KR101811993B1 - METAL-PLATED GLASS FIBER SMC(Sheet Moldings Compound) FOR EMI SHIELDING AND MANUFACTURING METHOD THEREBY - Google Patents

Abstract

The present invention relates to a process for preparing an electroless plating solution and a glass fiber comprising (a) an electroless plating solution containing a metal salt, a reducing agent and a complexing agent, (b) forming a metal plating layer on the surface of the glass fiber by a chemical reduction reaction using an electroless plating solution (C) a step of forming a metal plating layer, and (f) a step of forming a metal plating layer on the surface of the glass fiber on which the metal plating layer is formed, (D) a sizing treatment step of performing a silane coating treatment on the surface of the heat-treated metal-plated glass fiber; and (e) the step of (a) (d), the metal-plated glass fiber SMC for electromagnetic wave shielding is manufactured by using the metal-plated glass fiber having enhanced purity and metal bonding strength To a metal-coated glass fiber SMC for electromagnetic shielding.
The present invention also provides a metal-coated glass fiber SMC for electromagnetic wave shielding which is produced by a method of manufacturing a metal-coated glass fiber SMC for electromagnetic wave shielding.

Description

FIELD OF THE INVENTION [0001] The present invention relates to a metal-coated glass fiber SMC for electromagnetic shielding and a method of manufacturing the same. BACKGROUND OF THE INVENTION [0002]

The present invention relates to a method of manufacturing a semiconductor device comprising the steps of depositing nickel (Ni), copper (Cu), tin (Sn), zinc (Zn), gold (Au), silver (Ag), lead (Pb), aluminum (Al), cobalt Cr) and glass fiber SMC (Sheet Moldings Compound) manufactured using the same. More particularly, the present invention relates to a glass fiber-metal SMC (Sheet Molding Compound) A metal plating glass having enhanced purity for metal shielding and a metal bonding force capable of increasing the electrical conductivity and electromagnetic shielding ability by increasing the purity of the metal plating layer and increasing the mechanical bonding strength with the polymer resin due to the surface embossing effect of the metal plating layer Fiber, and a metal-coated glass fiber SMC (sheet molding compound) for shielding electromagnetic waves manufactured using the same.

In recent years, the demand for electromagnetic waves has increased due to the remarkable development of information technology. Wireless communication that uses electromagnetic waves as a communication medium is one of important living and industrial bases in modern society, making full use of the characteristics of electromagnetic waves that can transmit information immediately over time and distance.

However, if the electric and electronic devices are not resistant to the environment in such electromagnetic environment, it may cause malfunction or failure.

In addition, when the living body is exposed to a strong electromagnetic field, biological side effects such as increase in deep body temperature due to electromagnetic energy or nerve caused by current shock and muscle excitement may occur.

On the other hand, in recent years, the housing of the electronic device has been shifted from the metal to the plastic system in accordance with the demand for lighter weight.

When plastics introduction is applied, there is a slight advantage over metals. However, since plastic is an insulator without electricity, there is no electromagnetic shielding ability.

For this reason, the technology development and demand for the electromagnetic shielding ability of the plastic housing material is increasing.

In accordance with the above-mentioned circumstances, the conventional art has conventionally used a method of imparting conductivity to plastics to impart electromagnetic wave shielding ability.

For example, a method of incorporating glass fibers and graphite particles capable of absorbing electromagnetic waves is disclosed.

The prior art has a technical limitation in that it is limited to improving the interfacial bonding force with the resin by using the electroless plating method.

On the other hand, in the case of the housing of the electronic equipment, not only the electromagnetic wave shielding ability but also the strength against the external impact are required.

Thus, there has been a need for a fibrous filler having a high aspect ratio.

For this reason, development has been made in the direction of improving mechanical strength and electromagnetic shielding ability by using glass fiber as a leadfill to improve strength, plating metal directly on glass fiber, and using it as a filler.

