KR20220007550A - Fiber-based Functional Material - Google Patents

Abstract

The present invention relates to a fiber-based functional composite material that can be effectively used for electrical stimulation garments or electrical stimulation devices. A fiber-based functional composite material according to the present invention includes: a substrate including fibers; and a conductive layer disposed on the substrate and including a conductive rod.

Description

Fiber-based Functional Material

The present invention relates to a fiber-based functional material (composite material), and in detail, it is elastic and deformable, and its electrical properties are stably maintained even when repeatedly deformed, and it is washable and a fiber-based functionality that can apply uniform electrical stimulation. It's about composites.

The human body maintains a voltage of -30~-25mV, and weak bioelectricity of about 40~60㎂ flows through signal transmission between organs. Recently, by applying electric stimulation of similar strength to bioelectricity, effects such as wrinkle improvement, wound and fracture healing promotion, muscle fatigue improvement, inflammation improvement, blood circulation improvement, cell regeneration promotion, and abdominal fat reduction have been proven.

In order to apply electrical stimulation to a living body in the form of an electrical stimulation device or clothing, or to detect a signal generated in the human body, an electrode (hereinafter referred to as a contact electrode) capable of delivering electrical stimulation by contact with the skin is essential. Conventional contact electrodes usually have the form of a metal thin film, and the contact electrodes in the metal thin film form are partially lifted when in contact with the skin, making it difficult to uniformly apply electrical stimulation, as well as difficult to adhere and fix due to lack of elasticity and binding force. There is a problem that it is difficult to use in the dark skin area.

In order to solve this problem, a device or clothing that generates electrical stimulation is attached to an electrode or wetted in water to secure a uniform application of electrical stimulation and a constant binding force. There was an attempt.

However, in the case of hydrogel, it is easy to be contaminated due to its inherent adhesiveness and has sanitary problems, so it must be replaced with a new hydrogel when the number of uses increases or users change. As the electrode is damaged by washing as well as limited time and excessive movement, only simple volatilization drying is possible, causing sanitary problems such as odor generation.

Republic of Korea Patent Publication No. 10-2020-0067637

It is an object of the present invention to provide a fiber-based functional composite that can be effectively used for electrical stimulation devices or clothes that generate electrical stimulation and apply to animals including humans.

One specific object of the present invention is to provide a fiber-based functional composite to which electrical stimulation can be uniformly applied.

Another specific object of the present invention is to provide a fiber-based functional composite material having excellent adhesion and elasticity, and in which electrical stimulation can be uniformly applied even to a curved area.

Another specific object of the present invention is to provide a fiber-based functional composite material that is stably maintained in electrical properties and can be washed by conventional mechanical washing.

Another specific object of the present invention is to provide a fiber-based functional composite material in which electrical properties are stably maintained despite repeated physical deformation.

Another specific object of the present invention is that a separate element (eg, hydrogel, etc.) for uniform electrical stimulation delivery and separate pretreatment such as wetting are unnecessary, and when electrical stimulation is delivered, it is used in direct contact with the skin It is to provide a possible fiber-based functional composite.

A fiber-based functional composite according to an aspect of the present invention includes: a substrate including fibers; and a conductive layer positioned on the substrate and including a conductive rod.

A fiber-based functional composite according to another aspect of the present invention includes a substrate that is a fiber layer; and a conductive layer that contains anisotropic particles that are conductors and is bound to the substrate, and satisfies the physical properties of Equation 1 after the deformation test under the following conditions.

Strain test conditions: 10 to 100% of the area ratio of the substrate covered with the conductive layer, 120% unidirectional stretching deformation, 20 repetitions of deformation, 50 times of stretching deformation/min.

(Equation 1)

80 ≤ Rst/R0 x 100

R0 is the line resistance of the conductive layer before the strain test, and Rst is the line resistance of the conductive layer after the strain test.

In one embodiment of another aspect of the present invention, the anisotropic particle may include a conductive rod.

In one embodiment according to the present invention, the line resistance of the conductive layer may be 5 MΩ/cm or less.

In one embodiment according to the present invention, the conductive rod is a metal rod, a conductive polymer rod, a core-shell rod comprising a core of a first conductive material- a shell of a second conductive material, a shell of a non-conductive core-conductive material It may include a core-shell rod comprising a, hollow hollow rod, or a mixture thereof.

In one embodiment according to the present invention, the conductive rod may have a unimodal, bimodal or trimodal distribution in terms of size distribution converted to spheres of the same volume.

In one embodiment according to the present invention, the long axis length of the conductive rod may be 500 nm to 15 μm.

In one embodiment according to the present invention, the aspect ratio of the conductive rod may be 20 to 80.

In one embodiment according to the present invention, the conductive layer may include a network of conductive rods.

In one embodiment according to the present invention, the thickness of the conductive layer may be 0.1 μm to 500 μm.

In one embodiment according to the present invention, the conductive layer may further include a conductive structure selected from the group consisting of conductive particles, conductive plates, conductive fibers, and conductive tubes.

In one embodiment according to the present invention, the conductive layer may further contain a binder.

In one embodiment according to the present invention, the mass ratio of the conductive component to the binder component of the conductive layer may be 1: 0.5 to 2.5.

In one embodiment according to the present invention, the binder may include a urethane resin, a vinyl chloride resin, an acrylic resin, a cellulose resin, a phenol resin, or a mixture thereof.

In one embodiment according to the present invention, a second binder layer positioned between the conductive layer and the substrate may be further included.

In one embodiment according to the present invention, a portion of the conductive component of the conductive layer may be fixed to the second binder layer.

The functional composite material according to an embodiment according to the present invention may further include an upper conductive layer positioned on the lower conductive layer and the conductive layer as a lower conductive layer.

In one embodiment according to the present invention, the upper conductive layer may have a coefficient of friction of 1.5 or more.

In one embodiment according to the present invention, the upper conductive layer may include a dotted conductive material.

In one embodiment according to the present invention, the dotted conductive material of the upper conductive layer may include a carbon-based conductive material.

In one embodiment according to the present invention, the carbon-based conductive material may include carbon black.

In one embodiment according to the present invention, the dotted conductive material may further include a metal conductive material.

In one embodiment according to the present invention, the mass ratio of the carbon-based conductive material: the metal conductive material may be 1.0: 0.5 to 2.0.

In one embodiment according to the present invention, the upper conductive layer may further include a third binder, and the mass ratio of the dotted conductive material of the upper conductive layer to the third binder may be 1.0: 0.5 to 2.5.

In one embodiment according to the present invention, the conductive layer may be a patterned conductive layer.

In one embodiment according to the present invention, the fiber-based functional composite may include two or more conductive layers spaced apart from each other.

In one embodiment according to the present invention, the fibers of the substrate may include natural fibers, synthetic fibers, or a combination thereof.

In one embodiment according to the present invention, the natural fibers include one or more fibers selected from plant fibers, animal fibers and mineral fibers, and the synthetic fibers include nylon fibers, polyester fibers, acrylonitrile fibers, and polyvinyl fibers. It may include one or more fibers selected from alcohol fibers, polyvinyl chloride fibers, polyurethane fibers, rayon fibers, tencel fibers, modal fibers, blends thereof, and combinations thereof.

In one embodiment according to the present invention, the substrate may include a woven or nonwoven fabric of fibers.

In one embodiment according to the present invention, the substrate may be a stretchable fabric (fabric).

In one embodiment according to the present invention, the fiber-based functional composite material may be a fabric for electrical stimulation clothing, electrical stimulation device, or biosignal detection sensor.

The present invention includes the above-described fiber-based functional composite, and includes a device in which the conductive layer side of the fiber-based functional composite is in contact with animals including humans.

The present invention is a fiber-based functional composite as described above; and an electrical stimulation device including a; and an electrical signal generator electrically connected to the conductive layer of the fiber-based functional composite and generating an electrical signal.

The present invention includes the above-described fiber-based functional composite, wherein the substrate of the fiber-based functional composite is in a form that can be worn or worn by animals including humans, and the conductive layer of the fiber-based functional composite includes animals including humans of the substrate and It includes a covering located on the contacting side.

