KR20170112137A - Coating composition, conductive fiber aggregate manufactured therewith and method for manufacturing the conductive fiber aggregate - Google Patents

Abstract

More particularly, the present invention relates to a coating composition, and more particularly, to a coating layer that is easily formed even at a relatively low heat treatment temperature, so that damage to the support member due to heat treatment can be prevented, It is possible to produce a conductive fiber aggregate having excellent durability as a result of being excellent in formability and excellent adhesion even in the absence of a separate binder component and remarkably increasing the specific surface area of the formed coating layer as compared with the surface area of the support member, , A conductive fiber aggregate prepared therewith and a method for producing the same.

Description

TECHNICAL FIELD [0001] The present invention relates to a coating composition, a conductive fiber aggregate prepared by the method, and a method for manufacturing the conductive fiber aggregate.

More particularly, the present invention relates to a coating composition, and more particularly, to a coating layer that is easily formed even at a relatively low heat treatment temperature, so that damage to the support member due to heat treatment can be prevented, It is possible to produce a conductive fiber aggregate having excellent durability as a result of being excellent in formability and excellent adhesion even in the absence of a separate binder component and remarkably increasing the specific surface area of the formed coating layer as compared with the surface area of the support member, , A conductive fiber aggregate prepared therewith and a method for producing the same.

With the development of scientific civilization, the use of various electric, electronic and communication devices for the convenience of mankind is expanding. These devices cause the harmful effects of human life and the unwanted harmful factors simultaneously. In particular, electromagnetic waves generated from high-frequency electronic devices can adversely affect the human brain, and electromagnetic interference (EMI) with neighboring electronic devices may cause malfunction of electronic devices. In addition, when a human body is exposed to a microwave generated from a household electric appliance such as a microwave oven for a long time, it is reported that the human body is adversely affected by the heat of the microwave, resulting in serious consequences such as deterioration of reproductive ability.

In order to solve the damage of the electromagnetic wave, it is possible to shield the electromagnetic wave from the electronic device. A typical shielding product is a shielding paint, which is a product obtained by mixing metals such as Ni and Cu or a conductive material with a polymer material, and Korean Laid-Open Publication No. 2015-0077238 discloses a coating composition for shielding electromagnetic waves have. However, the disadvantage is that the thickness of the coating is relatively thick due to the low resistance compared with the plating and vapor deposition methods, there is a problem of falling and uniformity of the coating film, and the long-term shielding effect due to oxidation is inferior. Recently, as the harmful effects of electromagnetic waves are known, regulations for allowing electromagnetic waves in each country have become strict, and high performance of electromagnetic wave shielding coating agents is required. Background of the Invention In recent years, electromagnetic wave shielding materials have been actively developed to coat the surface of the metal to prevent oxidation of the metal and to improve the electrical conductivity, thereby exhibiting a good resistance value even at a low film thickness and exhibiting sufficient shielding efficiency.

However, there is a problem that process conditions such as high temperature, pressure, etc., which are applied when forming the coating layer, cause physical / chemical damage to the supporting member on which the coating layer is to be formed.

Accordingly, when the conditions for forming the coating layer are relaxed, the coating layer is formed only on the outer surface of the supporting member, which has a greater degree of heat or pressure, and a coating layer is not formed therein.

Further, the coating layer formed on the outer surface easily cracks and can be peeled off, so that the physical properties of electromagnetic wave shielding through the coating layer can not be sustained for a long time.

Further, when the support member, in which the coating layer is to be formed, is deformed by the external force such as a fibrous aggregate, the coating layer having a relatively high hardness and a hardness of a certain level or more is more easily cracked and peeled.

Accordingly, even if the coating layer is applied to a support member having excellent adhesion between the coating layer and the support member and free from deformations of the shape, the coating layer can be formed not only on the outside but also on the inner surface of the support member even under relaxed process conditions, It is urgently required to study a coating composition for electromagnetic wave shielding which has a small amount of electromagnetic wave shielding.

SUMMARY OF THE INVENTION The present invention provides a coating composition capable of preventing physical / chemical damage of a support member in a process for forming a coating layer as a coating layer is easily formed even under a relaxed coating layer formation condition, There is a purpose.

It is another object of the present invention to provide a coating composition capable of improving the coating layer formability due to the coating composition on the inner surface as well as the outer surface of the support member.

Another object of the present invention is to provide a coating composition capable of realizing a conductive fiber aggregate having excellent durability as a result of being excellent in adhesion even without a separate binder component.

It is a further object of the present invention to provide a coating composition capable of exhibiting excellent electromagnetic wave shielding performance by significantly increasing the specific surface area of the coating layer formed compared to the surface area of the supporting member.

In addition, the present invention provides a conductive fiber which is provided with a wide specific surface area and exhibits excellent electromagnetic wave shielding performance due to excellent coating properties on the outer and inner surfaces of the support member, Another object of the present invention is to provide an assembly, a method of manufacturing the same, and various electronic components and electronic apparatuses implemented thereon.

In order to solve the above-mentioned problems, the present invention provides a coating composition for forming a metal layer provided on a conductive fiber aggregate, wherein the coating composition comprises a first metal precursor and a second metal.

According to a preferred embodiment of the present invention, the second metal may be granular in order to improve the metal layer forming ability and the specific surface area of the metal layer in the fiber aggregate. In this case, the second metal may be a metal powder having a particle diameter of 100 to 100 nm.

According to another preferred embodiment of the present invention, the first metal precursor includes at least one selected from the group consisting of Cu, Ni, Co, Al and alloys thereof, and the second metal is Au, Pt, Pd , Ag, Cu, Ni, and alloys thereof.

According to another preferred embodiment of the present invention, the coating composition may include the first metal precursor and the second metal at a weight ratio of 1: 0.9 to 4.5.

According to another preferred embodiment of the present invention, the coating composition comprises at least one dispersing solvent selected from the group consisting of ethylene glycol, glycol ether and alcohol, and at least one solvent selected from the group consisting of polyvinyl alcohol (PVA), acrylic resin, urethane resin, And at least one binder compound selected from the group consisting of polyvinylpyrrolidone (PVP), ethylene vinyl acetate copolymer (EVA), and polyethylene oxide (PEO).