However, when such a method of incorporating metal particles is used, it is difficult to uniformly disperse the whole of the polymer resin due to the high density of the metal particles, so that the physical properties of the composite material to be finally produced can be lowered.

Therefore, research and development using metal as a filler on the surface of glass fiber was sought.

However, when fabricating the fiber-reinforced plastic composite material using the metal-plated glass fiber as described above, the metal plating layer is often separated from the glass fiber due to the frictional force with the polymer resin, resulting in difficulty in actual application.

Methods for producing a metal film by reducing and depositing metal ions from the metal salt solution on the object to be plated and producing highly conductive glass fibers include an electrolytic plating method in which electrolytic deposition is performed by external electric power, a chemical reduction method in which metal ions in a solution are reduced and precipitated by a chemical agent A plating method and a displacement plating method in which metal ions in a solution are displaced and precipitated through water as a plated body.

Here, in the case of the electrolytic plating method, the base layer must be a conductor, and there is a problem that the thickness becomes uneven in the surface phenomenon of the base layer due to the influence of the current density.

Further, when the electrolytic plating method is used in a complicated shape, uniform plating is difficult. In addition, when the glass fiber is plated with metal and mixed with the polymer to produce a composite material, the metal plating layer is peeled off due to the friction with the polymer, thereby deteriorating the physical properties of the composite material.

In order to solve such a problem, a technique has been sought for a metal-plated glass fiber for electromagnetic wave shielding which prevents the phenomenon of peeling of the metal plating layer and which has excellent physical properties of the composite material finally produced.

An invention such as that disclosed in Korean Patent Laid-Open Publication No. 2002-0063465 (Title of the Invention: Method for manufacturing upper layer having electromagnetic wave absorption and deodorization function) has been proposed by the prior art.

SUMMARY OF THE INVENTION The present invention has been made to solve the above problems and it is an object of the present invention to improve the electrical conductivity and electromagnetic shielding ability by increasing the purity of the metal plating layer while reducing the peeling phenomenon through the high interfacial bonding force of the glass fiber metal plating layer, Metal plating with enhanced purity and adhesion strength for electromagnetic shielding that can increase mechanical bonding strength with polymer resin by surface embossing effect Glass fiber and metal plating for electromagnetic wave shielding made by using it Glass fiber SMC ). ≪ / RTI >

According to an aspect of the present invention, there is provided a method of preparing a glass fiber, comprising the steps of: (a) preparing an electroless plating solution and a glass fiber including a metal salt, a reducing agent and a complexing agent; (b) forming a metal plating layer on the surface of the glass fiber through a chemical reduction reaction using the electroless plating solution; (c) fusion bonding is performed between the surface of the glass fiber on which the metal plating layer is formed and the metal plating layer with respect to the glass fiber on which the metal plating layer is formed through the metal plating layer formation step to improve the interfacial adhesion force, A metal-plated glass fiber heat treatment step of performing heat treatment so as to remove impurities present; (d) a sizing treatment step of performing silane coating treatment on the metal-plated glass fiber subjected to the heat treatment step; And (e) fabricating a metal-coated glass fiber SMC for shielding electromagnetic waves using the metal-plated glass fibers having enhanced purity and metal bonding strength through the steps (a) to (d) A method of manufacturing a plated glass fiber SMC can be provided.

The metal salt may be at least one selected from the group consisting of a nickel salt, a copper salt, a tin salt, a zinc salt, a gold salt, a silver salt, a lead salt, , Cobalt (Co) salt and chromium (Cr) salt.

The electroless plating solution may have a pH of 2 to 11.

The metal-plated glass fiber SMC may be any of unsaturated polyester resin, epoxy resin, phenol resin, polyurethane resin, urea resin, melamine resin melamine resin.

In the step (c), the heat treatment may be performed at a temperature of 300 to 800 degrees Celsius for 5 minutes to 60 minutes.

After step (c), the metal content in the plated metal layer of the glass fiber may be 95 wt% or more.