The present invention includes the above-described fiber-based functional composite, wherein the substrate of the fiber-based functional composite is in a form that can be worn or worn by animals including humans, and the conductive layer of the fiber-based functional composite is in contact with animals including humans of the substrate It includes an electrical stimulation garment comprising a; located on the side, electrically connected to the conductive layer and an electrical signal generator for generating an electrical signal.

The fiber-based functional composite according to the present invention has a conductive layer by a network of conductive rods on a substrate containing fibers, so that the conductive layer can apply electrical stimulation very uniformly, and electrical conductivity is stably It is maintained, the conductivity is not lowered when stretched and deformed, can be mechanically washed, etc., and exhibits excellent electrical properties even with a very thin layer, so that the inherent flexibility of the fiber-based substrate is not impaired.

Hereinafter, the fiber-based functional composite of the present invention will be described in detail. The drawings presented below may be exaggerated to clarify the spirit of the present invention. At this time, unless there are other definitions in the technical terms and scientific terms used, it has a meaning commonly understood by a person of ordinary skill in the art to which this invention belongs, and in the following description, it may unnecessarily obscure the subject matter of the present invention. A description of possible known functions and configurations will be omitted.

Also, the singular forms used in the specification and appended claims may also be intended to include the plural forms unless the context specifically dictates otherwise.

In this specification and the appended claims, terms such as first, second, etc. are used for the purpose of distinguishing one element from another, not in a limiting sense.

In this specification and the appended claims, terms such as include or have means that a feature or element described in the specification is present, and unless specifically limited, one or more other features or elements are added. This is not to rule out the possibility in advance.

In this specification and the appended claims, when a part of a film (layer), region, component, etc. is on or on another part, not only when it is directly on the other part in contact with it, but also another film ( layer), other regions, and other components are also included.

As a result of long-term research to form a flexible and deformable electrode directly on a fiber-based substrate, particularly a fiber-based substrate with elasticity, the present applicant has conducted a long-term study to form a network of conductive rods on the substrate. Overall, it was confirmed that electrical stimulation (electric field or current) was applied very uniformly, and furthermore, the electrical conductivity was stably maintained despite repeated stretching and deformation, and the conductive network was not substantially damaged even during physical treatment such as mechanical washing. , found that the inherent flexibility of the fiber-based substrate was maintained. In addition, it was found that, when a conductive network is formed with a conductive rod, even when a large amount of a hydrophilic binder is present, a current passage is formed stably and uniformly, so that a conductive surface formed by the conductive rod can have an appropriate binding force.

A fiber-based functional composite according to an aspect of the present invention based on the above findings includes: a substrate including fibers; and a conductive layer positioned on the substrate and including a conductive rod.

A fiber-based functional composite according to another aspect of the present invention based on the above-mentioned findings includes: a substrate which is a fiber layer; and a conductive layer that contains anisotropic particles that are conductors and is bound to the substrate, and satisfies the physical properties of Equation 1 after the deformation test under the following conditions.

Strain test conditions: 10 to 100% of the area ratio of the substrate covered with the conductive layer, 120% unidirectional stretching deformation, 20 repetitions of deformation, 50 times of stretching deformation/min.

(Equation 1)

80 ≤ Rst/R0 x 100

R0 is the line resistance of the conductive layer before the strain test, and Rst is the line resistance of the conductive layer after the strain test.

In this case, Rst/R0 x 100 may be 80 or more, 82 or more, 84 or more, 86 or more, 88 or more, 90 or more, 92 or more, 94 or more, or 96 or more, and may be substantially 100 or less. Rst and R0 may be average values of line resistances randomly measured 5 or more, 10 or more, 15 or more, or 20 or more times in each conductive layer before/after the test. When measuring the line resistance, the distance between the probes may be 0.5 cm to 10 cm, but is not limited thereto. The size of the test sample (the size of a substrate having conductive layers) is that an area of 1cm ² to be 1000cm ² levels, but not limited to these.

The anisotropic particle may mean a rectangular particle elongated in one direction, and the rectangular particle may have a uniform or non-uniform cross-sectional area in the elongated direction. For example, not only a rod shape having a uniform cross-sectional area in the elongated direction, but also a rice grain or needle shape having an uneven cross-sectional area may also belong to the rectangular particle. Anisotropic particles should be distinguished from irregularly shaped simple particles (non-anisotropic particles) or fiber or wire-type particles, and in the present invention, the anisotropic particles have an aspect ratio of 20 to 80 or less (20 to 80) , substantially 20 or more, 25 or more, or 30 or more, and 80 or less, 75 or less, 70 or less, 65 or less, 60 or less, 55 or less, 50 or less, or 45 or less. As a specific example, the anisotropic particle that is a conductor may be a conductive rod.

Hereinafter, the following description may correspond to each of all aspects, unless specifically limited to one aspect. Also, the substrate containing fibers may correspond to a substrate or fabric that is a fibrous layer.

In one embodiment, the aspect ratio (average aspect ratio=average length/average diameter) of the conductive rod or the anisotropic particle may be 20 to 80. Specifically, in terms of the formation of a large number of contact points due to the high aspect ratio, the aspect ratio may be 20 or more, and it maintains a stable bond state despite repeated stretching and physical shocks such as washing and prevents deterioration of electrical properties. In terms of aspect ratio, the aspect ratio may be 80 or less. In practical examples, the aspect ratio of the conductive rod or anisotropic particle is 20 to 75, 25 to 75, 30 to 75, 20 to 70, 25 to 70, 30 to 70, 20 to 65, 25 to 65, 30 to 65, 20 to 60 , 25 to 60, 30 to 60, 20 to 55, 25 to 55, 30 to 55, 20 to 50, 25 to 50, 30 to 50, 20 to 45, 25 to 45 or 30 to 45.

The major axis length (average length) of the conductive rod or anisotropic particle is 0.05FD to 100FD, specifically 0.05FD to 10FD, 0.05FD to 5FD, 0.05FD to 3FD, 0.05 based on the diameter (FD) of the fiber contained in the substrate. FD to 2FD, 0.05FD to 1.5FD, 0.05FD to 1.0FD, 0.05FD to 0.8FD, 0.05FD to 0.6FD, 0.1FD to 10FD, 0.1FD to 5FD, 0.1FD to 3FD, 0.1FD to 2FD, 0.1FD to 1.5FD, 0.1FD to 1.0FD, 0.1FD to 0.8FD, 0.1FD to 0.6FD, 0.3FD to 10FD, 0.3FD to 5FD, 0.3FD to 3FD, 0.3FD to 2FD, 0.3FD to 1.5FD, 0.3FD to 1.0FD, 0.3FD to 0.8FD, 0.3FD to 0.6FD, 0.5FD to 10FD, 0.5FD to 5FD, 0.5FD to 3FD, 0.5FD to 2FD, 0.5FD to 1.5FD, 0.5FD to 1.0FD, 0.5FD to 0.8FD, 0.5FD to 0.6FD, 0.7FD to 10FD, 0.7FD to 5FD, 0.7FD to 3FD, 0.7FD to 2FD, 0.7FD to 1.5FD, 0.7FD to 1.0FD, 0.9FD to 10FD, 0.9FD to 5FD, 0.9FD to 3FD, 0.9FD to 2FD, 0.9FD to 1.5FD, 1FD to 10FD, 1FD to 5FD, 1FD to 3FD, 1FD to 2FD, or 1FD to 1.5FD, but is not necessarily limited thereto. However, when the length of the conductive rod is 1FD or less, electrical property damage may hardly occur even in a state in which the base material containing the fiber is stretched and deformed, and substantially, the length of the conductive rod is 1FD or less, specifically 0.8FD, or 0.6 In the case of FD or less, the electrical properties of the conductive layer in the stretched and deformed state of the substrate may be improved than before the deformation. In this case, the reference fiber (fiber) may mean a fiber of water used for weft, warp, yarn, etc. when weaving or knitting.