According to another preferred embodiment of the present invention, the first metal precursor may be a copper precursor, and the second metal may be copper.

On the other hand, the present invention relates to (1) treating a fibrous aggregate with a coating composition according to the present invention; And (2) firing the coating composition to form a fibrous aggregate coated with a metal layer comprising a first metal and a second metal.

According to a preferred embodiment of the present invention, in the step (1), the coating composition may be treated with 200 to 1000 parts by weight based on 100 parts by weight of the fibrous aggregate.

According to another preferred embodiment of the present invention, the firing may be performed at a temperature of 180 to 220 ° C for 1 to 30 minutes.

The present invention also relates to a fiber aggregate comprising a plurality of strands of monosa; And a metal layer including a first metal and a second metal and covering at least the outside of the fiber aggregate.

According to a preferred embodiment of the present invention, the fibrous aggregate may be a fabric composed of a yarn comprising a plurality of strands of monosa, or a fabric comprising a plurality of strands of monosa, a knitted fabric and a nonwoven fabric.

According to another preferred embodiment of the present invention, the metal layer may be coated with at least a part of the surface of the monosaccharide which is not exposed to the outside of the fibrous assembly.

According to another preferred embodiment of the present invention, the second metal is provided in a granular form in order to improve the metal layer forming ability and the specific surface area of the metal layer inside the fiber aggregate, and the metal layer is composed of the granular second metal and the second metal And may be formed of a first metal connecting the particles.

According to another preferred embodiment of the present invention, the mono-sphere may have a diameter of 0.05 to 2.5 탆.

According to another preferred embodiment of the present invention, the particle diameter of the second metal may be 1/2 to 1/250 of the diameter of the monocomponent of the fiber aggregate.

According to another preferred embodiment of the present invention, the first metal includes at least one selected from the group consisting of Cu, Ni, Co, Al and alloys thereof, and the second metal is at least one selected from the group consisting of Au, Pt, Pd, Ag, Cu, Ni, and an alloy thereof.

According to another preferred embodiment of the present invention, the fiber aggregate includes a fiber bundle including a plurality of strands of monosa in warp and weft, and can satisfy the following conditions (a) and (b).

(a) 0.02? D (占 퐉) 2.5, (b) 40 占 (D) ^-1.9 ? Y? 60 占 (D) ^-2.0

D is the monocular diameter (占 퐉), and Y is the number of mono yarns per unit area (100 占 퐉 ² ) in the vertical section of the fabric.

According to another preferred embodiment of the present invention, the fiber aggregate can further satisfy the following condition (c).

(c)

D is the monocular diameter (占 퐉), Y is the number of mono yarns per unit area (100 占 퐉 ² ) in the vertical section of the fabric, and T is the thickness (占 퐉) of the fabric.

The present invention also provides an electronic part such as a conductive tape and a gasket having a conductive fiber aggregate according to the present invention and an electronic apparatus having the same.

According to the present invention, the coating composition according to one embodiment of the present invention can easily prevent the physical / chemical damage of the supporting member in the process for forming the coating layer as the coating layer is easily formed even under the condition of forming the relaxed coating layer. In addition, it is possible to improve the formation of the coating layer due to the coating composition on the inner surface as well as the outer surface of the supporting member, and it is possible to realize a conductive fiber aggregate having excellent durability have. Further, the specific surface area of the formed coating layer is remarkably increased compared to the surface area of the supporting member, thereby enabling to exhibit excellent electromagnetic wave shielding performance. In addition, since it is provided with a wide specific surface area and exhibits excellent electromagnetic wave shielding performance due to excellent coating properties on the outer and inner surfaces of the supporting member and is excellent in durability of the coating layer even though it is coated on the supporting member, , Electronic devices, and the like.

BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 is a flow chart of a process for producing a conductive fiber aggregate according to a preferred embodiment of the present invention;
FIG. 2 is a perspective view of a conductive fiber aggregate according to a preferred embodiment of the present invention. FIG. 2 (a) is a partially enlarged perspective view of a conductive fiber aggregate including a fiber aggregate, Fig. 2C is an SEM photograph showing a metal layer coated on mono yarns, Fig. 2B is a cross-sectional view of the metal layer covered with the mono yarns, Fig.
FIG. 3 is a view of a conductive fiber aggregate according to a preferred embodiment of the present invention. FIG. 3 (a) is a view showing a conductive fiber aggregate having a fiber aggregate as a fabric, FIG. 3 Fig.
4 is a SEM photograph of the copper nanoparticles contained in the coating composition according to one preferred embodiment of the present invention,
5 is a cross-sectional schematic diagram of a composite fiber for producing a fiber aggregate according to a preferred embodiment of the present invention.

Hereinafter, exemplary embodiments of the present invention will be described in detail with reference to the accompanying drawings, which will be readily apparent to those skilled in the art to which the present invention pertains. The present invention may be embodied in many different forms and is not limited to the embodiments described herein. In order to clearly illustrate the present invention, parts not related to the description are omitted, and the same reference numerals are assigned to the same or similar components throughout the specification.

First, the coating composition according to the present invention will be described.

The coating composition is a composition for forming a metal layer provided on a conductive fiber aggregate, and includes a first metal precursor and a second metal.

Conventionally, a method of forming a conductive layer to form a conductive substrate has been used, as described above, in which a conductive coating composition is formed on a substrate through a conductive coating composition and a conductive layer is formed through various plating or vapor deposition methods. However, the plating / deposition method has a problem of oxidation of the conductive layer and weakening of adhesion. In addition, there is a problem in that the conductive layer is not easily formed in the inner region of the support member made of a complicated and fine structure like the fiber aggregate through the plating / vapor deposition method.