After step (c), the metal plated glass fibers may have an electrical conductivity of 1 x 10 < 3 > (S / cm) to 6 x 10 < 5 >

The sizing treatment may be performed using a dilute solution using at least one silane selected from the group consisting of Amino-silane, Epoxy-silane, Methacrylate-silane, Vinyl-silane, Alkyl-silane and Phenyl- Plated glass fiber surfaces can be coated.

In addition, it is possible to provide a metal-coated glass fiber SMC for electromagnetic wave shielding, which is produced by a method of manufacturing a metal-plated glass fiber SMC for electromagnetic wave shielding.

The metal-coated glass fiber SMC for electromagnetic wave shielding may comprise 5.0 wt% to 80 wt% of the metal-plated glass fiber.

According to an embodiment of the present invention, metal-plated glass fiber reinforced with purity for electromagnetic wave shielding and metal bonding strength and metal-coated glass fiber SMC for shielding electromagnetic waves using the same can provide a molding material for a fiber-reinforced plastic part for shielding electromagnetic waves .

Further, the interfacial bonding force with the thermosetting resin can be increased due to the improvement of the interfacial adhesion between the glass fiber and the metal plating layer by the heat treatment of the metal-plated glass fiber of the present invention and the embossing effect of the surface of the metal plating layer. As a result, the strength of the fiber-reinforced plastic part manufactured using the metal-coated glass fiber SMC for shielding electromagnetic waves can be increased as a whole.

In addition, the present invention can improve the metal purity of the metal plating layer to be finally produced, and can have a relatively high electrical conductivity, as compared with the conventional chemically reduced metal plated glass fiber for use as an electromagnetic shielding material.

In addition, the present invention has an effect of preventing the peeling of the metal plating layer, which may occur, when the fiber-reinforced plastic using the metal-plated glass fiber is produced by increasing the interfacial bonding strength between the glass fiber surface and the metal plating layer.

BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 is a photograph showing a cross section of electroless nickel plated glass fiber produced according to the method of manufacturing a metal-plated glass fiber with enhanced purity and metal bonding strength according to an embodiment of the present invention;
FIGS. 2A and 2B are photographs showing a process of changing the surface shape of the heat-treated nickel-plated glass fiber produced according to the method of manufacturing a metal-plated glass fiber having enhanced purity and metal bonding strength according to an embodiment of the present invention.
3 is a photograph showing the principle of surface shape change of the heat-treated nickel plated glass fiber produced according to the method of manufacturing a metal-plated glass fiber with enhanced purity and metal bonding strength according to an embodiment of the present invention.
FIG. 4 is a photograph showing the interfacial bonding state between the glass fiber and the nickel layer after the heat treatment, which is produced according to the method of manufacturing the metal-plated glass fiber with enhanced purity and metal bonding strength according to the embodiment of the present invention.
5 is a schematic view showing a principle in which the interfacial fusion state of FIG. 4 is formed.
FIG. 6 is a graph showing a pattern of electromagnetic shielding ability of a nickel-plated glass fiber or polymer composite according to a heat treatment manufactured according to a method of manufacturing a metal-plated glass fiber with enhanced purity and metal bonding strength according to an embodiment of the present invention.
7 is a flowchart showing a method of manufacturing a metal-coated glass fiber SMC for electromagnetic wave shielding according to an embodiment of the present invention.

Hereinafter, the description of the present invention with reference to the drawings is not limited to a specific embodiment, and various transformations can be applied and various embodiments can be made. It is to be understood that the following description covers all changes, equivalents, and alternatives falling within the spirit and scope of the present invention.

In the following description, the terms first, second, and the like are used to describe various components and are not limited to their own meaning, and are used only for the purpose of distinguishing one component from another component.

Like reference numerals used throughout the specification denote like elements.

