KR20190131242A - Conductive fiber assemblies and manufacturing method thereof - Google Patents

Abstract

The present invention is to provide a conductive fiber assembly capable of efficiently performing metal salt reduction through metal organic decomposition. According to an embodiment of the present invention, the conductive fiber assembly includes a metal coating which has metal particles coated on the outermost surface of the fiber assembly and a fiber surface except for the outermost surface of the fiber assembly. The metal coating coated on the fiber surface except for the outermost surface of the fiber assembly is thinner than the metal coating coated on the outermost surface of the fiber assembly.

Description

CONDUCTIVE FIBER ASSEMBLIES AND MANUFACTURING METHOD THEREOF

The present invention relates to a conductive fiber assembly, and more particularly, to a conductive fiber assembly capable of reducing and sintering a metal under mild conditions.

With the development of scientific civilization, the use of various electric, electronic and communication devices for the convenience of mankind is expanding. These devices simultaneously cause various unwanted factors along with the convenience of human life, and the representative one is the damage of electromagnetic waves. In particular, electromagnetic waves generated from high frequency electronic devices may adversely affect the human brain, and may cause electronic devices to malfunction due to electromagnetic interference (EMI) with nearby electronic devices. In addition, when the human body is exposed to microwaves generated from household electrical appliances such as microwave ovens for a long time has been reported to adversely affect the human body by the heat action of the microwave, causing serious consequences, such as decreased fertility.

In order to eliminate the damage of electromagnetic waves, the electromagnetic waves must be shielded from the electronic equipment. A typical shielding product is a shielding paint, which is a product made by mixing a metal or conductive material such as Ni and Cu with a polymer material and coating it. Korean Unexamined Patent Publication No. 2015-0077238 discloses a coating composition for shielding electromagnetic waves. However, the disadvantage is that the thickness of the coating film is relatively thick, high thickness, compared to the plating and deposition method, there is a problem in the fall and uniformity of the coating film, there is a problem that the long-term shielding effect by oxidation is inferior. As the harmfulness of electromagnetic waves is known in recent years, the limits of electromagnetic wave allowances in each country have become strict, and the performance of electromagnetic wave shielding coatings has been required. Background of the Invention In recent years, the coating of the surface to prevent the oxidation of the metal and improve the electrical conductivity, the resistance value is good even at low film thickness, and the development of electromagnetic shielding material capable of expressing sufficient shielding efficiency has been actively made.

On the other hand, the electromagnetic wave removing material may be directly coated on an object that emits electromagnetic waves, but this method has a problem that the manufacturing process is complicated and the cost increases as the corresponding process must be performed separately for each component. Therefore, it is developed as a shielding part in a complex state by treating it on a separate support member. As the supporting member, a polymer film, a plastic, or a textile product is used. The polymer film has a limit on the amount of coating because the area capable of covering the electromagnetic wave removing material is limited to the surface, and the coating layer is used to coat a large amount. It is necessary to increase the thickness of, which is undesirable in the recent trend of light and short miniaturization. In addition, the plastic is not good flexibility is likely to cause cracks, there is a problem that can cause degradation of electromagnetic shielding properties due to cracks. In addition, the textile product, for example, a fabric such as a fabric is advantageous to express the electromagnetic wave removal performance superior to the film in that it can be provided with a certain amount of electromagnetic wave removal material inside the film even when the same thickness. In addition, the fabric may be woven into a yarn comprising several strands of fiber, in which case the multiple strands of fibers laminated at the cross section of the fabric may be more advantageous in terms of electromagnetic shielding as they form a structurally multilayer.

The excellent characteristics of the conductive fibers or fabrics are those manufactured by applying the electroless plating method, which has a disadvantage in that the process is complicated and a large amount of waste water is generated, thereby causing environmental pollution. In addition, the metal layer is formed in the form of a coating, but if a part of the coating is stressed or cracked, there is a problem that the whole peels off.

On the other hand, as a metal ink used for forming a metal circuit pattern, in most cases, a form in which metal particles are dispersed is used. At this time, the sintering temperature is 300 ° C or higher. In order to lower the sintering temperature, many researches are being made to reduce the size of metal to nano size, which is expensive and additionally needs to disperse metal particles to make ink.

Process conditions applied when forming the coating layer, for example, high temperature, pressure, etc. have a problem of causing physical and chemical damage to the support member on which the coating layer is to be formed. Accordingly, there is an urgent need for research on conductive fiber assemblies having excellent conductivity and durability under relaxed process conditions.