This problem also occurs in a method of forming a conductive layer through a coating composition. In particular, when a metal coating layer is formed through sintering in a metal precursor state, it is not very easy to form a metal coating layer in a fiber aggregate , There is a problem that a metal coating layer is formed only on the outer side of the fibrous aggregate. This is a result of poor heat resistance of the fibrous aggregate. Specifically, when heat is applied to the fibrous aggregate at a high temperature, there is a problem that the shape of the fibrous aggregate is deformed or the mechanical strength is weakened. In order to sinter the metal precursor There is a problem of not being able to apply a high temperature. In this case, the metal layer is easily formed on the outer surface of the fiber, which can be easily transferred even at a relatively low temperature, whereas a metal layer is difficult to be formed in the inner portion due to the difficulty of heat transfer. There is a problem that the shape of the fibrous aggregate is deformed or collapsed.

When the metal layer is formed only on the outer side of the fibrous aggregate, there is a problem that the improvement of the conductivity is insufficient when compared with the total volume of the conductive fibrous aggregate, and thus the electromagnetic wave chafing performance of the desired level is difficult to manifest.

As a result, the inventors of the present invention have conducted research to solve the above problems. As a result, it has been found that when the composition containing the metal precursor and the metal is treated and sintered, the inside of the fiber aggregate can be easily A coating layer is formed, and a conductive fiber aggregate having improved durability such as adhesion of a coating layer is realized, leading to the present invention.

The first all metal precursor may be a precursor such as a metal salt for the metal selected when preparing a conventional conductive substrate. For example, the first metal precursor may include at least one metal precursor selected from the group consisting of Cu, Ni, Co, Al, and alloys thereof.

The second metal may be one selected from the group consisting of Au, Pt, Pd, Ag, Cu, Ni, and alloys thereof. can do.

The second metal may preferably be a granular metal powder, and still more preferably a metal powder having a particle diameter of 10 to 100 nm. Since the granular metal powder can act as a growth nucleus when the first metal precursor is sintered, the formation of the coating layer can be remarkably improved even under the relaxed coating conditions even in a fiber aggregate in which heat is not easily reached. In addition, the adhesion between the fibrous aggregate and the coating layer also increases, thereby increasing the durability. Furthermore, the specific surface area of the coating layer can be remarkably increased due to the second metal of the granular phase, and the electromagnetic wave shielding performance can be further improved. However, when the particle diameter of the metal powder is less than 10 nm, there is a problem that the oxidation stability is greatly reduced and the conductivity is poor. When the particle diameter is more than 100 nm, the dispersibility is poor due to gelation, When the conductive fiber aggregate described below is composed of fibers having a diameter of nano unit, the second metal particles are located only on the surface of the fiber aggregate, There is a problem that it is difficult for the desired fiber aggregate to have excellent conductivity. The second metal is preferably contained in the composition in a gel state to prevent oxidation of the surface of the metal particles.

The coating composition may include the first metal precursor and the second metal at a weight ratio of 1: 0.9 to 4.5. If the second metal is less than 0.9 wt% as compared with the first metal precursor, formation of the metal layer on the inner surface of the fibrous aggregate is remarkably reduced, the specific surface area of the coating layer is insignificantly improved compared to the substrate surface area, There is a significant increase in the problem. In addition, if the second metal is contained in a ratio of more than 4.5 wt%, the content of the first metal precursor may be relatively small, so that the first metal may not be connected between the second metal particles, In this case, there is a problem that the sheet metal value increases rather than the second metal particles are gathered together and are not connected to each other. On the other hand, in this case, although the sheet resistance value is increased, the resistance value may not be measured because of the electrical short circuit as the metal layers can not be connected to each other. In addition, since the second metal particles can not be sparsely connected to each other and can be provided on the support, there may be a problem that adhesiveness to the fibrous aggregate to be described later is remarkably deteriorated.

According to a preferred embodiment of the present invention, the first metal precursor may be a copper precursor, and the second metal may be copper, more preferably copper powder. When the first metal precursor and the second metal are copper precursors and copper, respectively, they are excellent in dispersibility by a solvent and can exhibit excellent conductivity even when the unit cost is low.

 The coating composition may further comprise a dispersion solvent, and a binder compound.

The dispersion solvent functions to uniformly disperse the first metal precursor and the second metal. In the case of a solvent capable of uniformly dispersing the two components without affecting the first metal precursor and the second metal, Can be used. For example, the dispersion solvent may be at least one selected from the group consisting of ethylene glycol, glycol ether, and alcohol. Examples of the glycol ether include triethylene glycol dimethyl ether, triethylene glycol monobutyl ether, triethylene glycol monoethyl ether, diethylene glycol diethyl ether, diethylene glycol monobutyl ether, diethylene glycol dibutyl ether, ethylene Glycol monopropyl ether and dipropylene glycol methyl ether. The alcohol may be at least one selected from the group consisting of methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, Propanol, 1-pentanol, 1-pentanol, 3-pentanol, 2,2-dimethyl-1-propanol, Butanol, 2-methyl-1-butanol, 2,2-dimethyl-1-propanol, 3-hexanol, Butanol, 2-ethylbutanol, 2-ethylbutanol, 2-ethylbutanol, 2-ethylbutanol, Ol, may be at least one member selected from 2,6-dimethyl-4-heptanol, 2-methyl cyclohexanol, the group consisting of 3-methyl-cyclohexanol and 4-methyl-cyclohexanol.

In addition, the binder compound enables the second metal in the coating composition to more easily adhere onto the support before sintering, and can be pyrolyzed after sintering to be lost. The binder compound can be used without limitation as long as it is a component that can be pyrolyzed at a relatively low temperature. For example, at least one selected from the group consisting of polyvinyl alcohol (PVA), acrylic resin, urethane resin, polyester resin, polyvinylpyrrolidone (PVP), ethylene vinyl acetate copolymer (EVA) and polyethylene oxide (PEO) .

The dispersion solvent may be included in an amount of 600 to 700 parts by weight based on 100 parts by weight of the second metal, and the polymer may be included in an amount of 1 to 10 parts by weight based on 100 parts by weight of the second metal.