In one embodiment, the major axis length (average major axis length) of the conductive rod or anisotropic particle may be 500 nm to 15 μm, specifically 500 nm or more, 600 nm or more, 700 nm or more, 800 nm or more, 900 nm or more, 1 μm or more, 1.5 μm or more, 2 μm or more. and specifically 15 μm or less, 14 μm or less, 13 μm or less, 12 μm or less, 11 or less, 10 μm or less, 9 μm or less, 8 μm or less, 7 μm or less, 6 μm or less, 5 μm or less, or 4 μm or less.

Conductive rods having such a long axis length and aspect ratio are in contact with each other and form a continuous current movement path (network formation), so that an electrical stimulus (electric field or current) can be applied very uniformly to the entire conductive layer, and from the front surface of the conductive layer A uniform electrical stimulation may be applied to have a feeling of use (uniformity of electrical stimulation, sensation felt on the skin upon electrical stimulation) substantially equivalent to that when the hydrogel is attached.

In addition, since the conductive rods having such a long axis length and aspect ratio are in contact with each other and form a continuous current movement path (network formation), the conductive rod (anisotropic particle) does not permeate into the substrate containing the fiber even through a simple application process. A conductive network can be stably formed on the surface of the substrate.

In addition, since conductive rods having such a long axis length and aspect ratio are in contact with each other and form a continuous current movement path (network formation), electrical conductivity is stably maintained despite repeated stretching deformation, even during physical treatment such as mechanical washing The conductive network is not substantially damaged, and a very thin conductive layer is implemented, so that the flexibility inherent in the fiber-based substrate may not be impaired even in the region where the conductive layer is located.

As a result of additional experiments, when a network is formed by conductive wires (including conductive nanowires) or conductive tubes (including conductive nanotubes), a tingling pain can be felt during actual use due to the non-uniform electrical stimulation of the conductive layer. can In addition, when a network is formed of conductive nanowires or conductive tubes, a partial and random decrease in electrical conductivity occurs during repeated stretching and deformation, and this stinging pain may intensify. Furthermore, when the network is formed of conductive nanowires or conductive tubes, the conductive layer deteriorates during physical treatment such as machine washing, and thus there is a limitation in that it is practically impossible to wash. In addition, when a network is formed using simple conductive particles, a large amount of conductive particles permeate into the fiber-based substrate, and it is difficult to implement a thin conductive layer that does not impair the inherent flexibility of the substrate. Even if the conductive layer is formed on the stretchable substrate, it is difficult to use in the stretched state due to the large deterioration of the properties. In addition, when a conductive network is formed by a conductive plate (plate and/or flake), non-uniform electrical stimulation is applied like a network of wires or tubes, and electrical properties are severely damaged during stretching and deformation, even in the presence of a large amount of binder. There is a problem of poor adhesion. Furthermore, even when a network is formed by using a wire, a nanotube, a plate, a particle, etc. in combination, these problems still exist.

In the fiber-based functional composite according to the present invention, the conductive layer includes a network of conductive rods in which the conductive rods are in contact with each other and form a continuous current path in a random direction. While the conductive layer includes such a conductive rod network, if necessary, additional conductive layers include conductive particles, conductive plates, conductive fibers (including conductive wires and nanowires) and conductive tubes (including nanotubes, for example, CNTs) ) may further include one or more conductive structures selected from the group. At this time, the additional inclusion means that the conductive layer is further included in a state in which a stable current movement path is already formed in the conductive layer by the conductive rod, and even if there is no conductive structure, the conductive layer is 5 MΩ/cm or less by the conductive rod, Specifically, 3 MΩ/cm or less, 1MΩ/cm or less, 5KΩ/cm or less, 1KΩ/cm or less, 500 Ω/cm or less, 100Ω/cm or less, 90Ω/cm or less, 80Ω/cm or less, 70Ω/cm or less, It may mean that a line resistance (average line resistance) of 60 Ω/cm or less, 50 Ω/cm or less, 40 Ω/cm or less, 30 Ω/cm or less, and 25 Ω/cm or less is exhibited. When the conductive structure is further included together with the conductive rod, the amount of the conductive structure may be 0.01 to 0.1 parts by weight based on 1 part by weight of the conductive rod, but is not limited thereto.

In one embodiment, the line resistance of the conductive layer is 5 MΩ/cm or less, specifically, 3 MΩ/cm or less, 1 MΩ/cm or less, 5KΩ/cm or less, 1KΩ/cm or less, 500 Ω/cm or less, 100 Ω/cm or less, 90 Ω/cm or less, 80 Ω/cm or less, 70 Ω/cm or less, 60 Ω/cm or less, 50 Ω/cm or less, 40 Ω/cm or less, 30 Ω/cm or less, 25 Ω/cm or less, 20 Ω/cm It may be 15 Ω/cm or less, or 10 Ω/cm or less, and substantially, 0.1 Ω/cm or more, 0.5 Ω/cm or more, or 1.0 Ω/cm or more. The line resistance of the conductive layer may be an average value of line resistances randomly measured 5 or more times, 10 or more times, 15 or more times, or 20 or more times. When measuring the line resistance, the distance between the probes may be 0.5 cm to 10 cm, but is not limited thereto. The above-described line resistance of the conductive layer may be the line resistance when the conductive layer has no other conductive component other than the conductive rod network. That is, even if the conductive layer according to the present invention includes a conductive component other than the conductive rod, the basic conduction in the plane direction of the substrate may be due to the conductive rod network.

In one embodiment, the conductive rod is a metal rod, a conductive polymer rod, a core-shell rod comprising a shell of a first conductive material- a core-shell rod comprising a shell of a second conductive material, a core-shell comprising a shell of a non-conductive core-conductive material rods, hollow hollow rods, or mixtures thereof. In terms of excellent conductivity and low contact resistance inherent in the material, the conductive rod is a metal rod, a core of a first conductive material- a core-shell rod of a metal shell, a non-conductive core- a core-shell rod comprising a metal shell, a hollow hollow It is advantageous to be a metallic rod such as a type metal rod or a mixture thereof, but is not necessarily limited thereto. The metal of the metallic rod may be any metal known to be safe when in contact with the skin of animals, including the human body, and the bio-stability has been confirmed when in contact with the skin, such as copper, gold, silver, platinum, stainless steel, and aluminum. Practically, the metallic rod may include, but is not limited to, a copper rod or a silver rod.

In one embodiment, the conductive rod contained in the conductive layer may have a unimodal, bimodal, or trimodal distribution in terms of size distribution converted to spheres of the same volume. Advantageously, the unimodal, bimodal or trimodal distribution may comprise a distribution with a first conductive rod having an aspect ratio of 20 to 80 and a major axis length (average major axis length) of 500 nm to 15 μm. Further, the conductive layer may include a conductive network with a first conductive rod having an aspect ratio of 20 to 80 and a major axis length of 500 nm to 15 μm, and additionally a conductive rod having an average major axis length different from the first conductive rod (by It may further include a second conductive rod in the case of a modal, and second and third conductive rods in the case of a trimodal).

In one embodiment, the conductive rod contained in the conductive layer may be a water-soluble polymer, a surfactant, or a surface-modified state by a water-soluble polymer and a surfactant. The surface modification of the conductive rod may be due to an additive used in the liquid phase synthesis method of the conductive rod, such as a polyol method, or otherwise, may be due to surface modification of a manufactured or purchased conductive rod. The water-soluble polymer may be polyvinylpyrrolidone, polyvinylalcohol, polyarylamide, polyacrylic acid, and copolymers thereof, and the surfactant is an anionic surfactant, cationic It may be one or more substances selected from an amphoteric surfactant and an amphoteric surfactant. The anionic surfactant is sodium laureth sulfate (Sodium Laureth Sulfate), sodium (C14-C16) olefin sulfonate (Sodium (C14-C16) olefin sulfonate), and at least one from sodium dodecyl benzene sulfonate selected substances, and the cationic surfactant is an ester-containing quaternary ammonium salt (EQ), an amide group and ester group in Quaternary Ammonium salts ), pyridinium derivatives, betaine derivatives, imidazolium derivatives, quinolinium derivatives, piperazinium derivatives, and morpholinium derivatives. and the like, and the amphoteric surfactant is an amine salt, a quaternary ammonium salt, an onium compound, or a mixture thereof, wherein the hydrophilic part contains a primary to tertiary amine, and the quaternary ammonium salt is a nitrogen-containing compound with chain alkyl and It may include a nitrogen-containing heterocyclic compound of a cyclic nitrogen compound as well as a bonded one. In this case, the onium compound may include phosphonium, a sulfonium salt, or a mixture thereof, and the nitrogen-containing heterocyclic compound may include a pyridium salt, quinolium, imidazolium, or a mixture thereof.