Republic of Korea Patent Publication No. 2015-0077238

The present invention is to solve the problems of the prior art as described above, it is possible to reduce and sinter the metal under mild conditions to coat the metal on the fiber assembly is good in form flexibility, excellent electromagnetic shielding effect conductive fiber assembly To provide. In addition, metal can be coated on both the outermost surface of the fiber assembly and the fiber surface except this to maximize electromagnetic shielding efficiency, and conductive fiber capable of efficiently performing metal salt reduction through metal organic decomposition. We want to provide an aggregate. In particular, the present invention is to provide a conductive fiber assembly capable of exhibiting a sheet resistance of 1 Ω / □ or less and an electromagnetic shielding rate of 40 dB or more.

These and other objects and advantages of the present invention will become more apparent from the following description of preferred embodiments.

The object is to include a metal coating wherein the metal particles are coated on the outermost surface of the fiber assembly and the fiber surface except the same, and the metal coating coated on the fiber surface except the outermost surface of the fiber assembly is applied to the outermost surface of the fiber assembly. It can be achieved by conductive fiber assemblies that are coated thinner than the coated metal sheath.

Preferably, the metal particles may be reduced by heat treating a conductive composition including a metal salt, an organic solvent, an organic amine, and a reducing agent.

Preferably, the metal coating coated on the fiber surface other than the outermost surface of the fiber assembly may be coated with a thickness of 1/100 to 1/3 of the thickness of the metal coating coated on the outermost surface of the fiber assembly.

Preferably, the metal particles forming the metal coating may have a particle diameter of 50 nm to 500 nm.

Preferably, the metal coating coated on the outermost surface may be coated with a thickness of 1 to 20 times the particle size of the metal particles.

Preferably, the metal of the metal coating may include at least one or more selected from copper, nickel, silver, aluminum and cobalt.

Preferably, the fiber aggregate may comprise one selected from fibers, wovens, knits and nonwovens.

Preferably, the thickness of the fiber aggregate without the metal coating may be 10 μm to 200 μm.

Preferably, the diameter of the fibers constituting the fiber assembly may be 0.1 μm to 50 μm.

Preferably, the fiber aggregate is polyester resin, polyamide resin, polyimide resin, polyolefin resin, polyvinyl chloride resin, polyvinyl resin, polytetrafluoroethylene resin, polyvinyl alcohol resin It may include one selected from polyacrylonitrile resin, aramid resin, acrylic resin, polyurethane resin.

Preferably, the organic solvent may include one or more selected from the group consisting of alcohols and glycols.

Preferably, the organic amine may include one or more selected from primary amines having 3 to 10 carbon atoms, secondary amines having 2 to 6 carbon atoms, and cyclic amines having 3 to 8 carbon atoms.

Preferably, the reducing agent is formic acid, acrylic acid, phosphoric acid, citric acid, lactic acid, alanine, glycolic acid, glycine, acetic acid, formaldehyde, hydrazine, sodium borohydride, dimethylformamide, butylcarbitol, glucose, tannic acid, sodium hypophosphite, It may include one or more selected from phosphinic acid, oleylamine, polyol.

In addition, the object is (a) dispersing the metal salt in an organic solvent, (b) adding an organic amine to the solution obtained in step (a), (c) adding a reducing agent to the solution obtained in step (b) And stirring to prepare the conductive composition, (d) applying the conductive composition prepared in step (c) to the fiber assembly, (e) nitrogen to the fibrous assembly to which the conductive composition obtained in step (d) is applied. Heat treatment in an atmosphere may be achieved by a method for producing a conductive fiber assembly comprising the step of coating a metal coating on the outermost surface of the fiber assembly and the fiber surface except this.

Preferably, the heat treatment of step (e) may include a preheating step made at 30 ~ 100 ℃ and the main heat treatment step at 120 ~ 220 ℃.

Preferably, the molar ratio of the organic amine and the reducing agent may be 1: 1 to 1: 3.

The conductive fiber assembly and the method of manufacturing the same according to an embodiment of the present invention are capable of reducing and sintering a metal under mild conditions so that the metal can be coated on the fiber surface except the outermost surface as well as the outermost surface of the fiber assembly. The conductivity and electromagnetic shielding efficiency can be maximized, and a conductive fiber assembly with good form flexibility can be provided.

In addition, in one embodiment of the present invention, the conductive fiber assembly and the method of manufacturing the same can coat the metal on both the outermost surface of the fiber assembly and the fiber surface except the same, thereby maximizing electromagnetic shielding efficiency, and metal organic decomposition method (metal organic Metal salt reduction can be efficiently performed through a heat treatment method using decomposition).

