according to an embodiment of the present invention includes an electrospinning step (S110), a laminating step (S120), a slitting step (S130), coating A step S140 and a plying and twisting step S150 are included.

electrospinning step

In the electrospinning step (S110), a polymer resin is dissolved in a solvent to form a spinning solution, and then the spinning solution is spun by an electrospinning method to form a polymer nanofiber web.

As such, in the electrospinning step (S110), the polymer resin is dissolved in a solvent to prepare a spinning solution at a concentration capable of spinning, and then the spinning solution is spun using an electrospinning device to form a polymer nanofiber web.

This spinning solution preferably contains 20 to 60% by weight of the polymer resin and 40 to 80% by weight of the solvent. If the amount of the polymer resin added is less than 20% by weight of the total weight of the spinning solution, it is difficult to form a membrane by being sprayed onto beads rather than forming nanofibers, and if it exceeds 60% by weight, the viscosity of the spinning solution is too high to prevent spinning It may be difficult to form nanofibers due to poor quality. Therefore, it is preferable to control the morphology of the fiber by setting the spinning solution to a concentration that facilitates the formation of a fibrous structure.

The polymer resin includes at least one selected from a thermoplastic polymer resin and a thermosetting polymer resin. More preferably, the polymer resin is PVdF (polyvinylidene fluoride), nylon (nylon), nitrocellulose (nitrocellulose), PU (polyurethane), PC (polycarbonate), PS (polystryene), PAN (polyacrylonitrile), PEI (polyethyleneimine), PPI (polypropyleneimine), PMMA (Polymethylmethacrylate), PVC (polyvinylcholride), PVAc (polyvinylacetate), PVC (poly vinyl chloride), PVA (poly vinyl alcohol), and PVP (poly vinyl pyrrolidone).

In addition, the solvent is dimethylformamide (DMF), dimethylacetamide (DMAc), THF (tetrahydrofuran), acetone (Acetone), alcohol (Alcohol), chloroform (Chloroform), DMSO ( At least one selected from dimethyl sulfoxide, dichloromethane, acetic acid, formic acid, NMP (N-Methylpyrrolidone), fluorine-based alcohols, and water may be used, but is not limited thereto.

In this step, electrospinning is preferably performed at a voltage of 10 to 20 kV and an interval of 3 to 10 cm. When the electrospinning voltage is less than 10 kV, it may be difficult to form a uniform film, and when the electrospinning voltage exceeds 20 kV, it may act as a factor in using excessive energy without any further effect. In addition, when the electrospinning interval is less than 3 cm, there is a concern that the membrane properties of the polymer nanofiber web may not be good, and when the electrospinning interval exceeds 10 cm, there is a concern that a homogeneous membrane may not be secured.

laminating step

In the laminating step (S120), a polymer membrane is formed by laminating the polymer nanofiber web.

In this laminating step (S120), the polymer nanofiber web is laminated by one or more methods selected from compression, rolling, thermal bonding, ultrasonic bonding, etc. to form a polymer membrane to have a basis weight of 5 to 90 gsm. In this way, laminating may be defined as a process of forming a polymer nanofiber web into a film by fixing the spun individual fibers by means of compression, rolling, thermal bonding, ultrasonic bonding, etc. so that they do not move independently.

At this time, the basis weight is defined as the amount of radiation per unit area of the polymer. If the basis weight of such a polymer membrane is less than 5 gsm, there is a high probability of occurrence of defects during handling or slitting, and if it exceeds 90 gsm, the manufacturing cost increases, so it is not economical.

slitting step

In the slitting step (S130), nanofiber yarns are formed by slitting the polymer membrane.

In this slitting step (S130), the polymer membrane is slit to have a width of 0.5 to 10 mm using a cutter or slitter to form nanofiber yarn. If the width of the nanofiber yarn is less than 0.5 mm, it is difficult to cut smoothly using a slitter because the width is too small, and the probability of thread breakage increases when tension and twist are applied. In (S150), the probability of non-uniform twisting increases.

coating step

In the coating step (S140), the antifouling coating composition is coated on the surface of the nanofiber yarn and then dried to form an antifouling coating layer.