Hereinafter, a method for producing a conductive fiber aggregate through the coating composition according to one embodiment of the present invention will be described.

First, in step (1) according to the present invention, a step (S100) of treating the fiber aggregate according to the present invention is carried out.

A method of treating the fibrous aggregate with the coating composition may be a method of treating a liquid surface of a conventional ink or paste in the adherend surface. Non-limiting examples of this include blade coating, flow coating, casting, printing methods, transfer methods, brushing, dipping, silk screening or spraying The coating composition may be added. At this time, the amount of the coating film can be set differently depending on the thickness of the metal layer to be formed, so that the present invention is not particularly limited thereto. However, it may be treated with 200 to 1000 parts by weight per 100 parts by weight of the fibrous aggregate. If the coating composition is treated at less than 200 parts by weight, there is a problem that a metal layer can not be formed at a desired level. Further, when the treatment exceeds 1000 weight, the thickness becomes thick, the flexibility of the fibrous aggregate decreases, and there is a problem that the metal layer can be easily peeled off due to bending of the fibrous aggregate.

Next, in step (2), the coating composition is baked to form a fiber aggregate coated with a metal layer comprising a first metal and a second metal.

The calcination in the step (2) should be determined in consideration of not only the sintering temperature of the metal precursor and the metal particles in the coating composition but also the thermal properties of the fiber aggregate. However, the fiber-forming component that forms a typical fiber aggregate may have a shape change of the fiber aggregate at a temperature of 250 占 폚 or higher, and sometimes 230 占 폚 or higher, if necessary, except for some components such as para-aramid. , There is a problem that damage may occur. Whereby the sintering temperature of the metal precursor contained in the coating composition can not be increased to the desired level. Accordingly, the firing temperature is preferably 230 ° C. or lower, and more preferably 180 ° C. to 220 ° C. If the firing temperature is less than 180 ° C, there is a problem that the thermal decomposition of the dispersion solvent and the polymeric binder compound contained in the coating composition is not smooth and may remain in the metal layer. Also, the metal layer may not be produced at a desired level, or the adhesion between the metal layer and the fiber may be weak. Further, since the metal layer can not be firmly formed, cracks can easily occur. If the firing temperature is higher than 220 캜, there is a problem that the coating composition can not be applied to a fibrous aggregate formed of a fiber-forming component having poor thermal properties.

The calcination may preferably be performed for 10 to 30 minutes. However, the firing time may be selected depending on the firing temperature and is not limited thereto.

Meanwhile, the present invention relates to a fiber aggregate comprising a plurality of strands of monosa fabricated through the above-described manufacturing method; And a metal layer including a first metal and a second metal and covering at least the outside of the fiber aggregate.

The fibrous aggregate may be a fabric composed of a yarn comprising a plurality of strands of monosa, or a fabric including a plurality of strands of monosa, a knitted fabric and a nonwoven fabric.

The monosaccharide may be formed of a known fiber forming component. As a non-limiting example, the fiber forming component may be selected from the group consisting of nylon 4, nylon 6, nylon 7, nylon 11, nylon 12, nylon 66, nylon 6 10, polymetaxylene adipamide, polyparaxylanedecanamide Based polyesters such as polyamide-based, polyethylene terephthalate, polytetramethylene terephthalate, polybutylene terephthalate, polyethylene oxybenzoate and poly 14-dimethylcyclohexane terephthalate, polyolefins such as polyethylene and polypropylene, poly One kind of compound selected from the group consisting of polyvinyl, polyurethane and polyurea such as vinyl chloride, polyvinylidene chloride, polyvinyl alcohol, polyvinylidene cyanide, polyacrylonitrile and polystyrene, Or more copolymers.

The mono yarn may have a diameter of 0.02 탆 or more, and the yarn may include at least two mono yarns.

Also, the fabric may be a fabric, a knitted fabric, and a nonwoven fabric.

If the fabric is a fabric, the fabric may be a single yarn or a combination of warp and weft. The fabric may be any one selected from the group consisting of plain weave, twilled weave, water weave, and double weave. If the plain weave, twill weave, and water weave are three-dimensional tissue, the specific weaving method of each of the three-dimensional tissue is determined by a conventional weaving method, and it is possible to modify the tissue based on the three- There are, for example, changing jobs, changing jobs, changing jobs, changing jobs, changing jobs, non-working jobs, and twisting jobs. . The double yarn is a method of weaving a fabric in which either one of warp yarns or weft yarns is doubled or both yarns are doubled. The specific method may be a conventional double yarn weaving method. However, the present invention is not limited to the description of the fabric structure.

In addition, when the fabric is knitted, the fabric may be a knitted fabric knitted or knitted with the yarn. For example, the stitched knit / circular knit / warp knitted fabric may be a warp knitted fabric, and the knit fabric and the warp knit may each have a known structure.

If the fabric is a nonwoven fabric, the nonwoven fabric may be a nonwoven fabric prepared by providing a yarn in the form of a long fiber or a yarn cut into a short fiber by a known method.

Since the basis weight, thickness, etc. of the fabric can be selected differently according to the purpose, the present invention is not particularly limited thereto.

The metal layer includes a first metal and a second metal, and is provided to cover at least the outside of the fiber aggregate. More specifically, as shown in FIG. 2A, when the conductive fiber aggregate 100 is a yarn, a metal layer 120 including the outer surface of the yarn having the plurality of mono fibers 111, 112 and 113 is provided. The metal layer 120 may be formed by disposing the second metal particles 122a and 122b discontinuously on the surface of the mono-sphere as shown in Fig. 2B where the fourth mono-shed 114 of Fig. The first metal 121a may be connected to a space between the first and second metal particles to form a metal layer.