In particular, the conductive fiber assembly according to the present invention can provide a conductive fiber assembly that can exhibit a sheet resistance of 1 Ω / □ or less and an electromagnetic shielding ratio of 40 dB or more.

In addition, the conductive fiber assembly and the method of manufacturing the same according to an embodiment of the present invention are provided with a wide specific surface area, and exhibit excellent electromagnetic shielding performance as the coating property of the outer and inner surfaces of the support member is excellent, and the shape change is Even if coated on a free support member, it is possible to provide a conductive fiber assembly having excellent durability of the coating layer, and various electronic components and electronic devices embodied therein.

However, the effects of the present invention are not limited to the above-mentioned effects, and other effects not mentioned will be clearly understood by those skilled in the art from the following description.

1A is a surface view of a conductive fiber assembly according to an embodiment of the present invention.
FIG. 1B is an enlarged view of the surface view of the conductive fiber assembly of FIG. 1A. FIG.
FIG. 2A is a cross-sectional view of the conductive fiber assembly of FIG. 1A. FIG.
FIG. 2B is an enlarged view of a cross-sectional view of the conductive fiber assembly of FIG. 2A. FIG.
3 is a flowchart of a method of manufacturing a conductive fiber assembly according to an embodiment of the present invention.

Hereinafter, the present invention will be described in detail with reference to embodiments and drawings of the present invention. These examples are only presented by way of example only to more specifically describe the present invention, it will be apparent to those skilled in the art that the scope of the present invention is not limited by these examples. .

In the drawings, the thickness of layers, films, panels, regions, etc., are exaggerated for clarity. Like parts are designated by like reference numerals throughout the specification. When a part of a layer, film, region, plate, etc. is said to be "on" another part, this includes not only the other part being "right over" but also another part in the middle. On the contrary, when a part is "just above" another part, there is no other part in the middle.

Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. In case of conflict, the present specification, including definitions, will control. Also, although methods and materials similar or equivalent to those described herein can be used in the practice or testing of the present invention, suitable methods and materials are described herein.

Hereinafter, various aspects and various embodiments of the present invention will be described in more detail with reference to FIGS. 1A to 2B. 1A and 1B are surface views of a conductive fiber assembly according to an embodiment of the present invention, and show a surface of which a metal coating is coated on the outermost surface of the fiber assembly. 2A and 2B are cross-sectional views of the conductive fiber assembly of FIG. 1A, showing a metal sheath 120 coated on the outermost surface of the fiber assembly and the fiber surface except it.

The present invention relates to a conductive fiber assembly, and more particularly to a conductive fiber assembly capable of reducing and sintering a metal under mild conditions to coat the metal on the fiber assembly, thereby having good form flexibility and excellent electromagnetic shielding effect. will be. In addition, the outermost part of the fiber assembly and the surface of the fiber except for it can be coated with metal to maximize the electromagnetic shielding efficiency, and the metal salt reduction can be efficiently performed through the heat treatment method using metal organic decomposition. It is characterized by being.

The conductive fiber assembly according to the embodiment of the present invention includes a metal sheath 120 coated on the outermost surface of the fiber assembly and the fiber surface except for the same.

Fiber assembly is a substrate of a conductive fiber assembly according to an embodiment of the present invention. The fiber assembly is preferably formed of any one of silver fibers, woven fabrics, knitted fabrics and nonwoven fabrics.

Metal coating 120 is a configuration in which a metal is applied to the surface of the fiber 110 constituting the fiber assembly. The metal coating 120 is coated on the fiber surface except for the outermost surface and the outermost surface of the fiber assembly composed of a plurality of fibers (110). In this case, the metal coating 120 may be coated on the entire fiber assembly to increase the shielding effect. That is, the outermost surface of the fiber assembly is limited to the outside of the fiber assembly, not the entire surface of the outermost fiber, among the surfaces of the outermost fiber among the plurality of fibers (strands) 110 constituting the fiber assembly. It means only surface. The fiber surface except for the outermost surface of the fiber assembly means all surfaces except for the outermost surface of the plurality of fibers 110 constituting the fiber assembly.

The metal coating 120 may be coated by the reduced metal particles during the heat treatment of the conductive composition including the organic solvent, the metal salt, the organic amine, and the reducing agent applied to the fiber assembly. In addition, the conductive composition including an organic solvent, a metal salt, an organic amine, and a reducing agent applied to the fiber assembly may be a composition used for metal organic decomposition (MOD). A composition containing an organic solvent, a metal salt, an organic amine, and a reducing agent will be described in detail with reference to FIG. 3 described later.