As used herein, the singular forms "a", "an" and "the" include plural referents unless the context clearly dictates otherwise. It is also to be understood that the terms " comprising, "" comprising, "or" having ", and the like are intended to designate the presence of stated features, integers, And should not be construed to preclude the presence or addition of one or more other features, integers, steps, operations, elements, components, or combinations thereof.

Hereinafter, embodiments of the present invention will be described in detail with reference to FIGS. 1 to 7. FIG.

In order to accomplish the object of the present invention, glass fibers plated with a chemical reduction method such as nickel, copper, tin, zinc, gold, silver, lead, aluminum, cobalt, chrome and alloys thereof are heat treated. Specifically, the heat treatment is carried out at an appropriate time and temperature to form a suitable thickness of the plating layer, to strengthen the bonding strength between the glass fiber and the plating layer through the change of the plating layer shape due to the heat treatment, The bonding strength can be improved, and finally, the electromagnetic wave shielding ability of the polymer composite material can be improved.

The method characteristic of the present invention is that the glass fiber can be metal plated through a chemical reduction method and then strengthened in the bonding strength between the plated metal surface and the glass fiber surface through a heat treatment process.

In addition, the present invention can increase the purity of the metal to be plated, increase the particle diameter of the metal, and increase the roughness of the surface of the metal layer (which may cause an increase in the mechanical interface strength with the resin ) Finally, it is a method capable of producing a functional fiber having improved toughness and electromagnetic shielding ability.

In addition, in the conventional chemical reduction metal plating method, impurities such as phosphorus (P) and boron (B) are added to the metal plating layer by a reducing agent such as dental phosphates and sodium borohydride such as sodium hypophosphoric acid, sodium hypophosphite, The present invention provides a method of manufacturing a metal-glass-fiber-reinforced composite material which has high electrical conductivity, high metal-grain size, And can impart an embossing effect to a metal surface.

The present invention also relates to a method of manufacturing a metal-coated glass fiber having enhanced purity and metal bonding strength, which comprises immersing a glass fiber in an electroless plating solution using a chemical reduction reaction including a metal salt, a reducing agent and a complexing agent.

In addition, the method of manufacturing a metal-plated glass fiber having enhanced purity and metal bonding strength is a method in which a glass is subjected to metal plating by a chemical reduction method, which is effective not only in plating the glass fiber, which is an insulator, Of the metal plating film.

In addition, according to the embodiment of the present invention, a method of manufacturing a metal-plated glass fiber having enhanced purity and metal bonding strength is characterized in that a metal plating solution in which a metal salt, a reducing agent and a complexing agent coexist is subjected to a chemical reduction metal plating treatment, Which is capable of improving the electrical conductivity while forming a metal film having a constant thickness.

The method of manufacturing a metal-coated glass fiber with enhanced metal bonding strength for shielding electromagnetic waves according to an embodiment of the present invention may be performed through a preparation step, a metal layer formation step, and a heat treatment (impurity removal and metal bonding power enhancement) steps.

The preparation step is a step of preparing an electroless plating solution containing a metal salt, a reducing agent and a complexing agent, and a glass fiber.

The metal salt may be at least one selected from the group consisting of a nickel salt, a copper salt, a tin salt, a zinc salt, a gold salt, a silver salt, a lead salt, A salt of cobalt (Co), and a salt of chromium (Cr).

The metal layer forming step is a step of forming a metal layer on the glass fiber surface through a chemical reduction reaction using an electroless plating solution.

The heat treatment step is a step of performing a predetermined heat treatment to remove impurities in the metal layer and improve interfacial adhesion between the surface of the glass fiber and the metal layer with respect to the glass fiber having the metal layer formed through the metal layer forming step.

Further, in the heat treatment step of post-plating heat treatment, the heat treatment temperature may be in the range of 300 to 800 degrees Celsius under the active or inactive state. That is, it is not easy to increase the bonding strength between the glass fiber and the metal plating layer at a temperature below 300 ° C., and the glass fiber may be damaged at a temperature above 800 ° C., so that it is preferable to perform the heat treatment between 300 ° C. and 800 ° C. More specifically, in the case of nickel plating, about 600 deg. C is preferable.