In addition, the metal layer may be covered with at least a part of the surface of the monosaccharide which is not exposed to the outside of the fibrous aggregate. Specifically, as shown in FIG. 2C in which the first mono yarn 111, the second mono yarn 112 and the third mono yarn 113 of FIG. 2A are partially enlarged, a third mono yarn The metal layers 121b and 122c are also formed on the outer surface of the first monocular yarn 113 and between the second monocular yarn 112 and the third monocular yarn 113 So that a more improved specific surface area and thus excellent electrical conductivity can be exhibited. Specifically, as shown in FIG. 2D, it can be confirmed that a metal layer is formed very well on the surface of a plurality of strands of monosaccharide.

3A, the fibrous assembly includes a weft yarn 211 and a warp yarn 212 that include a plurality of strands of monosma, and the fabric layer 220 includes a metal layer 220 ) Can be formed, and the fabric can satisfy the following conditions (a) and (b).

(a) 0.02? D (占 퐉)? 2.5

(b) 40 占 (D) ^-1.9 ? Y? 60 占 (D) ^-2.0

In the condition (a), D means the diameter (mu m) of the mono yarn. Unlike conventional yarns, the mono yarns (11, 12, 13) satisfying the preferred diameter range according to the present invention are ultra-fine fibers or nano-sized ultrafine fibers. Therefore, the outer and inner specific surface areas of the fiber bundles It is significantly improved compared to mono yarns of the same diameter as the bundle. The increase of the specific surface area of the fiber bundle has an advantage that the absolute amount of the conductive material that can be provided to the fabric can be increased as the area of the conductive material can be covered. In addition, in the case of microfine fibers having a diameter of nano-particles coated with a conductive material, there is an advantage that the scattering of electromagnetic waves incident on the fabric is increased to further enhance the electromagnetic wave removing performance. Furthermore, in the fiber bundle formed of ultrafine fibers having a diameter of nanoseconds, the spacing between the fibers is very narrow in micro or nano units, and an electromagnetic wave incident on such a narrow gap, for example, having a frequency of several to several tens of Hz Since the electromagnetic wave can be attenuated and shielded, there is an advantage that the electromagnetic wave removing performance can be further improved. Accordingly, it is preferable that the diameter of the mono yarns contained in the fiber bundles of the fabric satisfies the condition (a) according to the present invention. If the diameter of the monofilament is less than 0.02 탆, it is very difficult to manufacture at the current level of technology. Even if it can be realized through electrospinning, the production of yarn by electrospinning as compared with melt spinning may cause a decrease in productivity, , There is a technical problem that it is difficult to wind the electrospun nanofiber together with the filament yarn. In addition, if the diameter of the mono-filament yarn is too small, there may be a problem of remarkable lowering of the mechanical strength. In addition, the number of yarns that can be provided to the same thickness fabric may increase, and thus the specific surface area that can be covered with the conductive material may be increased. However, in this case, the amount of the conductive material to be coated is excessively increased, There is a problem that an electromagnetic wave shielding effect is generated which is small compared to the amount of the conductive material which is increased in weight and increased. In addition, if the diameter of the mono-sphere exceeds 2.5 탆, the scattering effect of the electromagnetic wave through the mono-sine can be remarkably reduced, and the electromagnetic wave shielding effect through the mono-sine spacing gap is not manifested, There is a problem. Further, as the number of fibers that can be provided in the thickness direction in the cross section of the fabric decreases, there is a problem that the electromagnetic wave shielding effect according to the layered fiber structure is reduced.

In addition, in the above condition (b), D is the monocular diameter (占 퐉), and Y is the monocular diameter (占 퐉) included per unit area (S, 100 占 퐉 ² ) (M).

As described above, when the conductive fibrous aggregate is a laminated structure, the electromagnetic wave removing performance is excellent according to the difference of the amount of the conductive material to be coated as compared with the monolayer structure of the same thickness. Particularly, there is a more advantageous structural advantage in high frequency and broadband electromagnetic wave shielding. Accordingly, the number of mono yarns per unit area (100 mu m < ² >) in the cross section of the fabric is set to satisfy the condition ( 2). If the number of mono yarns per unit area (100 탆 ² ) in the cross section of the fabric is less than the lower limit in consideration of the diameter of the mono yarn, electromagnetic wave shielding performance at a desired level of high frequency and wide band can not be exhibited. There is a problem that the removal performance can not be expressed. Also, if the number of mono yarns per unit area (100 μm ² ) in the cross section of the fabric exceeds the upper limit in consideration of the diameter of the mono yarn, the amount of the conductive material provided in the fabric is excessively increased to increase the production cost, There is a problem that an electromagnetic wave shielding effect is generated which is small compared to the amount of the conductive material which is increased in weight and increased.

On the other hand, the number of mono yarns per unit area (100 mu m < ² >) of the fabric is counted as one mono yarn completely contained in the unit area, and when only a part thereof is included, And counts the number. As an example, and assuming that the cross-sectional area's mono 10㎛ ^2, the use of mono when not being fully contained only a part cross-sectional area's include the mono total 56.7㎛ over ² days, number per unit area contained mono's over only a part included in the unit area is 56.7㎛ ^2/10 ㎛ ² = 5.67 ≒ 6 counts. On the other hand, as an example, when included with a mono's cross-sectional area exceeds 100㎛ ^2, a mono yarn on a unit area (100㎛ ²⁾ Y is only a part will be counted as one. In the case of a fabric having a mono yarn of different diameters, the number of mono yarns per unit area is determined by taking the cross-sectional area of each of the mono yarns into consideration, as described above. For example, suppose that a mono yarn A having a cross-sectional area of 2 mu m < ² > and a mono yarn B having a cross-sectional area of 6 mu m < ² > The total cross-sectional area of the mono-yarns A and the total cross-sectional area of the mono-yarns B on the basis of the difference in the radii can be obtained and the total number of mono yarns spanning the cross-sectional areas can be calculated.

In addition, according to a preferred embodiment of the present invention, sufficient mechanical strength is ensured even though it is realized to be slim to be suitable for the recent trend of authors having a small size and a small size, and more excellent high-frequency and wide- The fabric may further satisfy the following condition (c).

(c)

D is the monocular diameter (占 퐉), Y is the number of mono yarns per unit area (100 占 퐉 ² ) in the cross section of the fabric, and T is the thickness (占 퐉) of the fabric.