The applied conductive composition is applied not only to the outermost surface of the fiber assembly, but also to the inside of the fiber assembly and to the fiber surface except the outermost surface. As such, the metal salt contained in the conductive composition is reduced to metal particles by heat-treating the outermost surface of the fiber assembly and the conductive composition applied to the fiber surface except for the same, so that the metal coating is applied to the outermost surface of the fiber assembly and the fiber surface except the same. 120) is coated.

The metal coating 120 has a thickness different from a portion coated on the outermost surface of the fiber assembly and a portion coated on the fiber surface except for the same. Unlike the outermost surface of the fiber assembly, the fiber surface except the outermost surface is limited to the fiber surface except the outermost surface because the amount of conductive composition penetrated into the inside is limited by the space between the fiber strands constituting the fiber assembly. The coated metal sheath 120 is thinner than the metal sheath 120 coated on the outermost surface. More specifically, the space inside the fiber assembly is less spaced than the outermost because the fiber 110 is located closely, the metal coating 120 coated on the outermost surface of the fiber assembly is a fiber except the outermost surface It is thicker than the metal sheath 120 coated on the surface.

More specifically, referring to FIGS. 2A and 2B, in the plurality of fibers 110 constituting the fiber assembly, a metal coating 120 is thickly coated on the outermost surface of the fiber assembly, while the fiber surface except for the fiber ( Since the 110 are in close contact with each other, there is less space, so that the metal coating 120 is relatively thinly coated. That is, the metal sheath 120 is thickest on the outermost surface of the fiber assembly, and the fiber surface that is not the outermost surface is thinner than the outermost surface.

The conductive fiber assembly according to an embodiment of the present invention has a structural feature in which metal is coated on both the outermost surface of the fiber assembly and the fiber surface except for this, and thus an excellent shielding effect can be achieved.

The process in which the metal coating 120 is coated on the fiber assembly will be described in detail in the manufacturing method of FIG. 3 to be described later.

According to one embodiment, the metal particles of the metal coating 120 coated on the fiber assembly is preferably a particle size of 50nm to 500nm, more preferably 50nm to 400nm. If the particle size of the metal particles is less than 50 nm, it occurs when the metal salt is insufficient or the heat treatment rate is too fast. If the metal salt is insufficient, the desired conductivity cannot be exhibited. If the heat treatment rate is too fast, the fiber assembly may be damaged. Can be. If the particle diameter exceeds 500 nm, the heat treatment must be performed at a higher temperature for the sintering of the metal particles, in which case the fiber assembly may be damaged.

According to another embodiment, the metal coating 120 coated on the outermost surface of the fiber assembly is preferably coated with a thickness of 1 to 20 times the particle size of the metal particles, and is coated with a thickness of 1 to 10 times More preferred. If the thickness of the metal coating 120 coated on the outermost surface is less than 1 times the particle size of the metal, the metal is not coated and thus the desired conductivity cannot be exhibited. On the other hand, when the thickness of the metal coating 120 coated on the outermost surface exceeds 20 times the metal particle diameter, more energy and time are consumed to reduce and sinter the metal salt, which is not preferable, thereby damaging the fiber assembly. It may cause a problem that the bonding force between the metal particles is weakened and the metal is separated from the fiber assembly.

The metal coating 120 coated on the fiber surface except the outermost surface is preferably coated with a thickness of 1/100 to 1/3 of the thickness of the metal coating 120 coated on the outermost surface. More preferably, it is coated with a thickness of 1/3. If the metal coating 120 coated on the fiber surface except the outermost surface is less than 1/100 of the thickness of the metal coating 120 coated on the outermost surface, the amount of metal is small so that the desired conductivity cannot be exhibited. Since the metal coating 120 penetrates into the inside of the fiber assembly and is coated on the surface of the fiber 110 constituting the fiber assembly, the metal coating 120 is coated on the surface of the fiber 110 except for the outermost surface of the fiber assembly. The thickness of is influenced by the space between the fibers 110 of the fiber assembly. Therefore, when the thickness of the metal coating 120 coated on the fiber surface except the outermost surface exceeds 1/3 of the thickness of the metal coating 120 coated on the outermost surface, the fibers 110 constituting the fiber assembly. It can be implemented when the space between them is wide, but when the space between the fibers 110 is widened, the density of the fiber assembly is lowered and eventually the surface area of the fiber assembly is reduced, so that the coating amount of the metal coating 120 is also reduced, resulting in a shielding effect. Reduced, which is undesirable.

According to another embodiment, the metal particles included in the metal coating 120 may include any one metal selected from copper, nickel, silver, aluminum, cobalt, iron, and zinc, or may include two or more alloys selected therefrom. can do.