In one embodiment, the thickness of the conductive layer is 0.1 μm to 500 μm, specifically 0.5 μm to 500 μm, 1 μm to 500 μm, 5 μm to 500 μm, 10 μm to 500 μm, 20 to 400 μm, 20 to 300 μm, 20 to 200 μm, 20 to 150 μm, 30 to 150 μm, 40 to 150 μm, 50 to 150 μm, 60 to 150 μm, 70 to 150 μm, or 80 to 130 μm. Due to the thickness of the conductive layer, electrical properties may be stably maintained even when stretched and deformed, and the inherent flexibility of the fiber-based substrate may not be impaired.

In one embodiment, the conductive layer may further include a binder together with the conductive rod or anisotropic particles. The binder may serve to bind the conductive rods and between the conductive rods and the fiber-based substrate to each other. The binder may be an organic binder, the organic binder may be a polymeric binder, and the polymeric binder may be a water-soluble binder or a non-water-soluble binder. Water-soluble binders are environmentally friendly, safer and more economical, enabling the manufacture of fiber-based functional composites, making them more commercial. As an example of the binder, polyvinylidene fluoride, polyvinylpyrrolidone, polyacrylonitrile, polymethyl methacrylate, polyethylene oxide, polyimide, polyvinyl alcohol, polyvinylpyrrolidone, polyethylene, polypropylene, fluorine rubber, styrene-butadiene rubber, styrene-acrylic rubber, acrylated styrene-butadiene rubber, and the like. , preferably a rubber-based binder such as acrylated styrene-butadiene rubber. The weight average molecular weight of the polymer binder may be at a level of 50,000 to 500,000 g/mol, and may be in the form of an emulsion, but is not limited thereto.

The mass ratio of the conductive component of the conductive layer: the binder component may be 1: 0.5 to 2.5, but is not necessarily limited thereto. In this case, the conductive component refers to all of the conductor components contained in the conductive layer, and may include anisotropic particles that are conductive rods or conductors.

In one embodiment, the fiber-based functional composite may further include a second binder layer positioned between the conductive layer and the substrate. The second binder may form an interface layer between the conductive layer and the substrate. The binder layer (second binder layer) located at the interface between the conductive layer and the substrate enables the formation of a thinner conductive layer, and the binder layer (second binder layer) allows the conductive layer and the substrate to have a stronger binding force. can be combined In addition, a part of the conductive rod contained in the conductive layer is fixed to the second binder (second binder layer), and the fixed conductive rods extend above the interface between the conductive layer and the substrate when the fiber-based functional composite is stretch-deformed. Electrical properties can be more stably maintained during stretching and deformation by providing electrical nodes. The second binder may be an organic binder, the organic binder may be a polymer binder, the polymer binder may be a water-soluble binder or a non-water-soluble binder, and may be the same as or different from the binder of the lower conductive layer. However, in terms of stronger bonding between the conductive layer and the substrate, the third binder and the binder (first binder) of the conductive layer may be the same material.

In one embodiment, the fiber-based functional composite material may further include an upper conductive layer positioned on the lower conductive layer by using the aforementioned conductive layer as a lower conductive layer. That is, the fiber-based functional composite includes a substrate including fibers; a lower conductive layer positioned on the substrate and including a conductive rod; and an upper conductive layer positioned on the lower conductive layer.

When the fiber-based functional composite comes into contact with animals, including humans, even if the lower conductive layer contains non-anisotropic particles along with conductive rods (anisotropic particles), there is a limit in increasing the friction coefficient due to the anisotropic shape. . However, in order to apply electrical stimulation or detect biological information by contacting the skin of animals including humans, stable and unchanging contact between the conductive layer and the skin must be maintained not only in daily movements but also in extreme movements such as exercise. In particular, when detecting biometric information, a change or movement of the contact state of the conductive layer immediately causes an increase in noise. The upper conductive layer is to supplement the disadvantages of the lower conductive layer and to maintain a fixed and stable contact with the contact surface including the skin. The upper conductive layer may have a friction coefficient of 1.5 or more, and advantageously 2.0 or more, 2.5 or more or greater, 3.0 or greater, 3.5 or greater, 3.6 or greater, 3.7 or greater, 3.8 or greater, 3.9 or greater, 4.0 or greater, 4.1 or greater, 4.2 or greater, 4.3 or greater, 4.4 or greater, or 4.5 or greater, and substantially less than or equal to 7.0, or It may have a friction coefficient of 6.0 or less. In this case, the friction coefficient means a static (static) coefficient of friction.

The above-described coefficient of friction may be implemented by the upper conductive layer using a point-shaped conductive material, advantageously a carbon-based dotted conductive material, and most advantageously, a carbon-based dotted conductive material having a very high specific surface area and an irregular agglomerated shape.

Since the upper conductive layer contains the dotted conductive material as a conductive component, it can serve to provide a path of conduction (thickness direction conduction path) together with the lower conductive layer and increase the friction coefficient. In this case, the dotted conductive material means a particulate conductive material, and the particulate conductive material may be in the form of spherical or polyhedral particles, irregularly shaped particles, or an agglomerate in which primary particles are irregularly aggregated.

In detail, the upper conductive layer may include a carbon-based conductive material (carbon-based dot-type conductive material) as the dotted conductive material. The carbon-based conductive material can increase the coefficient of friction when it comes into contact with animals, including humans, and can lower the contact resistance between the conductive layer (upper conductive layer and lower conductive layer) and the contact object by creating a large number of contact points. It does not impair the flexibility and elasticity of the fiber-based functional composite, uniformly forms a large number of contact points on the surface, and by the increased friction coefficient, the previously-contacted fiber-based functional composite can stably and In terms of maintaining contact, it is preferable that the carbon-based conductive material be light and conductive carbon black having a very large specific surface area and irregular agglomeration shape. Examples of the conductive carbon black include, but are not limited to, acetylene black, Ketjen black, channel black, furnace black, lamp black, summer black, or a mixture thereof. Conductive carbon black is an ^{agglomerate having a diameter of 10 0} to 10 ^{1 nanometer level, for example, about 10 0} to 10 ¹ micrometer level in which carbon particles having a diameter of 10 to 30 nm are irregularly aggregated, specifically about 5 to 30 μm. form, but is not necessarily limited thereto.

In an advantageous example, the upper conductive layer may further include a metal conductive material (metal dotted conductive material) together with the carbon-based conductive material as the dotted conductive material. The metal conductive material is for a stable electrical connection between the upper conductive layer and the lower conductive layer. When the upper conductive layer contains only a carbon-based conductive material as a dotted conductive material, a relatively large amount of dotted conductive material is located near the surface of the upper conductive layer rather than near the interface between the upper conductive layer and the lower conductive layer, and the conductive layer (upper conductive layer and There is a risk that the resistance in the thickness direction of the lower conductive layer) will increase. When the upper conductive layer further contains the metal conductive material together with the carbon-based conductive material as the dotted conductive material, the increase in resistance in the thickness direction can be prevented by the metal conductive material located in a larger amount relatively near the interface. The metal of the metal conductive material can be any metal known to be safe when in contact with the skin of animals, including the human body, and metals with bio-stability when in contact with the skin include copper, gold, silver, platinum, stainless steel, aluminum, etc. Practically, it may be a copper particle or a silver particle, but is not necessarily limited thereto. However, when the conductive rod is a metal in terms of resistance reduction, it is preferable that the metal of the metal conductive material and the metal of the conductive rod be the same type of metal. As described above, in terms of stable electrical connection between the lower conductive layer and the surface layer, the metal conductive material is preferably in the form of coarse particles rather than nanoparticles, as a practical example, particles having an average diameter of 0.5 μm to 5.0 μm, as a more practical example, It may be particles having an average diameter of 1.0 to 3.0 μm, but is not necessarily limited thereto.