If the numerical value of the condition (c) is less than 8, the thickness of the fabric becomes too thin, so that even when the laminated fiber structure in the cross section of the fabric is layered into several hundreds or more layers, There is a problem that the electromagnetic wave removing performance is lowered as a whole, and mechanical strength is significantly lowered. If the value of the above equation (c) exceeds 20, the thickness of the fabric is excessively large, which is not suitable for being mounted on electronic parts and electronic devices which have recently become thinner and thinner, and the product cost increases .

3B, the fibrous assembly may be a nonwoven fabric in which a plurality of monosilings 311 are formed in a three-dimensional network structure, and a metal layer 330 is provided on the outer and inner surfaces of the nonwoven fabric, 300).

The above-described conductive fiber aggregate according to the present invention can be well suited for shielding excellent electromagnetic conductance and high frequency and wide frequency band electromagnetic waves. Accordingly, the conductive fiber aggregate according to the present invention can be applied to a gasket having the same, an electronic product having the same, and the like. In addition, the conductive fiber aggregate is provided with at least one adhesive layer on at least one surface thereof, and can be widely applied to various electronic products by being embodied as an electromagnetic wave shielding tape.

The present invention will now be described more specifically with reference to the following examples. However, the following examples should not be construed as limiting the scope of the present invention, and should be construed to facilitate understanding of the present invention.

≪ Example 1 >

To prepare the coating composition, the first solution of the copper precursor prepared in Preparation Example 1 below and the copper nanoparticle gel prepared in Preparation Example 2 were mixed so that the weight of the copper precursor and the copper nanoparticles became 1: 1 . Thereafter, ethylene glycol was added in an amount of 660 parts by weight based on 100 parts by weight of the copper nanoparticles. The mixed solution was dispersed by high-frequency vibration for 1 hour and stirred for 2 hours to prepare a dispersed coating composition as shown in Table 1 below.

* Preparation Example 1

To prepare the copper precursor solution 1, 9.6 g of copper acetate was added to 10 ml of a 1: 1 volume ratio of ethanol and ethylene glycol, followed by stirring to completely dissolve the solution. To this solution, 8 ml of cyclohexylamine was added dropwise for 1 minute, and after 10 minutes, 4.4 ml of formic acid was added and the mixture was reacted for 1 hour to prepare a first solution whose color changed from blue to green .

* Preparation Example 2

To prepare the copper nano-gel, 200 ml of a mixed solvent of distilled water and ethylene glycol in a volume ratio of 1: 1 was raised to 60 ° C, and 2.75 g of Cu (NO ₃ ) ₂ .3H ₂ O was added and stirred to dissolve completely . To this solution, 7.5 g of polyvinylpyrrolidone (PVP MW 40,000, SIGMA-ALDRICH) was added and stirred vigorously. 12.5 ml of hydrazine (JUNSEI) was added dropwise to the solution containing polyvinylpyrrolidon for 1 minute and stirred for 1 hour, followed by centrifugation at 5,000 rpm for 10 minutes through a centrifuge to obtain 2 g of a precipitate. As a result, it was confirmed that copper nanoparticles having an average diameter of 100 nm as shown in Fig. 4 were produced

≪ Example 2 >

The coating composition was prepared in the same manner as in Example 1 except that the weight ratio of copper precursor to copper nanoparticles in the coating composition was varied as shown in Table 1 below.

≪ Comparative Examples 1 and 2 &

Except that the copper precursor and copper nanoparticles in the coating composition were used in the same manner as in Example 1, and the coating compositions as shown in Table 1 were prepared without using the copper nanoparticles as shown in Table 1 below.

≪ Preparation Example 1 &

The coating compositions prepared in Examples and Comparative Examples were coated with 600 parts by weight of the coating composition per 100 parts by weight of the fibrous aggregate using a bar coater in the fiber aggregate prepared in Preparative Example 3 below, Followed by firing to prepare a conductive fabric as shown in Table 1 below.

* Preparation Example 3

First, in order to produce the composite fiber having the cross-section as shown in FIG. 5, the composite fiber having 37 fiber-forming portions in a single composite fiber can be irradiated with a total of 24 fibers, The terephthalate was introduced into the component supplying part and the alkali-soluble component prepared in Preparation Example 4 was charged into the component supplying part as the eluting component (22). The components were melted at 285 DEG C and spinning temperature was 275 DEG C, mpm to obtain a composite fiber bundle having a total fineness of 75 denier 24 strands and a diameter of about 2 mu m in the fiber forming portion in a single composite fiber.

The obtained composite fiber bundle was used as warp and weft to weave a fabric having an oblique density of 212 yarns / inch and a weft density of 86 yarns / inch, a plain weave, a width of 20 cm, and a thickness of 0.16 mm.

The woven fabric was cut to a width of 20 cm x 20 cm and immersed in a 5 wt% sodium hydroxide aqueous solution at 90 ° C for 1 hour, and then the alkali-soluble component, which is a decomposition product of the composite fiber, was reduced. After the weight loss, the fabrics were washed with water and dried, and then immersed in an aqueous solution of 2% by weight of a surfactant (Dow Chemical, triton20), refined at 40 ° C for 20 minutes, washed again with distilled water, Aggregates were prepared.

* Preparation Example 4

Terephthalic acid (TPA) and ethylene glycol (EG) were adjusted to a molar ratio of 1: 1.2, and sodium 3,5-dicarbomethoxybenzenesulfonate was added in an amount of 1.5 moles based on the total amount of terephthalic acid and sodium 3,5-dicarbomethoxybenzenesulfonate %. Further, 10.0 parts by weight of lithium acetate as a catalyst relative to 100 parts by weight of sodium 3,5-dicarbomethoxybenzenesulfonate was mixed and esterified at 250 ° C under a pressure of 1140 Torr to obtain an ester reaction product. The reaction rate was 97.5%.