According to another embodiment, the thickness of the fiber aggregate in the state in which the metal coating 120 is not coated is preferably 10 μm to 200 μm, more preferably 10 μm to 150 μm. If the thickness of the fiber assembly is less than 10㎛ it is difficult to maintain the form as a base material, if the thickness exceeds 200㎛ there is a problem that does not meet the light and small size required in the electronic device, etc. to which the conductive fiber assembly manufactured by the present invention is applied. .

According to another embodiment, the diameter of the fiber 110 constituting the fiber assembly is preferably 0.1㎛ 50㎛, more preferably 0.5㎛ 30㎛. If the diameter of the fiber 110 constituting the fiber assembly is less than 0.1 μm, the particle size may be similar to or smaller than the particle diameter of the metal particles constituting the metal coating 120, thereby making it difficult to attach the metal particles to the fiber 110. If the diameter of the (110) exceeds 50㎛ may cause a problem that the thickness of the fiber assembly is thick.

According to another embodiment, the fiber assembly is a polyester resin, polyamide resin, polyimide resin, polyolefin resin, polyvinyl chloride resin, polyvinyl resin, polytetrafluoroethylene resin, polyvinyl It may be formed of any one resin selected from alcohol resin, polyacrylonitrile resin, aramid resin, acrylic resin, polyurethane resin.

3 is a flowchart of a method of manufacturing a conductive fiber assembly according to an embodiment of the present invention.

Referring to FIG. 3, the method for preparing a conductive fiber assembly shown in FIG. 1 includes (a) dispersing a metal salt in an organic solvent, (b) adding an organic amine to the solution obtained in step (a), ( c) adding and stirring a reducing agent to the solution obtained in step (b) to prepare a conductive composition, (d) applying the conductive composition prepared in step (c) to the fiber assembly, (e) the (d) Heat treating the fibrous assembly to which the conductive composition obtained in the step) is applied under a nitrogen atmosphere to coat the metal coating 120 on the outermost surface of the fibrous assembly and the fiber surface except for the same.

In the method for producing a conductive fiber assembly according to an embodiment of the present invention, the organic amine forms a complex with copper ions, and serves to reduce the reduction at a low temperature. The organic amine may include one or more selected from the group consisting of a primary amine having 3 to 10 carbon atoms, a secondary amine having 2 to 6 carbon atoms, and a cyclic amine having 3 to 8 carbon atoms. The size of the copper particles produced is determined according to the carbon number of the organic amine. The higher the carbon number, the smaller the particle size tends to be, and the smaller the particle, the easier the sintering is at a lower temperature. When the amine having a lower carbon number than the organic amine is used, there is a problem in that the sintering of the metal particles is not performed well, so that the particles exist in the state of the particles alone, resulting in low conductivity and peeling resistance. If used, the amine remains unremoved in the heat treatment step, thereby lowering the conductivity.

According to another embodiment, the organic amine and the reducing agent are used in a molar ratio of 1: 1 to 1: 3, preferably in a molar ratio of 1: 1 to 1: 2. If the reducing agent is less than the molar ratio relative to the organic amine, there may be a problem that the reduction of the metal complex is not made well, and if the reducing agent exceeds the molar ratio relative to the organic amine, a side reaction occurs due to an excess of the reducing agent resulting in sheet resistance. And there may be a problem that the peeling resistance worsens.

According to another embodiment, the reducing agent is formic acid, acrylic acid, phosphoric acid, citric acid, lactic acid, alanine, glycolic acid, glycine, acetic acid, formaldehyde, hydrazine, sodium borohydride, dimethylformamide, butylcarbitol, glucose, tannic acid, It may be at least one selected from sodium hypophosphite, phosphinic acid, oleylamine, polyol.

In step (d), the method of applying the conductive composition to the fiber assembly may include bar coating, slot die coating, spray coating, dip coating, blade coating, comma coating, squeeze ) Coating and the like can be used.

According to another embodiment, the organic solvent may be selected from alcohols, glycols, or a mixed solvent of these two.

Examples of alcohol solvents include methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, 2-methyl-1-propanol, 2-methyl-2-propanol, 1-pentanol, and 2-pentane Ol, 3-pentanol, 2,2-dimethyl-1-propanol, 1-hexanol, cyclopentanol, 3-methyl-1-butanol, 3-methyl-2-butanol, 2-methyl-1-butanol, 2,2-dimethyl-1-propanol, 3-hexanol, 2-hexanol, 4-methyl-2-pentanol, 2-methyl-1-pentanol, 2-ethylbutanol, 2,4-dimethyl-3 -Pentanol, 3-heptanol, 4-heptanol, 2-heptanol, 1-heptanol, 2-ethyl-1-hexanol, 2,6-dimethyl-4-heptanol, 2-methylcyclohexanol , 3-methylcyclohexanol, 4-methylcyclohexanol, isopropyl alcohol, benzyl alcohol, cyclohexanol and mixtures thereof, but is not limited thereto.