In addition, the heat treatment time can be made within 5 to 60 minutes. That is, when the heat treatment time is too short, the removal of impurities such as phosphorus or boron present in the metal plating layer is not sufficient and the bonding force between the metal plating layer and the glass fiber can not be maintained. There is no big problem in more than 60 minutes, but the heat treatment for 60 minutes or more is meaningless because no additional effect occurs.

In addition, impurities (such as phosphorus and boron components) on the heat-treated metal-plated glass fiber are preferably 5 wt% or less.

In addition, in the heat treatment step, impurities of the phosphorus and boron components are removed, and the plating layer is changed to an embossed form, and the plating layer of the embossed structure is made of fiber reinforced plastics manufactured using glass fiber according to the embodiment of the present invention It is possible to improve the interfacial bonding force with the polymer resin.

As a result, the present invention aims at minimizing impurities through a heat treatment process after plating treatment by general chemical reduction, thereby achieving a desired object of the invention (strengthening of adhesion between the metal plating layer and the glass fiber, improvement of electric conductivity, Improvement) can be achieved.

As a result, the electromagnetic wave shielding material can be effectively manufactured through the composite sample of the heat-treated metal-coated glass fiber and the resin (epoxy resin, etc.). However, the resin as the base material is not limited to any specific resin.

Through the above steps, the present invention can effectively manufacture metal-plated glass fibers having enhanced purity and metal bonding strength and composite fibers using the same.

Further, the method may further include a secondary plating step and a secondary heat treatment step of performing metal plating on the metal-plated glass fiber having enhanced purity and metal bonding strength according to an embodiment of the present invention through an electrolytic plating method.

Further, the glass fiber produced by the metal-plated glass fiber having enhanced purity and metal bonding strength according to the embodiment of the present invention can be used as a glass fiber having electrical conductivity of 1 * 10 ³ (S / cm) to 6 * 10 ⁵ It is preferable to have conductivity.

The pH of the electroless metal plating solution of the present invention is preferably in the range of 2 to 11 although it depends on the type of metal to be plated. This is because, when the pH is higher than 11, the liquid is self-decomposed to prevent plating, and when the pH is lower than 2, the quality of the plating layer is lowered.

In the method of the present invention, the thickness of the plating layer is preferably 0.1 to 2.0 mu m. If the thickness is less than 0.1 탆, the metal film (metal layer) is formed too thin, which is disadvantageous for measuring the electrical conductivity. If the thickness is more than 2.0 탆, the metal film becomes too thick, .

Further, in the metal-plated glass fiber having enhanced purity and metal bonding strength according to the embodiment of the present invention, the respective characteristic values can be measured by the following method.

1. Electrical Conductivity of Metal Plated Glass Fiber

)를 계산하였다.(V / I) using a 4-probe volume resistivity tester (MITUBISHI Chemical Co., MCP-T610) to measure the electrical conductivity of the fabricated metal- The cross-sectional area of the fiber side, and L: the distance between the voltage-contacting portions)

) Were calculated.

2. Observation of surface structure, thickness change and other characteristics of metal-plated glass fiber

Scanning electron microscope (SEM JEOL JSM-840A) and X-ray diffraction (XRD) analysis were performed to observe the changed surface microstructure, thickness variation and other characteristics of glass fiber due to the introduction of metal. Rigaku Model D / MAX-Ⅲ was used.

3. Evaluating electromagnetic shielding ability

The electromagnetic wave shielding characteristics were analyzed in the frequency range of 0.3-6.0 GHz by ASTM D4935-89 method using electromagnetic interference (EMI) (AGILENT, USA). The shielding experiment confirmed the reflection and absorption characteristics of the electromagnetic wave, respectively, and conducted the experiment by separating the reflection characteristic into S11 and the absorption characteristic into S12. Each experiment took data based on the point of stabilization through three repeated experiments.