Here, the antifouling coating layer includes a urethane oligomer containing 20 to 45% by weight of a binder resin, 5 to 15% by weight of an antifouling agent, 0.5 to 3.0% by weight of a slip agent, and the remaining fluorine component.

In addition, the antifouling coating layer has a thickness of 50 to 1,000 nm, more preferably 300 to 500 nm. When the thickness of the antifouling coating layer is too thin, less than 50 nm, it is difficult to exhibit the antifouling function properly, and when the thickness of the antifouling coating layer is formed too thick, exceeding 1,000 nm, there is a problem of reducing strength.

In addition, the antifouling coating layer may further include at least one of 0.1 to 2.0% by weight of polytrimethyltriphenyl cyclosiloxane and 0.1 to 1.5% by weight of 4-hydroxymethylcyclohexylmethylacrylate.

As the coating, one or more methods selected from spin coating, spray coating, roll coating, and comma coating may be used, but the present invention is not limited to these methods. In addition, drying is preferably carried out at 70 ~ 90 ℃ for 1 ~ 20 hours. If the drying temperature is less than 70℃ or the drying time is less than 1 hour, sufficient drying may not be achieved, resulting in difficulties in securing strength. If the drying temperature exceeds 90℃ or the drying time exceeds 20 hours, It is not economical because it can act as a factor that increases only the manufacturing cost without further increasing the effect.

Plying and twisting stages

In the plying and twisting step (S150), nanofiber composite yarns are formed by plying and twisting nanofiber yarns having an antifouling coating layer formed thereon.

Here, the screening includes 15 to 35% by weight of the flame retardant, 0.01 to 3.0% by weight of the heat stabilizer, 0.1 to 2.0% by weight of the process stabilizer, 3 to 10% by weight of the strength reinforcing agent, and the rest of the polyester resin.

Strength enhancers are added to enhance strength. The strength reinforcing agent includes at least one selected from among talc, alumina, calcium carbonate, magnesium carbonate, magnesia, calcium silicate, glass fiber, titanium oxide, and antimony oxide.

The strength reinforcing agent preferably has an average diameter of 0.1 to 5 μm. When the average diameter of the strength reinforcing agent is less than 0.1 μm, the particle size is refined and the dispersibility of the particles is not uniform, which can cause uneven strength. When the average diameter of the strength reinforcing agent exceeds 5 μm, physical properties such as heat resistance may be lowered

At this time, the polyester resin includes a high-viscosity PET (polyethylene terephthalate) resin having an intrinsic viscosity of 0.75 to 0.90 and a low-viscosity PET resin having an intrinsic viscosity of 0.50 to 0.60, but based on 100 parts by weight of the high-viscosity PET resin, 10 to 30 parts by weight of the low-viscosity PET resin It is desirable to include wealth.

In this plying and twisting step (S150), it is preferable to apply a tension of 10 to 50 g to the nanofiber yarn, and apply a non-armored force to the plying and twisting. When plying and twisting are performed by applying a tension of less than 10g to the nanofiber yarn, the probability of partial protrusion of the screening yarn increases, resulting in friction between the heald and the body during weaving or friction between the knitting needle and the weaving needle during weaving. And there is a possibility of a rapid decrease in knitting efficiency, and when a tension exceeding 50 g is applied, it may cause yarn breakage during plying, which is undesirable.

As a method of applying tension to the nanofiber yarn, tension may be applied by passing the nanofiber yarn between the up disc tensioner and the down disc tensioner. In addition, when plying, it is possible to perform the process of screening the armed force and winding the nanofiber yarns to which the tension of 10 to 50g is applied to a separate bobbin and then twisting them. After that, the twisting process may be performed continuously.

The high-strength wig fiber nanofiber composite yarn of the present invention prepared by the above-described method has a core-sheath type structure including a core constituting the core portion and a nanofiber yarn having an antifouling coating layer constituting the sheath portion.

As a result, when the high-strength wig yarn nanofiber composite yarn produced by the method according to the embodiment of the present invention has a fineness of 50 denier (de), it exhibits a strength of 3.20 to 3.90 g / de and an elongation of 68 to 75%. In addition, the nanofiber composite yarn for high-strength wig fibers prepared by the method according to an embodiment of the present invention has excellent curl forming properties and excellent curl retention properties.