Examples of glycol solvents include ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, butylene glycol, hexylene glycol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, and ethylene. Glycol monobutyl ether, ethylene glycol dimethyl ether, diethylene glycol methyl ether, diethylene glycol ethyl ether, diethylene glycol butyl ether, diethylene glycol diethyl ether, diethylene glycol dibutyl ether, triethylene glycol dimethyl ether, triethylene Glycol monobutyl ether, triethylene glycol monoethyl ether, propylene glycol monomethyl ether, propylene glycol dimethyl ether, dipropylene glycol methyl ether, and mixtures thereof.

According to another embodiment, the heat treatment in step (e) may include a preheating step made at 30 ~ 100 ℃ and the main heat treatment step made at 120 ~ 220 ℃. If not preheated or if the temperature is below 30 ° C., a large amount of solvent remains in the metal salt ink component. When the metal salt is reduced in the main heat treatment step, the solvent present between the metals is removed. At this time, the remaining solvent may interfere with the sintering of the metal particles, and the space from which the solvent is removed may remain as a void, thereby lowering conductivity. If the temperature exceeds 100 ° C, the same problem may occur if the temperature is less than 30 ° C because the preheating process is the same as the main heat treatment without the preheating process.

In addition, when the heat treatment temperature is lower than 120 ° C., organic matter and reaction by-products in the metal salt ink may not be removed, and thus the sheet resistance may be increased. When the heat treatment temperature is higher than 220 ° C., the fiber assembly is excluded except for components having good heat resistance such as para-aramid. It is undesirable because it is damaged at high temperatures.

In addition, according to the present invention, the temperature increase rate of the preheating step is not particularly limited.

In addition, the temperature increase rate of the heat treatment step is preferably 5 ° C / min to 50 ° C / min, more preferably 10 ° C / min to 40 ° C / min. If the temperature increase rate is less than 5 ℃ / minute, the growth time of the metal particles is increased, the particle size is increased, if the particle size is large, it adversely affects the sintering between particles, if the temperature rise rate exceeds 50 ℃ / minute fiber as a substrate This is because there is a problem that the aggregates are damaged, which is not preferable.

The conductive fiber assembly according to an embodiment of the present invention may be formed by metal organic decomposition as described above. According to another embodiment, the organometallic decomposition method may be performed by reducing the metal salt using an organic amine and a reducing agent.

According to the most preferred embodiment of the present invention, (i) the metal coating constituting the conductive fiber assembly must be formed by organometallic decomposition using an organic amine and a reducing agent, and (ii) when the organic amine is a primary amine 3 to 10, 2 to 6 for secondary amines, 3 to 8 for cyclic amines, (iii) the molar ratio of organic amine used to reducing agent is 1: 1 to 1: 2, and (iv) The heat treatment performed by applying a dispersion containing a metal precursor, an organic amine, and a reducing agent to a substrate and performing in an inert gas atmosphere consists of a preheating step performed at 30 to 100 ° C. and a main heat treatment step performed at 120 to 220 ° C.

Another aspect of the present invention relates to a gasket comprising a conductive fiber assembly according to various embodiments of the present invention.

Another aspect of the invention relates to a conductive tape comprising a conductive fiber assembly according to various embodiments of the present invention.

Another aspect of the invention relates to an electronic device including a conductive fiber assembly according to various embodiments of the present invention.

Hereinafter, the present invention will be described in more detail with reference to examples and the like, but the scope and contents of the present invention are not limited or interpreted by the following examples. In addition, if it is based on the disclosure of the present invention including the following examples, it will be apparent that those skilled in the art can easily carry out the present invention, the results of which are not specifically presented experimental results, these modifications and modifications are attached to the patent It goes without saying that it belongs to the claims.

In addition, the experimental results presented below are only representative of the experimental results of the above Examples and Comparative Examples, and the effects of each of the various embodiments of the present invention not explicitly set forth below will be described in detail in the corresponding sections.

In Examples 1-8 and Comparative Examples 1-6 described later, experiments were performed by varying the heat treatment conditions as shown in Table 1 below. More specific Examples 1 to 8 and Comparative Examples 1 to 6 are as follows.