The resulting ester reactant was transferred to a condensation polymerization reactor and 10.0 parts by weight of polyethylene glycol (PEG) having a molecular weight of 6000 was added to 100 parts by weight of the ester reactant. Then, 400 ppm of antimony trioxide was added as a condensation polymerization catalyst so that the final pressure became 0.5 Torr The temperature was raised to 285 DEG C while gradually reducing the pressure, and the condensation polymerization reaction was carried out to obtain an alkali-soluble copolyester resin.

<Experimental Example 1>

The following properties of the conductive fabric prepared in Production Example are evaluated and shown in Table 1 below.

1. Surface resistance

Resistivity values were measured using a surface resistance meter (SR2000N).

2. Formation amount of metal layer

The weight of the fibrous aggregate before the formation of the metal layer was measured and the weight of the fibrous aggregate after the formation of the metal layer was measured to divide the weight (g) of the metal layer provided by the weight of the fibrous aggregate (g) Respectively.

3. Adhesion evaluation

The scotch tape was attached to the fabricated conductive fabric and peeled off to evaluate the state of transfer of the metal layer to the adhesive surface. When no transfer was found on the adhesive surface of the tape, the tape was transferred to the adhesive surface at a rate of 30% or less of the total adhesive surface of the tape, separated from the substrate, and exceeded 30% And when it is transferred, it is indicated by x.

Example 1 Example 2 Example 3 Example 4 Example 5 Comparative Example 1 Comparative Example 2 covering
Composition Copper precursor:
Copper nanoparticle weight ratio 1: 1 1: 0.8 1: 2 1: 4 1: 5 Copper nanoparticles not included Copper
Without precursor conductivity
Fibrous aggregate The amount of metal layer formation per unit weight of the fibrous aggregate
(g / g) 1.8 1.1 5.6 8.0 8.2 1.4 0.8 Properties Resistivity (Ω / □) 2.4 4.6 0.4 4 12 10 Measure
no Adhesiveness ○ △ ○ ○ △ △ ×

As can be seen in Table 1,

The conductive fiber aggregate coated with the coating composition containing no copper nanoparticles had a resistivity of 10 Ω / □, which means that the physical properties thereof were markedly lowered than in Example 1, and the adhesiveness was also lowered.

Further, the conductive fiber aggregate coated with the coating composition containing no copper precursor was not measured for its resistivity, and it is expected that even though the copper nanoparticles were baked to form a metal layer, the connectivity between them was very weak and resistance was not measured by the electrical short circuit , It can be confirmed that the adhesiveness is significantly lowered compared with the examples. Particularly, as the adhesion of the metal layer is weak and it is easily separated from the fibrous aggregate after being fired, it can be confirmed that the weight of the metal layer formed per unit weight of the fibrous aggregate is very small.

 In Examples 2 and 5, in which the weight ratio between the copper precursor and the copper nanoparticles in the coating composition deviates from the preferred range of the present invention, the resistivity was very high as compared with Examples 1, 3 and 4, I can confirm that it is not good.

&Lt; Preparation Examples 2 to 8 &

The fibrous aggregate was prepared in the same manner as in Production Example 1 except that the fibrous aggregate was prepared by modifying the fibrous aggregate as shown in Table 2 below and then fired under the same treatment and the same treatment conditions as in Example 1, Fiber aggregates were prepared.

<Experimental Example 2>

The following properties of the conductive fiber aggregates prepared in Production Examples 1 to 8 were evaluated and shown in Table 2 below.

1. Surface resistance

Resistivity values were measured using a surface resistance meter (SR2000N) and are shown in Table 2 below. At this time, the resistivity values of the fibrous aggregates according to other production examples were relatively expressed based on the resistivity value in Production Example 1 as 100. [

2. Condition satisfied

The following conditions (a) to (c) were evaluated.

(a) 0.02? D (占 퐉)? 2.5

(b) 40 占 (D) ^-1.9 ? Y? 60 占 (D) ^-2.0

(c)

D is the monocular diameter (占 퐉), Y is the number of mono yarns per unit area (100 占 퐉 ² ) in the vertical section of the fabric, and T is the thickness of the fabric (占 퐉).

At this time, Y cuts the fabric in an oblique direction and a weft direction, and counts the number of mono yarns per unit area through a SEM photograph of the cut surface. At this time, the number of mono yarns per unit area counted by cutting in the oblique direction is expressed as a condition (b) for weft yarn, and the number of mono yarns per unit area counted by cutting in the weft direction is set as a condition (b) Respectively.

3. Formation amount of metal layer

The weight of the fibrous aggregate before the formation of the metal layer was measured, and the weight of the fibrous aggregate was measured after the formation of the metal layer to calculate the weight of the provided metal layer. At this time, the weight of the metal layer in Production Example 1 was relatively expressed based on the weight of the metal layer in Production Example 1 as 100.

Production Example 1 Production Example 2 Production Example 3 Production Example 4 Production Example 5 Production Example 6 Production Example 7 Production Example 8 Weaving yarn The fiber forming part in the composite fiber
(Number / diameter (占 퐉)) 37/2 37/2 37/2 37/2 37/2 - 37/3 37/2 Composite fiber bundle
(Total fineness (de ') /
Strand number) 75/24 75/24 75/24 75/24 75/24 - 75/24 75/24 Non-conjugated fiber bundle
(Number / diameter (占 퐉)) - - - - - 48/12 - - Before weight loss
textile Inclined density
(Number / inch) 212 180 170 170 620 - 212 150 Weft density
(Number / inch) 86 70 65 50 430 - 86 45 Thickness (㎛) 160 130 116 100 300 - 160 80 Fabric after weight loss Inclined density
(Number / inch) 188,256 159,840 150,960 150,960 550,560 122 188,256 159,840 Weft density
(Number / inch) 76,368 62,160 57,720 44,400 381,840 98 76,368 44,400 Thickness (㎛) 80 65 58 50 150 60 80 40 Properties Condition (1) Satisfaction ○ ○ ○ ○ ○ × × ○ Condition (2) Range 10.7 ~ 15 10.7 ~ 15 10.7 ~ 15 10.7 ~ 15 10.7 ~ 15 0.36-0.42 5.0 to 6.7 10.7 ~ 15 Condition (2) Satisfaction
(Slope direction section / weft direction section section) ○
(13/13) ○
(12/12) ○
(12/12) ○
(10/10) ○
(15/15) ○
(1/1) ○ (6/6) ×
(9/9) Condition (3) Satisfaction
(value) ○ /
11.09 ○ /
9.01 ○ /
8.37 X /
7.91 X /
20.80 X /
5.00 ○ /
11.16 ○ /
10.00 Resistivity (%) 100 106 109 121 94 128 126 133 Weight of metal layer (%) 100 110 96 90 180 60 90 90