In one embodiment, the conductive component in the upper conductive layer may be made of a dotted conductive material, and the dotted conductive material may be made of a carbon-based conductive material and a metal conductive material. That is, the upper conductive layer does not contain a material having an anisotropic shape such as nanorods, nanoplates, nanoribbons, nanowires, nanotubes, etc., and may be composed of a conductive component and a binding component, and the conductive component is a dotted conductive material. can be done

In one embodiment, the mass ratio of the carbon-based conductive material contained in the upper conductive layer to the metal conductive material is 1.0: 0.5 to 2.0, specifically 1.0: 1.0 to 2.0, but is not limited thereto.

In one embodiment, the upper conductive layer may further contain a third binder together with the dotted conductive material. The third binder may serve to bind between the dotted conductive material and between the dotted conductive material and the lower conductive layer.

The third binder may be an organic binder, the organic binder may be a polymer binder, and the polymer binder may be a water-soluble binder or a non-water-soluble binder. Specifically, as an example of the third binder, polyvinylidene fluoride, polyvinylpyrrolidone, polyacrylonitrile, polymethyl methacrylate, polyethylene oxide, polyimide, polyvinyl alcohol, polyvinylpyrrolidone, polyethylene , polypropylene, fluororubber, styrene-butadiene rubber, styrene-acrylic rubber, acrylated styrene-butadiene rubber, etc., and fluororubber, styrene-butadiene rubber to maintain more stable binding when the base material is stretched and deformed. , styrene-acrylic rubber, acrylated styrene-butadiene rubber, etc. is preferably a rubber-based binder. When the binder is a rubber-based binder, the binder may be in the form of an emulsion. The third binder may be of the same material or a different material as that of the first binder, and may be of the same material as the first binder in terms of improving interlayer bonding between the lower conductive layer and the upper conductive layer.

In one embodiment, in the upper conductive layer, the mass ratio of the dotted conductive material: the third binder may be 1.0: 0.5 to 2.5, specifically 1.0: 0.7 to 1.8, but is not necessarily limited thereto. In this case, the mass of the point-shaped conductive material may be the total mass of the carbon-based conductive material and the mass of the metal conductive material.

In one embodiment, the thickness of the upper conductive layer may be 0.2T _LC to 2T _LC , specifically 0.5T _LC to 1.5T _{LC , with the thickness of the lower conductive layer being T LC} , but is not limited thereto.

In one embodiment, a conductive layer may be positioned on one surface or one surface of the substrate and each of the opposite surfaces. The conductive layer may partially or entirely cover one surface of the substrate. The conductive layer may include a lower conductive layer and an upper conductive layer. In the conductive layer, the upper conductive layer may cover part or all of the lower conductive layer, and may have a shape substantially corresponding to the lower conductive layer.

In one embodiment, the conductive layer may be a patterned conductive layer. That is, the overall shape of the substrate and the overall shape of the conductive layer may be different from each other, and the conductive layer may be patterned in a shape suitable for the specific use in consideration of the specific use of the fiber-based functional composite. As a practical example, when considering the use of a low-frequency muscle massage device or diet clothes or belly bands through micro-electrical stimulation, the conductive layers are spaced apart from each other by a pre-designed electrode distance, and the first conductive layer has a pre-designed electrode shape and size. and a second conductive layer. In addition, if necessary, a wiring portion for electrical connection between the component generating electrical stimulation and the conductive layer portion serving as an electrode may also be integrally implemented by patterning the conductive layer.

However, when considering the use of a device or coating that applies electrical stimulation or detects biosignals in contact with the skin of animals including the human body, the fiber-based functional composite is composed of two or more conductive layers (first conductive layer, second conductive layer) spaced apart from each other. It is advantageous to include a second conductive layer), and the first conductive layer and the second conductive layer may be located on the same surface or different surfaces of the substrate.

In one embodiment. The fibers of the substrate may include natural fibers, synthetic fibers, or combinations thereof. The natural fibers may include one or more fibers selected from plant fibers, animal fibers and mineral fibers, and the synthetic fibers include nylon fibers, polyester fibers, acrylonitrile fibers, polyvinyl alcohol fibers, polyvinyl chloride fibers, and polyurethanes. It may include one or more fibers selected from fibers, rayon fibers, tencel fibers, modal fibers, blends thereof, and combinations thereof, but is not necessarily limited thereto. Practically, synthetic fibers include polyvinyl acetate (PVAc), polyvinylpyrrolidone (PVP), polyvinyl alcohol (PVA), polyethylene oxide (PEO), polymethyl methacrylate (PMMA), polyacrylic acid (PAA), Polycarbonate (PC), poly(m-phenylene isophthalamide) (PMIA), polyethylamine (PEI), PET, polytrimethylene tetraphthalate (PTT), polybutylene tetraphthalate (PBT), polysulfone (PSF), poly(etheretherketone) (PEEK), polystyrene (PS), polyvinylidene fluoride (PVDF), polyurethane, poly(vinyl butyral)resin (PVB), polyvinyl ester (PVE), PFDMS (polyferrocenyldimethylsilane), polyimide, poly{(pyrrole-2,5-diyl)[p-nitrobenylidene]}(PPy), polyoxymethylene (POM), PEI (polyethyleneimine), polyacrylamine (PAM), polyethylene glycol (PEG), PLLA/PDLA ( polylactides), polycaprolactone (PCL), polyglycolic acid (PGA), PHA (poly-β-hydroxyalkanoates), poly(butylene succinate) (PBS), poly(ether urethane urea) (PEUU), polyvinyl chloride (PVC) ), artificial regenerated cellulose (rayon), or a mixture thereof. In addition, natural fibers may include plant fibers such as cotton and flax, animal fibers such as silk (silk) and wool, and mineral fibers such as asbestos. The fibers may be microfibers or ordinary fibers having a small diameter. Specifically, the thickness (diameter) of the fiber substrate may be 0.1 to 50 μm, specifically, an ultrafine fiber thickness of 0.1 to 4 μm, a microfine fiber thickness of 3 to 10 μm, or a general fiber thickness of 10 to 50 μm. it is not going to be

In one embodiment, the substrate may include a woven, knitted or non-woven fabric of fibers, and the fabric may include a plain weave, a yarn weave, a main weave, a twill weave, a three-dimensional weaving or knitting form, etc. In addition, the knitted fabric may include a warp knitted fabric including a weft knitted fabric, a tricord or a raschel, and the nonwoven fabric may include a felt, but the present invention is not limited by the spherical weave type of the substrate. As a practical example, the substrate may be a stretch fabric (including stretch fabric) used for clothing such as yoga clothes or leggings.

In one embodiment, the fiber-based functional composite material may be a fabric for electrical stimulation clothing, electrical stimulation device, or biosignal detection sensor.

The present invention includes a device comprising the fiber-based functional composite as described above.

Specifically, the device includes a fiber-based functional composite, the conductive layer side of the fiber-based functional composite may be a device in contact with animals, including humans, and the device detects an electrical stimulation application device or a biosignal of an animal, including a human. It may be a device (including a sensor) that

The present invention is a fiber-based functional composite as described above; and an electrical stimulation device comprising a; and an electrical signal generator electrically connected to the conductive layer of the fiber-based functional composite and generating an electrical signal. In this case, the electrical signal generated from the electrical signal generator may be a low frequency to a medium frequency. The electrical stimulation device includes a low-frequency muscle massage device.

The present invention includes a coating comprising the above-described fiber-based functional composite.