Example 1

5 mL of a solvent consisting of 1: 1 of ethanol and ethylene glycol was added to 4.8 g of copper acetate, followed by stirring for 5 minutes. Cyclohexylamine was added dropwise 1.5 times compared to the number of moles of copper acetate for 4 minutes, and then formic acid was added to F / A 1.5 and stirred for 2 hours to prepare a copper salt ink as a conductive composition. In the present invention, F / A represents the molar ratio of formic acid to the injected amine.

Copper salt ink prepared on a 50 μm-thick PET fabric was applied using a bar coater to a thickness of 100 μm. The PET fabric coated with copper salt ink was placed in a rapid heat treatment apparatus (Hantech Co., Ltd.) to make a nitrogen atmosphere for 10 minutes. Then, after the heat treatment under the conditions shown in Table 1, by slowly cooling to room temperature to form a metal coating on the PET fabric to prepare a conductive fiber assembly.

Example 2-8

Conductive fiber aggregates were prepared in the same manner as in Example 1 except that the heat treatment conditions were performed under the conditions shown in Table 1.

Comparative Example 1-5

Conductive fiber aggregates were prepared in the same manner as in Example 1 except that the heat treatment conditions were performed under the conditions shown in Table 1.

Comparative Example 6

A conductive fiber assembly was prepared in the same manner as in Example 1 except that the copper salt ink was applied to the fabric at a thickness of 500 μm.

The conductive fiber aggregates according to Examples 1 to 8 and Comparative Examples 1 to 6 were used to measure physical properties through the following experimental examples, and the results are shown in Table 1 below.

Experimental Example

(1) Surface resistance measurement

Surface resistance was measured using a surface resistance meter (SR2000N).

(2) Electromagnetic shielding rate measurement

Electromagnetic shielding rate was measured by ASTM D-4935 S-parameter measurement method using Network Analyzer (E8364B).

(3) Measurement of particle size and metal coating thickness

: The prepared conductive fiber assembly was analyzed by scanning electron microscope (SEM) to obtain an image, and then the particle diameter and the metal coating thickness were measured.

division Heat treatment condition Properties Metal sheath Preheating Heat treatment Temperature
(℃) Elevated temperature
speed
(℃ / min) maintain
time
(minute) Temperature
(℃) Elevated temperature
speed
(℃ / min) maintain
time
(minute) Sheet resistance
(Ω / □) Electromagnetic
Shielding rate
(dB) Average
Particle diameter
(nm) Metal coating thickness of outermost surface (nm) Of the fiber surface except the outermost surface
Average thickness of metal sheath
(nm) Example 1 50 One 30 190 10 10 0.23 61 180 1150 250 Example 2 50 40 30 190 10 10 0.29 59 192 950 200 Example 3 80 One 10 190 10 10 0.28 58 205 930 190 Example 4 80 4 10 190 10 10 0.31 55 193 1300 180 Example 5 80 40 10 190 10 10 0.32 54 237 1500 180 Example 6 80 40 30 190 20 10 0.22 65 90 870 170 Example 7 80 40 30 170 10 10 0.54 50 170 740 160 Example 8 80 40 30 170 10 15 0.43 52 157 810 150 Comparative Example 1 80 40 30 110 10 10 23000 One 250 F2 F2 Comparative Example 2 80 40 30 230 10 10 F1 F1 443 F1 F1 Comparative Example 3 80 40 30 190 55 10 F1 F1 35 F1 F1 Comparative Example 4 20 - 30 190 10 10 5099 2 266 3050 100 Comparative Example 5 110 40 30 190 10 10 87 5 255 2560 110 Comparative Example 6 50 One 30 190 10 10 45100 One 350 8100 160

In Table 1, F1 shows a result in which the comparative examples 2 and 3 melted and were not measured, and F2 shows a result in which the metal salt remained in Comparative Example 1 and thus could not be measured.

As can be seen from Table 1, Examples 1 to 8 of the present invention, the conductive fiber assembly according to the present invention achieves the particle diameter of the desired metal particles, the thickness of the metal coating and the resulting sheet resistance and electromagnetic shielding rate. On the other hand, Comparative Examples 1 to 5 that do not satisfy the heat treatment conditions included in the method for producing a conductive fiber assembly according to the present invention does not achieve this.

Comparative Examples 1 and 2 were produced under conditions in which the heat treatment temperature was outside the preferred temperature range. In Comparative Example 1, the metal salt remained in the sample, so that the average thickness of the coated metal 120 could not be measured. In Comparative Example 2, the conductive fiber assembly serving as the substrate was damaged, and thus sheet resistance, electromagnetic shielding rate, and metal coating thickness could not be measured.