In the above-described method for manufacturing nanofiber composite yarn for wig yarn using the electrospinning method according to the embodiment of the present invention, nanofiber yarn is prepared using the electrospinning method, and then the yarn is plied in a twist form using a conventional twisting machine to form a sheath. -Since it is possible to manufacture core-type composite yarn, it is possible to use ready-made equipment as it is, thereby reducing manufacturing cost and improving handling, mass productivity, and uniformity.

In addition, the manufacturing method of high-strength wig raw nanofiber composite yarn using the electrospinning method according to an embodiment of the present invention uses a polyester resin as a main component as a core part, and nanofibers plied in a twist form along the outer circumferential surface of the screening material. By using the yarn as the sheath portion, not only can it have excellent mechanical properties and curling properties, but also it is possible to secure excellent stain resistance by coating the surface of the nanofiber yarn with an antifouling coating composition.

Example

Hereinafter, the configuration and operation of the present invention will be described in more detail through preferred embodiments of the present invention. However, this is presented as a preferred example of the present invention and cannot be construed as limiting the present invention by this in any sense.

Contents not described herein can be technically inferred by those skilled in the art, so descriptions thereof will be omitted.

1. Manufacture of nanofiber composite yarn for wig yarn

Example 1

After preparing a spinning solution by dissolving 50 g of PVdF (polyvinylidene fluoride) in 100 ml of acetone, the spinning solution was electrospun under conditions of a spinning voltage of 17 kV and a spinning interval of 7 cm at 30 ° C to prepare a polymer nanofiber web.

Next, a polymer membrane was prepared by laminating the polymer nanofiber web at a pressure of 90 g/cm 2 using a roller heated to 100° C.

Next, nanofiber yarns were prepared by slitting the polymer membrane to a width of 3 mm using a slitter.

Next, the antifouling coating composition was spray-coated on the surface of the nanofiber yarn and dried at 85° C. for 8 hours to form an antifouling coating layer having a thickness of 300 nm. At this time, the antifouling coating composition used a urethane oligomer containing 33% by weight of a polyimide resin, 14% by weight of a fluorine-containing alkyl compound, 1.5% by weight of a slip agent (trade name: BYK-333, BYK), and the remaining amount of fluorine. . At this time, as the urethane oligomer containing a fluorine component, a copolymer obtained by copolymerizing a urethane component and an ester component at a weight ratio of 1:1 was used.

Next, the nanofiber composite yarn for wig yarn was prepared by plying and twisting the nanofiber yarn on which the antifouling coating layer was formed.

At this time, the screening is a flame retardant, 25% by weight of polybromoepoxy (Mw = 70,000, about 67.8% by weight of bromine content) composed of a polymer of brominated bisphenol A diglycidyl ether and brominated bisphenol A, a heat stabilizer (trade name: Iganox 1010 ) 1.5% by weight, 0.7% by weight of a process stabilizer (trade name: Stutukt 065), 4% by weight of alumina (Al ₂ O ₃ ) having an average diameter of 3.0 μm as a strength reinforcing agent, and a balance of polyester resin were used. In addition, a polyester resin containing 30 parts by weight of a low-viscosity PET resin having an intrinsic viscosity (IV) of 0.58 with respect to 100 parts by weight of a high-viscosity PET resin having an intrinsic viscosity (IV) of 0.78 was used.

Example 2

A nanofiber composite yarn for wig yarn was prepared in the same manner as in Example 1, except that electrospinning was performed under conditions of a radiation voltage of 15 kV and a radiation interval of 8 cm.

Example 3

A nanofiber composite yarn for wig yarn was prepared in the same manner as in Example 1, except that the nanofiber yarn was prepared by slitting the polymer membrane to a width of 5 mm using a slitter.

Example 4

A nanofiber composite yarn for wig origin was prepared in the same manner as in Example 1, except that the polymer membrane was prepared by laminating the polymer nanofiber web at a pressure of 100 g / cm 2 using a roller heated to 110 ° C. .

Example 5

The polyester resin includes 25 parts by weight of a low-viscosity PET resin having an intrinsic viscosity (IV) of 0.58 and 7 parts by weight of PCTG (polycyclohexylene dimethylene terephthalate) based on 100 parts by weight of a high-viscosity PET resin having an intrinsic viscosity (IV) of 0.78. A nanofiber composite yarn for a wig source was prepared in the same manner as in Example 1, except for that.