The coating according to the present invention includes a fiber-based functional composite, the substrate of the fiber-based functional composite is in a form that can be worn or worn by animals including humans, and the conductive layer of the fiber-based functional composite is in contact with animals including humans of the substrate. located on the side

The present invention includes the above-described fiber-based functional composite, wherein the substrate of the fiber-based functional composite is in a form that can be worn or worn by animals including humans, and the conductive layer of the fiber-based functional composite is the side that comes into contact with animals, including humans, of the substrate. Located in, electrically connected to the conductive layer, an electrical signal generator for generating an electrical signal; includes an electrical stimulation coating comprising. In this case, the electrical signal generated from the electrical signal generator may be a low frequency to a medium frequency. Specific examples of the coating include electrical stimulation leggings.

The present invention includes clothing including the above-described fiber-based functional composite material. In detail, the clothing according to the present invention includes a fabric that can be worn or worn by animals including humans; and a fiber-based functional composite positioned or fixed to the inner side of the fabric (the side facing animals, including humans).

In the present invention, clothing or clothing includes not only underwear, bottoms, tops, etc., but also fabric-based articles that can be worn by animals, including humans, such as hats, protectors (including bellybands), scarves, gloves, wrist bends, etc. should be interpreted

The present invention includes a method for manufacturing a fiber-based functional composite.

The fiber-based functional composite according to the present invention comprises the steps of: a) forming a coating film by applying a mixture containing a conductive rod, a binder and a solvent on a substrate including fibers; and b) drying the coating film to form a conductive layer.

The mass ratio of the conductive rod and the binder in the mixture may be 1 (conductive rod): 0.5 to 2.5 (binder), but is not necessarily limited thereto.

In the mixture, the solvent may dissolve the binder and may be any solvent in which the conductive rod is easily dispersed. Specifically, the solvent is methanol, ethanol, isopropyl alcohol, butanol, 1-methoxypropanol, ethylhexyl alcohol, terpineol, 2-methoxyethanol, 2-ethoxyethanol, 1-methoxy-2-propanol Alcohol-based (including alkoxy alcohol-based) solvents such as; ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, methyl propyl ketone, cyclohexanone, dimethylformamide, and 1-methyl-2-pyrrolidone; Propylene glycol monopropyl ether, propylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethyl glycol monoethyl ether, diethyl glycol monopropyl ether , ether solvents such as diethyl glycol monobutyl ether, diethylene glycol-2-ethylhexyl ether, methyl cellosolve, butyl cellosolve, hexyl cellosolve, diethyl ether, tetrahydrofuran, and dioxane; carbitol-based solvents such as 2-(2-alkoxyethoxy)ethanol-based compounds (wherein the alkoxy group is derived from ethyl, methyl, propyl or butyl); cellosolve solvents such as 2-alkoxyethoxyethanol-based compounds (wherein the alkoxy group is derived from methyl, ethyl, butyl, and hexyl); acetate-based solvents such as ethyl acetate, butyl acetate, methoxypropyl acetate, carbitol acetate, and ethyl carbitol acetate; glycol solvents such as ethylene glycol and glycerin; hydrocarbon solvents such as hexane, heptane, dodecane, paraffin oil, and mineral spirits; halogen-substituted solvents such as chloroform, methylene chloride, and carbon tetrachloride; aromatic solvents such as benzene, toluene, and xylene; water (distilled water); or a mixed solvent thereof, but is not limited thereto. For example, when preparing a mixture with an aqueous solvent having process safety and economy, various water-miscible solvents such as lower alkanols, diols, other polyols, ethers, and amines may be used together with or instead of water. . Examples of water-miscible solvents include ethanol, propanol, isopropanol, 2-methyl pyrrolidinone, benzyl alcohol, ethers and diethers having 4 to 14 carbon atoms, glycols, alkoxylated glycols, alkoxylated aromatic alcohols, aromatic alcohols, aliphatic side chains alcohols, alkoxylated aliphatic branched alcohols, alkoxylated straight chain C1-5 alcohols, straight chain C1-5 alcohols, C8-14 alkyl and cycloalkyl hydrocarbons, C6-16 glycol ethers, carbitol (eg, 2-(2-butoxy ethoxy) ethanol (butyl carbitol, methyl carbitol, hexyl carbitol, etc.), cellosolve (methyl cellosolve, butyl cellosolve, hexyl cellosolve, etc.) or mixtures thereof no. However, in terms of improving the dispersibility of the conductive rod in the mixture, the solvent of the mixture may include an auxiliary solvent for improving dispersibility such as carbitol, cellosolve, or a mixture thereof, and when the mixture contains an auxiliary solvent , the mixture may contain an auxiliary solvent in an amount of 20 to 70 parts by weight based on 100 parts by weight of the conductive rod, but is not necessarily limited thereto.

The mixture may contain 1 to 90 parts by weight, more specifically 1 to 70 parts by weight, and still more specifically 1 to 50 parts by weight of the conductive rod, based on 100 parts by weight of the solvent, but is not limited thereto, and is not limited thereto. Of course, it can be appropriately adjusted in consideration of

Of course, the step of homogeneously mixing the mixture before application of the mixture may be further performed, and of course, an ultrasonic disperser, a stirrer, a ball mill, a three-roll mill, etc. Mixing may be performed, but is not limited thereto.

For the purpose of increasing dispersion stability, and/or preventing agglomeration or settling, and/or adjusting printing properties such as viscosity or volatility, the mixture may, if necessary, contain stabilizers, dispersants, surfactants, etc. , wetting agent (wetting agent), leveling agent (leveling agent), cross-linking agent (cross-linking agent) and / or thickening agent (thickening agent), such as conventional additives, etc. may further contain one or more kinds, but the present invention Of course, it cannot be limited by the presence or absence or the specific type of the additive.

Drying of the coating film may be heat drying or non-heat drying (room temperature drying). In this case, gas including air may be blown during drying without heating. When drying by heat, the drying temperature may be 80 to 140 °C, specifically 100 to 130 °C. Drying may be performed by applying Joule heat during heating and drying, applying hot air, or irradiating a heat-ray such as near-infrared (NIR), but the present invention is not limited by a spherical heat source during heating and drying. . In addition, it is sufficient if the drying is performed for a time during which the solvent of the coating film can be sufficiently removed by volatilization, for example, may be performed for 10 minutes to 5 hours, but is not limited thereto.

In one embodiment, the method for manufacturing a fiber-based functional composite includes the steps of: a) before step, I) applying a solution (binder solution) containing a binder (second binder) of the same or different type as the binder contained in the mixture ; may be further included. The binder of the binder solution may be an aqueous (water-soluble) binder, and the solvent of the binder solution may be an alcohol-based (including alkoxy alcohol-based) solvent independently of the solvent of the mixture; ketone solvents; etheric solvents; acetate-based solvents; glycol-based solvents; hydrocarbon-based solvents; halogen-substituted solvents; aromatic solvents; water (distilled water); Or it may be a mixed solvent thereof, and the like, and the binder solution may contain 30 to 70% by weight of the binder, but is not limited thereto.

When the binder solution is applied, drying may be performed in step I), or the coating film formed in step I) may be dried simultaneously with the coating film of step a) when drying in step b). When the conductive rod contained in the mixture is intended to form a partially fixed structure on the second binder layer, it is preferable to dry the coating film formed in step I) at the same time as the coating film in step a) when drying step b). When drying is performed in step I), drying in step I) may be heating or non-heating drying (room temperature drying), and heat drying is performed at 80 to 140° C., specifically 100 to 130° C. for 5 minutes to 3 hours. It may be carried out during the period, but is not limited thereto.

The application of the mixture or application of the binder solution is spin coating, roll coating, spray coating, dip coating, flow coating, doctor blade, dispensing, inkjet Printing, offset printing, screen printing, pad printing, gravure printing, reverse gravure printing, gravure offset printing, flexography printing, stencil printing, imprinting, xerography, slot die coating , but may be performed by one or more methods selected from bar coating and roll-to-roll coating, but is not limited thereto.

After step b) is performed, the manufacturing method according to one embodiment uses the conductive layer prepared in step b) as a lower conductive layer, and forming an upper conductive layer on the lower conductive layer (step (c)); may include more.

According to an advantageous example, step c) may include applying and drying an upper mixture containing a dotted conductive material, a third binder, and a solvent on the lower conductive layer.