As can be seen from Table 2 above,

It can be seen that the specific resistance values of the conductive fiber aggregates according to Production Examples 6 to 8 prepared from the fibrous aggregates which do not satisfy either the condition a or the condition b according to the present invention are significantly increased as compared with those of Production Example 1. [

In the case of Production Examples 1 to 5, which satisfy the conditions a and b according to the present invention at the same time, Production Examples 1 to 3 satisfying Condition c are superior in conductivity to Production Example 4. In addition, in the case of Production Example 5, even though the thickness of the fabric and the weight of the metal layer loaded on the surface of each mono-sheet are significantly larger than those of Production Example 1, the degree of improvement in conductivity is increased And thus it can be confirmed that the conductive material of Example 1 exhibits excellent conductivity even though it is thinner and slimly realized.

While the present invention has been particularly shown and described with reference to exemplary embodiments thereof, it is to be understood that the invention is not limited to the disclosed exemplary embodiments, It will be understood by those skilled in the art that various changes in form and details may be made therein without departing from the spirit and scope of the invention as defined by the appended claims.

15: fiber forming component 22: eluted component
100, 200, 300: Conductive fiber aggregates 111, 112, 113, 114, 311:
120: metal coating layers 121a and 121b: first metal
122a, 122b, 122c: second metal particles

Claims (20)

A coating composition for forming a metal layer on a conductive fiber aggregate,
Wherein the coating composition comprises a first metal precursor and a second metal. The method according to claim 1,
Wherein the second metal is a particulate coating composition for improving the metal layer forming ability and the specific surface area of the metal layer in the fiber aggregate. The method according to claim 1,
Wherein the first metal precursor includes at least one selected from the group consisting of Cu, Ni, Co, Al and alloys thereof,
Wherein the second metal comprises at least one selected from the group consisting of Au, Pt, Pd, Ag, Cu, Ni, and alloys thereof. The method according to claim 1,
Wherein the coating composition comprises a first metal precursor and a second metal in a weight ratio of 1: 0.9 to 4.5.
The method according to claim 1,
The coating composition may contain at least one dispersing solvent selected from the group consisting of ethylene glycol, glycol ether and alcohol,
At least one binder compound selected from the group consisting of polyvinyl alcohol (PVA), acrylic resin, urethane resin, polyester resin, polyvinylpyrrolidone (PVP), ethylene vinyl acetate copolymer (EVA) and polyethylene oxide (PEO) &Lt; / RTI &gt; 3. The method of claim 2,
And the second metal is a metal powder having a particle diameter of 10 to 100 nm. The method of claim 3,
Wherein the first metal precursor is a copper precursor and the second metal is copper. (1) treating the fibrous aggregate with the coating composition according to any one of claims 1 to 7; And
(2) firing the coating composition to form a fibrous aggregate coated with a metal layer comprising a first metal and a second metal. 9. The method of claim 8,
Wherein the coating composition is treated with 200 to 1000 parts by weight based on 100 parts by weight of the fibrous aggregate in the step (1). 9. The method of claim 8,
Wherein the firing is performed at a temperature of 180 to 220 DEG C for 1 to 30 minutes. A fibrous aggregate comprising a plurality of strands of monosa; And
And a metal layer including a first metal and a second metal and covering at least the outside of the fiber aggregate. 12. The method of claim 11,
Wherein the fibrous aggregate is a fabric of any one of a yarn comprising a plurality of strands of monosa, or a fabric comprising a plurality of strands of monosa, a knitted fabric and a nonwoven fabric. 12. The method of claim 11,
Wherein the metal layer comprises at least a part of a surface of a monosaccharide which is not exposed to the outside of the fibrous aggregate. 12. The method of claim 11,
The second metal is provided in a granular form in order to improve the metal layer forming ability and the specific surface area of the metal layer in the fiber aggregate,
Wherein the metal layer comprises a second metal in the granular form and a first metal connecting the second metal particles. 15. The method of claim 14,
Wherein a diameter of the second metal is 1/2 to 1/250 of the diameter of a monocomponent provided in the fibrous aggregate. 12. The method of claim 11,
Wherein the first metal includes at least one selected from the group consisting of Cu, Ni, Co, Al and alloys thereof,
Wherein the second metal comprises at least one selected from the group consisting of Au, Pt, Pd, Ag, Cu, Ni, and alloys thereof. 12. The method of claim 11,
Wherein the fibrous aggregate comprises a bundle of fibers comprising a plurality of strands of monosar in the warp and weft, and satisfies the following conditions (a) and (b):
(a) 0.02? D (占 퐉)? 2.5
(b) 40 占 (D) ^-1.9 ? Y? 60 占 (D) ^-2.0
D is the monocular diameter (占 퐉), and Y is the number of mono yarns per unit area (100 占 퐉 ² ) in the vertical section of the fabric. 18. The method of claim 17,
Wherein the fibrous aggregate further satisfies the following condition (3):
(3)

D is the monocular diameter (占 퐉), Y is the number of mono yarns per unit area (100 占 퐉 ² ) in the vertical section of the fabric, and T is the thickness (占 퐉) of the fabric. A gasket comprising the conductive fiber assembly according to claim 11 or 18. An electronic device comprising a conductive fiber assembly according to claim 11 or 18.

Images