In Comparative Example 3, the temperature increase rate of the main heat treatment was 55 ° C., and the fiber aggregate, which was the substrate, was damaged beyond the preferable range of 5 ° C./min to 50 ° C./min. .

Comparative Examples 4 to 5 were generated under conditions where the preheating temperature was outside the desired temperature range, and it was found that the electromagnetic shielding rate was very low as compared with Examples 1-8.

In Comparative Example 6, the thickness of the copper salt ink coating was high, and the thickness of the metal coating on the outermost surface exceeded a preferable range with respect to the particle size of the metal particles, and the electromagnetic shielding rate was also low.

Although the preferred embodiments of the present invention have been described in detail above, the scope of the present invention is not limited thereto, and various modifications and improvements of those skilled in the art using the basic concepts of the present invention defined in the following claims are also provided. It belongs to the scope of rights.

110: fibers constituting the fiber assembly
120: metal sheath

Claims (16)

The metal particles include a metal sheath coated on the outermost surface of the fiber assembly and the fiber surface except this;
A conductive fiber assembly coated on the surface of the fiber except the outermost surface of the fiber assembly is thinner than the metal coating coated on the outermost surface of the fiber assembly. The method of claim 1,
The metal particles are reduced by heat treatment of a conductive composition comprising a metal salt, an organic solvent, an organic amine, a reducing agent. The method of claim 1,
And a metal coating coated on the fiber surface except the outermost surface of the fiber assembly is coated with a thickness of 1/100 to 1/3 of the thickness of the metal coating coated on the outermost surface of the fiber assembly. The method of claim 1,
The metal particles forming the metal coating is a conductive fiber assembly having a particle diameter of 50nm to 500nm. The method of claim 1,
The metal coating coated on the outermost surface of the fiber assembly is a conductive fiber assembly is coated with a thickness of 1 to 20 times the particle size of the metal particles. The method of claim 1,
The metal of the metal coating is a conductive fiber assembly comprising at least one selected from copper, nickel, silver, aluminum and cobalt. The method of claim 1,
The fiber assembly is a conductive fiber assembly comprising one selected from fibers, woven fabrics, knitted fabrics and nonwoven fabrics. The method of claim 1,
The fiber assembly has a thickness of 10 μm to 200 μm. The method of claim 1,
The diameter of the fibers constituting the fiber assembly is 0.1 ㎛ to 50 ㎛ conductive fiber assembly. The method of claim 1,
The fiber aggregate is polyester resin, polyamide resin, polyimide resin, polyolefin resin, polyvinyl chloride resin, polyvinyl resin, polytetrafluoroethylene resin, polyvinyl alcohol resin, polyacryl A conductive fiber assembly comprising at least one selected from a low nitrile resin, an aramid resin, an acrylic resin, and a polyurethane resin. The method of claim 2,
The organic solvent is a conductive fiber assembly comprising one or more selected from the group consisting of alcohols and glycols. The method of claim 2,
The organic amine is a conductive fiber aggregate comprising at least one selected from a primary amine having 3 to 10 carbon atoms, a secondary amine having 2 to 6 carbon atoms, and a cyclic amine having 3 to 8 carbon atoms. The method of claim 2,
The reducing agent is formic acid, acrylic acid, phosphoric acid, citric acid, lactic acid, alanine, glycolic acid, glycine, acetic acid, formaldehyde, hydrazine, sodium borohydride, dimethylformamide, butylcarbitol, glucose, tannic acid, sodium hypophosphite, phosphinic acid, A conductive fiber aggregate comprising at least one selected from oleylamine and polyol. (a) dispersing a metal salt in an organic solvent;
(b) adding an organic amine to the solution obtained in step (a);
(c) preparing a conductive composition by adding and stirring a reducing agent to the solution obtained in step (b);
(d) applying the conductive composition prepared in step (c) to the fiber assembly;
(e) heat-treating the fibrous assembly to which the conductive composition obtained in step (d) is applied under a nitrogen atmosphere to coat a metal coating on the outermost surface of the fibrous assembly and the fiber surface except for this;
Method for producing a conductive fiber assembly comprising a. The method of claim 14,
Heat treatment of the step (e),
Preheat treatment step made at 30 ~ 100 ℃; And
A heat treatment step at 120 ° C. to 220 ° C .;
Method for producing a conductive fiber assembly comprising a The method of claim 14,
The molar ratio of the organic amine and the reducing agent is 1: 1 to 1: 3 manufacturing method of the conductive fiber assembly.

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