In the upper mixture, the mass ratio of the point-shaped conductive material and the third binder may be 1.0 (point-shaped conductive material): 0.5 to 2.5 (third binder), specifically 1.0: 0.7 to 1.8, but is not necessarily limited thereto.

In the upper mixture, the solvent can dissolve the third binder, and any solvent in which the dotted conductive material is easily dispersed may be used. In an embodiment, the solvent is an alcohol-based (including alkoxy alcohol-based) solvent; ketone solvents; etheric solvents; carbitol-based solvents; cellosolve solvent; acetate-based solvents; glycol-based solvents; hydrocarbon-based solvents; halogen-substituted solvents; aromatic solvents; water (distilled water); or a mixed solvent thereof, but is not limited thereto. Similar to the mixture (submixture) of step a), when preparing a mixture with an aqueous solvent having process safety and economy, with or instead of water, such as lower alkanols, diols, other polyols, ethers, amines, etc. A variety of water-miscible solvents may be used. The water-miscible solvent is similar to or the same as described above with respect to the sub-mixture.

Similar to the sub-mixture, the upper admixture may, if desired, also contain stabilizers, dispersants, surfactants, wetting agents, leveling agents, cross-linking agents and/or thickening agents. agent) may further contain one or more additives commonly used in the field of conductive ink, such as, of course, but the present invention cannot be limited by the presence or absence of additives or specific types of additives.

The lower mixture may contain 1 to 90 parts by weight, more specifically 1 to 70 parts by weight, and even more specifically 1 to 50 parts by weight of the dotted conductive material based on 100 parts by weight of the solvent, but is not limited thereto, and the application method Of course, it can be appropriately adjusted in consideration of the use or use.

Before application of the lower mixture, similarly to the above in the upper mixture, the step of homogeneously mixing the mixture may be further performed, of course, mixing with an ultrasonic disperser, a stirrer, a ball mill, a three-roll mill, etc. when preparing a slurry or ink Mixing may be performed using a device commonly used for the purpose, but is not limited thereto.

Application of the top mixture is spin coating, roll coating, spray coating, dip coating, flow coating, doctor blade, dispensing, inkjet printing, offset printing , screen printing, pad printing, gravure printing, reverse gravure printing, gravure offset printing, flexography printing, stencil printing, imprinting, xerography, slot die coating, bar coating and It may be performed by one or more methods selected from roll-to-roll coating, etc., but is not limited thereto.

Drying of the coating film to which the upper mixture is applied may be heat drying or non-heat drying (room temperature drying) independently of the drying in step a). During non-heat drying, gas including air may be blown, and during heating and drying, the drying temperature may be 60 to 140°C, specifically 70 to 120°C. The drying may be performed by applying Joule heat during heating and drying, applying hot air, or irradiating a heat-ray such as near-infrared (NIR), but is not limited thereto. In addition, it is sufficient if the drying is performed for a time during which the solvent of the coating film can be sufficiently removed by volatilization, for example, may be performed for 10 minutes to 5 hours, but is not limited thereto.

(Example 1)

A mixture containing 34 wt% of Ag rod (average length = 2.5 μm, average aspect ratio = 41), 32 wt% of a styrene-acrylic rubber binder, 21 wt% of butylcarbitol and the remainder of water was applied to one side of the leggings fabric, By drying at 120° C. for 30 minutes, a fiber-based functional composite with a conductive layer having a thickness of 103 μm was prepared.

(Example 2)

A fiber-based functional composite was prepared in the same manner as in Example 1, except that a mixture containing 27 wt% of Ag rod, 45 wt% of a styrene-acrylic rubber binder, 13 wt% of butylcarbitol and the remaining amount of water was used.

(Example 3)

The same procedure as in Example 1 was performed except that, before applying the mixture to the leggings fabric, a styrene-acrylic rubber emulsion was applied, and after applying the same mixture as in Example 1, the binder coating film and the mixture coating film were heated at 120 ° C. A fiber-based functional composite was prepared in which a styrene-acrylic rubber binder layer having a thickness (coating thickness) of 12 μm on the leggings fabric and a conductive layer with a thickness of 91 μm laminated on the binder layer were formed by batch drying for 30 minutes.

(Example 4)

After preparing a conductive layer in the same manner as in Example 1, on the prepared conductive layer (lower conductive layer) ^{, 7.0 wt% of conductive carbon black (specific surface area of about 254 m 2} /g), Ag particles (average diameter of 1.8 μm) A mixture (second mixture) containing 9.8% by weight, 24% by weight of a styrene-acrylic rubber binder, 15% by weight of butylcarbitol and the remaining amount of water was applied and dried at 100° C. for 60 minutes, and the upper conductive layer with a thickness of 92 μm was applied. The formed fiber-based functional composite was prepared.

The wire resistance of the conductive layer of the fabricated fiber-based functional composite was measured using a pocket tester, and the probe interval was 2.5 cm, and the measurement was performed 10 times at random locations on the conductive layer and averaged.

In Examples 1, 2, 3 and 4, the conductive layer formed by binding to the leggings fabric had a smooth surface, and even when the mixture was directly applied to the leggings fabric as in Examples 1 and 2, silver It was confirmed that the rod did not penetrate into the fabric and formed a surface layer on the surface of the fabric. The line resistance of the conductive layer prepared in Example 1 was 2.8 Ω/cm, the line resistance of the conductive layer prepared in Example 2 was 22 Ω/cm, and the line resistance of the conductive layer prepared in Example 3 was 1.6 Ω/cm. cm, and the line resistance of the conductive layer prepared in Example 4 was 350 KΩ/cm.

In addition, a sample cut to have leggings fabric in a width of 2 cm in all directions in the conductive layer (rectangular shape of 4 cm x 6 cm) was subjected to 120% unidirectional stretching deformation at a rate of 50 elastic deformations/min. After 20 repetitions of deformation, the resistance change rate was measured. As a result, all of Examples 1, 2, 3 and 4 maintained a line resistance of 90% or more of resistance immediately after manufacturing, and in particular, Example 3 maintained a line resistance of 97% or more. In addition, as a result of observing the surface of the conductive layer after repeated stretching and deformation testing, it was confirmed that defects such as cracks were not formed in all of the conductive layers prepared in Examples, and the shape was maintained intact without floating or separated parts. did

The functional composite prepared in Example 1 maintained a 120% unidirectional stretched state for 3 hours, and as a result of measuring the wire resistance of the conductive layer in the stretched state, a significant increase in wire resistance was not observed. In the case of the sample prepared in 3, it was confirmed that the wire resistance was rather lowered to 1.1 Ω/cm in the stretched state, and compared to the samples prepared in Examples 1 or 2, the original size was recovered faster when the tension for stretching was removed. confirmed that.

The fiber-based functional composite prepared in Examples 1, 2, and 3 was washed with water for 10 minutes using a washing machine, dehydrated for 3 minutes, and dried at 120 ° C. for 30 minutes as a unit washing process, The washing process was repeated 10 times. As a result of observing the conductive layer through an optical microscope after repeated washing 10 times, it was confirmed that no peeling, damage, or color transfer of the conductive layer occurred. As a result of measuring the line resistance of the sample prepared in Example 1 by the number of repetitions of the unit washing process, a significant increase in resistance did not occur until 4 repetitions, and at 10 repetitions, the line resistance of 2.8 Ω/cm was 4.6 It was confirmed that there was a slight increase in Ω/cm, and the samples prepared in Examples 2 and 3 also showed similar results.

A functional composite was prepared in the same manner as in Examples 1, 2 and 3, except that two conductive layers having a width x width = 4 cm x 6 cm were applied to the leggings fabric to be spaced apart from each other to prepare a functional composite material. Then, by separating only the electrical stimulation generator from a commercial EMS (Electrical Muscle Stimulation) massage device that attaches a hydrogel patch to both electrodes, two conductive layers of a fiber-based functional composite prepared as in Examples 1, 2 or 3 After being electrically connected to each, two conductive layers of a fiber-based functional composite were placed so that the arms were wrapped to operate the electrical stimulation generator. As a result, no skin tingling occurred during operation, and it was confirmed that the feeling of use (degree of stimulation, uniformity of stimulation, etc.) was substantially the same as when using a commercial device with a hydrogel patch attached to both electrodes. In addition, as a result of operating the electrical stimulation generator by forming Velcro on the leggings fabric and fixing the fiber-based functional composite in a one-way stretched state of 120%, it was confirmed that pain such as tingling did not occur in the same way.