Example 6

As a flame retardant, brominated bisphenol A diglycidyl ether and polybromoepoxy composed of a polymer of brominated bisphenol A (Mw = 70,000, bromine content of about 67.8% by weight) 25% by weight, heat stabilizer (trade name: Iganox 1010) 1.5 % by weight, 0.7% by weight of process stabilizer (trade name: Stutukt 065), 6% by weight of alumina (Al ₂ O ₃ ) with an average diameter of 3.5 μm as a strength reinforcing agent, and the remaining amount of polyester resin. In the same manner as in Example 1, a nanofiber composite yarn for wig yarn was prepared.

Example 7

A nanofiber composite yarn for wig origin was prepared in the same manner as in Example 4, except that a second master batch chip to which 8% by weight of calcium carbonate (CaCO ₃ ) having an average diameter of 1.5 μm was added as a strength reinforcing agent was prepared.

Example 8

Antifouling coating composition 35% by weight of polyimide resin, 12% by weight of fluorine-containing alkyl compound, 2.0% by weight of slip agent (trade name: BYK-333, BYK), 1.0% by weight of polytrimethyltriphenyl cyclosiloxane and the remaining fluorine component A nanofiber composite yarn for a wig source was prepared in the same manner as in Example 1, except that a urethane oligomer containing a was used.

Example 9

Antifouling coating composition 33% by weight of polyimide resin, 14% by weight of fluorine-containing alkyl compound, 1.5% by weight of slip agent (trade name: BYK-333, BYK), 0.5% by weight of polytrimethyltriphenyl cyclosiloxane and 4-hydroxymethyl A nanofiber composite yarn for a wig source was prepared in the same manner as in Example 1, except for using a urethane oligomer containing 0.7% by weight of cyclohexylmethyl acrylate and the remaining amount of fluorine.

Comparative Example 1

After preparing a spinning solution by dissolving 50 g of PVdF (polyvinylidene fluoride) in 100 ml of acetone, the spinning solution was electrospun under conditions of a spinning voltage of 17 kV and a spinning interval of 7 cm at 30 ° C to prepare a polymer nanofiber web.

Next, a polymer membrane was prepared by laminating the polymer nanofiber web at a pressure of 90 g/cm 2 using a roller heated to 100° C.

Next, nanofiber yarns were prepared by slitting the polymer membrane to a width of 3 mm using a slitter.

Next, nanofiber composite yarn for wig source was prepared by plying and twisting the nanofiber yarn in the screening.

At this time, the screening is a flame retardant, 25% by weight of polybromoepoxy (Mw = 70,000, about 67.8% by weight of bromine content) composed of a polymer of brominated bisphenol A diglycidyl ether and brominated bisphenol A, a heat stabilizer (trade name: Iganox 1010 ) 1.5% by weight, process stabilizer (trade name: Stutukt 065) 0.7% by weight and the balance of polyester resin were used. In addition, a polyester resin containing 30 parts by weight of a low-viscosity PET resin having an intrinsic viscosity (IV) of 0.58 with respect to 100 parts by weight of a high-viscosity PET resin having an intrinsic viscosity (IV) of 0.78 was used.

Comparative Example 2

A nanofiber composite yarn for wig yarn was prepared in the same manner as in Comparative Example 1, except that electrospinning was performed under conditions of a radiation voltage of 16 kV and a radiation interval of 6 cm.

Comparative Example 3

A nanofiber composite yarn for wig origin was prepared in the same manner as in Comparative Example 1, except that a polymer membrane was prepared by laminating the polymer nanofiber web at a pressure of 100 g / cm 2 using a roller heated to 110 ° C. .

2. Property evaluation

Tables 1 and 2 show the results of evaluating the physical properties of nanofiber composite yarns for wig origin prepared according to Examples 1 to 9 and Comparative Examples 1 to 3.

1) Strength and Religion

It was measured using an automatic tensile tester (Textechno) at a speed of 50 cm/min and a gripping distance of 50 cm. Strength and elongation are the value (g/de) obtained by dividing the load applied to the fiber by the denier when it is stretched until it is cut by applying a certain force to the fiber (g/de), and the value expressed as a percentage of the initial length relative to the elongated length (%). ) was defined as Shindo.

2) Curl formation and curl retention

For curl formation, a bundle of 40,000 denier (160 strands × 50 denier × 5 strands) of bundled wig yarn is cut to a length of 30 cm, fixed in a clamp, wound with an electric curling iron heated to 200 ℃ 5 times, and then held for 5 seconds. Then, the curling iron was removed and the curl state immediately after curling was evaluated. This was based on the curling length of the wig yarn prepared with 100 parts by weight of natural hair. (◎: When the curling length of artificial wigs made of natural hair is the same, ○: 1 ~ 2 cm stretched compared to standard, △: 3 ~ 4 cm stretched compared to standard, ×: 5 cm or more stretched compared to standard)

Curl retention was evaluated after repeating 10 times of washing and drying the wig yarn used in the evaluation of curl formation with cold water, and then maintaining the formed curl. (◎: Very good curl retention, ○: Excellent curl retention, △: Fair, ×: Loose curl)

3) Long-term heat resistance (min): Oxidation initiation time was measured at 200 ° C using OIT (Oxygen induced time).

4) contact angle

The water contact angle was measured using Phoenix 300 (SEO Co.).

5) Fouling resistance

The visual inspection level was evaluated when writing or erasing with an oil pen (Monami's blue color pen). At this time, stain resistance was evaluated based on writing/erasing. (◎: Excellent, ○: Excellent, △: Normal, ×: Poor)

6) Number of delegations

During the manufacturing process through plying and twisting, the number of thread breaks occurring during 24 hours was counted and measured.

division Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 Intensity (g/de) 3.36 3.35 3.37 3.42 3.51 3.52 Confidence (%) 72.4 71.7 72.2 71.6 71.5 70.3 curl formation ◎ ◎ ○ ◎ ◎ ◎ curl retention ◎ ◎ ◎ ○ ◎ ◎ Long-term heat resistance (min) 105 104 107 108 106 106 contact angle 106 107 108 107 106 109 stain resistance ◎/◎ ◎/○ ◎/◎ ○/◎ ◎/◎ Number of delegations (times/24 hours) 0 One 0 One 0 0

division Example 7 Example 8 Example 9 Comparative Example 1 Comparative Example 2 Comparative Example 3 Intensity (g/de) 3.56 3.62 3.67 2.79 2.81 3.10 Confidence (%) 70.1 69.8 69.3 71.8 67.3 66.8 curl formation ◎ ◎ ◎ △ △ × curl retention ◎ ◎ ◎ △ × △ Long-term heat resistance (min) 105 107 108 97 99 96 contact angle 112 114 115 93 91 89 stain resistance ◎/◎ ◎/◎ ◎/◎ △/X △/△ X/Δ Number of delegations (times/24 hours) 0 0 0 3 4 5

As shown in Tables 1 and 2, the nanofiber composite yarn for wig origin according to Examples 1 to 9 has excellent mechanical properties satisfying strength of 3.20 to 3.90 g/de and elongation of 68 to 75%, while having curl forming properties. And curl retention was excellent, and long-term heat resistance was excellent, and the number of trimmings was measured less than once, confirming that productivity was excellent.

On the other hand, compared to Examples 1 to 9, the nanofiber composite yarn for wig origin according to Comparative Examples 1 to 3 has low strength, poor curl formation, curl retention and long-term heat resistance, and the number of trimmings is measured at 3 or more times. It was confirmed that productivity was not good.

In addition, the nanofiber composite yarn for wig origin according to Examples 1 to 9 had a contact angle measured as high as 104 ° or more, whereas the nanofiber composite yarn for wig yarn according to Comparative Examples 1 to 3 had a contact angle measured as low as 93 ° or less. can confirm that In particular, it can be seen that the contact angle of the nanofiber composite yarn for wig yarn according to Example 9 was measured at 115 °, which is the composite addition of polytrimethyltriphenyl cyclosiloxane and 4-hydroxymethylcyclohexylmethylacrylate. It is judged to be caused by

In addition, the nanofiber composite yarn for wig origin according to Examples 1 to 9 is due to the formation of an antifouling coating layer, and compared to the other nanofiber composite yarn for wig origin in Comparative Examples 1 to 3, the antifouling performance for contaminants is significantly improved. was able to confirm that

Although the embodiments and comparative examples of the present invention have been described in detail as described above, the scope of the present invention is not limited thereto, and the scope of the present invention extends to those within the scope substantially equivalent to the embodiments of the present invention. .