The friction coefficient (static friction coefficient) of the fiber-based functional composites prepared in Examples 1 and 4 was measured. The coefficient of friction may be a static friction coefficient under a load of 200 g according to ASTM D-1894. Specifically, according to ASTM D1894, it is applied to the SUS friction material at a speed of 150 mm/min using a universal test machine equipped with a 29N load cell. It was measured under a 200 g load. The coefficient of friction was measured at 25°C and 60% relative humidity. The friction coefficient of the lower conductive layer of Example 1 was measured by preparing a test sample by forming a lower conductive layer (only) with a thickness of about 100 μm on the SUS substrate in the same manner as in Example 1, and the upper conductive layer of Example 4 The friction coefficient of the layer was measured by preparing a test sample by forming an upper conductive layer (only) with a thickness of about 100 μm on a SUS substrate in the same manner as in Example 4. The size of the sample used to measure the friction coefficient was 10 cm x 10 cm.

The coefficient of friction of the functional composite prepared in Example 1 was 1.2, and the coefficient of friction of the functional composite prepared in Example 4 was 4.7.

To measure the skin contact resistance, conductive terminals were provided on the composite material prepared in each example, and the composite material with the terminal was fixed to be in close contact with the wrist. was used to measure resistance. At this time, the distance between the probes was kept constant at 15 cm, and a total of 10 measurements were made for each composite material, and the average value was taken as the human skin contact resistance.

Upon contact between the composite material and the skin, the contact resistance of the functional composite prepared in Example 1, measured by the above-described method, was 412 KΩ, and the contact resistance of the functional composite prepared in Example 4 was 428 KΩ.

As described above, the present invention has been described with specific details and limited examples and drawings, but these are only provided to help a more general understanding of the present invention, and the present invention is not limited to the above embodiments, and the present invention is not limited to the above embodiments. Various modifications and variations are possible from these descriptions by those of ordinary skill in the art.

Therefore, the spirit of the present invention should not be limited to the described embodiments, and not only the claims described below, but also all of the claims and all equivalents or equivalent modifications to the claims will be said to belong to the scope of the spirit of the present invention. .

Claims (33)

a substrate comprising fibers; and
A fiber-based functional composite comprising; a conductive layer disposed on the substrate and including a conductive rod. a substrate that is a fibrous layer; and anisotropic particles that are conductors.
A fiber-based functional composite material that includes, and satisfies the physical properties of Equation 1 after a deformation test under the following conditions.
Deformation test conditions: 10 to 100% of the area ratio of the substrate covered with the conductive layer, 120% unidirectional stretching deformation, 20 repetitions of deformation, 50 times of stretching deformation/min.
(Equation 1)
80 ≤ Rst/R0 x 100
(R0 is the line resistance of the conductive layer before the strain test, and Rst is the line resistance of the conductive layer after the strain test) 3. The method of claim 2,
The anisotropic particle is a fiber-based functional composite including a conductive rod. 4. The method according to any one of claims 1 to 3,
The wire resistance of the conductive layer is 5 MΩ / cm or less of a fiber-based functional composite. 4. The method of claim 1 or 3,
The conductive rod includes a metal rod, a conductive polymer rod, a core-shell rod including a shell of a first conductive material-a shell of a second conductive material, a core-shell rod including a shell of a non-conductive core-conductive material, a hollow A fiber-based functional composite comprising a hollow rod, or a mixture thereof. 4. The method of claim 1 or 3,
The conductive rod is a fiber-based functional composite having a unimodal, bimodal or trimodal distribution in terms of size distribution converted to spheres of the same volume. 4. The method of claim 1 or 3,
The long axis length of the conductive rod is a fiber-based functional composite of 500 nm to 15 μm. 8. The method of claim 7,
An aspect ratio of the conductive rod is 20 to 80 of a fiber-based functional composite. 4. The method of claim 1 or 3,
The conductive layer is a fiber-based functional composite comprising a network of conductive rods. 4. The method according to any one of claims 1 to 3,
The thickness of the conductive layer is a fiber-based functional composite material of 0.1 μm to 500 μm. 10. The method of claim 9,
The conductive layer is a fiber-based functional composite further comprising at least one conductive structure selected from the group consisting of conductive particles, conductive plates, conductive fibers, and conductive tubes. 4. The method according to any one of claims 1 to 3,
The conductive layer is a fiber-based functional composite further containing a binder. 13. The method of claim 12,
The conductive component of the conductive layer: the mass ratio of the binder component is 1: 0.5 to 2.5 fiber-based functional composite material. 14. The method of claim 13,
The binder is a fiber-based functional composite comprising a urethane resin, a vinyl chloride resin, an acrylic resin, a cellulose resin, a phenol resin, or a mixture thereof. 4. The method according to any one of claims 1 to 3,
A fiber-based functional composite further comprising a second binder layer positioned between the conductive layer and the substrate. According to claim 15,
A fiber-based functional composite in which a portion of the conductive component of the conductive layer is fixed to the second binder layer. 4. The method according to any one of claims 1 to 3,
The functional composite is a fiber-based functional composite further comprising an upper conductive layer positioned on the lower conductive layer by using the conductive layer as a lower conductive layer. 18. The method of claim 17,
The upper conductive layer is a fiber-based functional composite having a friction coefficient of 1.5 or more. 18. The method of claim 17,
The upper conductive layer is a fiber-based functional composite comprising a dotted conductive material. 20. The method of claim 19,
The dotted conductive material of the upper conductive layer is a fiber-based functional composite including a carbon-based conductive material. 21. The method of claim 20,
The carbon-based conductive material is a fiber-based functional composite comprising carbon black. 21. The method of claim 20,
The dotted conductive material is a fiber-based functional composite further comprising a metal conductive material. 23. The method of claim 22,
The carbon-based conductive material: the mass ratio of the metal conductive material is 1.0: a fiber-based functional composite material of 0.5 to 2.0. 20. The method of claim 19,
The upper conductive layer further includes a third binder, and the mass ratio of the dotted conductive material: the third binder is 1.0: a fiber-based functional composite material of 0.5 to 2.5. 4. The method according to any one of claims 1 to 3,
The conductive layer is a patterned fiber-based functional composite. 4. The method according to any one of claims 1 to 3,
The fiber-based functional composite is a fiber-based functional composite comprising two or more conductive layers spaced apart from each other. 4. The method according to any one of claims 1 to 3,
The fiber of the base material is a fiber-based functional composite comprising a natural fiber, a synthetic fiber, or a combination thereof. 28. The method of claim 27,
The natural fibers include one or more fibers selected from plant fibers, animal fibers and mineral fibers, and the synthetic fibers include nylon fibers, polyester fibers, acrylonitrile fibers, polyvinyl alcohol fibers, polyvinyl chloride fibers, and polyurethane. A fiber-based functional composite comprising one or more fibers selected from fibers, rayon fibers, tencel fibers, modal fibers, blends thereof, and combinations thereof. 4. The method according to any one of claims 1 to 3,
The substrate is a fiber-based functional composite comprising a woven or non-woven fabric of fibers. 4. The method according to any one of claims 1 to 3,
The base material is a fiber-based functional composite material that is an elastic fabric (fabric). 4. The method according to any one of claims 1 to 3,
The fiber-based functional composite material is a textile-based functional composite material for electrical stimulation clothing, electrical stimulation device, or biosignal detection sensor. A device comprising the fiber-based functional composite according to any one of claims 1 to 3, wherein the conductive layer side of the fiber-based functional composite is in contact with animals including humans. A fiber-based functional composite according to any one of claims 1 to 3, wherein the substrate of the fiber-based functional composite is in a form that can be worn or worn by animals including humans, and the conductive layer of the fiber-based functional composite is A coating positioned on the side that comes into contact with animals, including humans, of the above description.