100: Nanofiber composite yarn for wig yarn
120: screening 140: nano fiber yarn
160: antifouling coating layer S110: electrospinning step
S120: Laminating step S130: Slitting step
S140: coating step S150: plying and twisting step

Claims (10)

(a) forming a spinning solution by dissolving a polymer resin in a solvent, and then spinning the spinning solution by electrospinning to form a polymer nanofiber web;
(b) forming a polymer membrane by laminating the nanofiber web;
(c) forming nanofiber yarns by slitting the polymer membrane;
(d) coating an antifouling coating composition on the surface of the nanofiber yarn and then drying to form an antifouling coating layer;
(e) forming a nanofiber composite yarn by plying and twisting the nanofiber yarn on which the antifouling coating layer is formed;
Method for manufacturing high-strength wig yarn nanofiber composite yarn using electrospinning, characterized in that it comprises a. According to claim 1,
In step (a),
The polymer resin is
A method for manufacturing high-strength wig yarn nanofiber composite yarn using an electrospinning method, characterized in that it comprises at least one selected from a thermoplastic polymer resin and a thermosetting polymer resin. According to claim 1,
In step (c),
The nanofiber yarn
Method for manufacturing high-strength wig yarn nanofiber composite yarn using electrospinning, characterized in that it has an average diameter of 10 ~ 300nm. According to claim 1,
In step (e),
The screening is high strength using electrospinning, characterized in that it comprises 15 to 35% by weight of flame retardant, 0.01 to 3.0% by weight of heat stabilizer, 0.1 to 2.0% by weight of process stabilizer, 3 to 10% by weight of strength reinforcing agent and the rest of the polyester resin. Manufacturing method of nanofiber composite yarn for wig yarn. According to claim 4,
The strength enhancer includes at least one selected from talc, alumina, calcium carbonate, magnesium carbonate, magnesia, calcium silicate, glass fiber, titanium oxide, and antimony oxide,
The strength enhancer is a high-strength wig yarn nanofiber composite yarn manufacturing method using an electrospinning method, characterized in that it has an average diameter of 0.1 ~ 5㎛. According to claim 1,
In step (e),
A method for producing high-strength wig yarn nanofiber composite yarn using an electrospinning method, characterized in that applying a tension of 10 to 50g to the nanofiber yarn, and applying an armed force to the screening for plying and twisting. As a nanofiber composite yarn for high-strength wig yarn using electrospinning,
judge;
Nanofiber yarns plied in a twist form along the outer circumferential surface of the screening; and
Including; antifouling coating layer formed to cover the surface of the nanofiber yarn,
The screening includes 15 to 35% by weight of flame retardant, 0.01 to 3.0% by weight of heat stabilizer, 0.1 to 2.0% by weight of process stabilizer, 3 to 10% by weight of strength reinforcing agent and the rest polyester resin,
The nanofiber yarn is a high-strength wig fiber composite yarn using an electrospinning method, characterized in that it comprises at least one selected from a thermoplastic polymer resin and a thermosetting polymer resin. According to claim 7,
The nanofiber yarn
Nanofiber composite yarn for high-strength wig yarn using electrospinning, characterized in that it has an average diameter of 5 ~ 300nm. According to claim 7,
The strength enhancer includes at least one selected from talc, alumina, calcium carbonate, magnesium carbonate, magnesia, calcium silicate, glass fiber, titanium oxide, and antimony oxide,
The strength enhancer is a high-strength wig fiber composite yarn using an electrospinning method, characterized in that it has an average diameter of 0.1 ~ 5㎛. According to claim 7,
The antifouling coating layer includes a urethane oligomer containing 20 to 45% by weight of a binder resin, 5 to 15% by weight of an antifouling agent, 0.5 to 3.0% by weight of a slip agent and the remaining fluorine component,
The antifouling coating layer is a nanofiber composite yarn for high-strength wig yarn using an electrospinning method, characterized in that it has a thickness of 50 ~ 1,000nm.

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