[Example]

The embodiments of the present invention have been described below for the purpose of illustration and not for limiting the present invention.

An embodiment of the method of manufacturing nickel-plated glass fiber with enhanced purity and metal bonding strength according to the present invention will be described in detail below.

The glass fiber used in this experiment was a preheated HD324-01 (23 * 23 count / inch, weight 248 g / m ² ) produced by Hyundai Fiber Co., Were used.

The glass fiber was pretreated with 0.2 M HNO ₃ for 30 minutes to remove impurities on the surface before the metal plating.

In addition, electroless plating method was used for the nickel plating of glass fiber by continuous process, activated with SnCl ₂ and PdCl ₂ , and washed with distilled water.

In this process, Sn / Pd nuclei are formed on the glass fiber surface, and Sn / Pd nuclei formed on the glass fiber surface promote metal deposition.

Further, the treated glass fibers were placed in a nickel electroless plating solution having a composition of NiCl ₂ .6H ₂ O, NaH ₂ PO ₂ .H ₂ O, NaC ₆ H ₅ O ₇ .2H ₂ O, After the electroless-treated glass fibers were completely dried, they were heat-treated under the conditions shown in Table 2 in an inactive state.

The nickel - plated glass fiber prepared by the above procedure was mixed with a polymer resin and samples were prepared and the electromagnetic wave shielding effect was measured.

Specifically, the following will be described based on Tables 1 to 3 and FIGS. 1 to 6 attached hereto.

BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 is a photograph showing a cross section of electroless nickel plated glass fiber produced according to the method of manufacturing a metal-plated glass fiber with enhanced purity and metal bonding strength according to an embodiment of the present invention, FIG. 3 is a photograph showing a process of changing the surface shape of the heat-treated nickel plated glass fiber produced according to the method of manufacturing a metal-plated glass fiber with enhanced purity and metal bonding strength according to an embodiment of the present invention. FIG. 4 is a photograph showing the principle of surface shape change of the heat-treated nickel plated glass fiber produced according to the method of manufacturing a metal-plated glass fiber with enhanced purity and metal bonding strength according to an embodiment of the present invention. FIG. 5 is a photograph showing the interfacial bonding state between the glass fiber and the nickel layer after the heat treatment prepared according to the method of manufacturing a metal-plated glass fiber reinforced with a bonding force, FIG. 6 is a schematic view showing the principle of the electromagnetic wave shielding of the nickel-plated glass fiber or polymer composite according to the heat treatment prepared according to the method of manufacturing the metal-plated glass fiber with enhanced purity and metal bonding strength according to the embodiment of the present invention. Fig.

The electroless nickel plating conditions, the thickness of the nickel plating on the glass fiber surface and the electrical conductivity, the change in the surface shape of the heat-treated nickel plated glass fiber, and the principle of change will be described in detail below based on Tables 1 to 3 and FIGS. .

1 shows a state of a glass fiber plated with nickel in an electroless nickel plating solution for one minute.

Further, as shown in FIG. 2, it can be seen that the surface shape of the nickel plated glass fiber after the heat treatment after the heat treatment is changed to the embossed form before the heat treatment. Such an embossed surface shape can have an advantage that the bonding force can be further improved upon bonding with the resin in the future.

The principle that the surface shape of the nickel plated glass fiber is changed through heat treatment is as shown in Fig. 3, in which the nickel component and the impurities (phosphorus and boron components, etc.) constituting the nickel plating layer formed on the glass fiber surface due to the heat treatment process (Such as phosphorus and boron components) are removed from the nickel-plated glass fiber, and the surface shape of the nickel-plated glass fiber is changed into an embossed form due to removal of such impurities (phosphorus and boron components and the like). 3, the left part is the state of the nickel plated glass fiber before the heat treatment, and the right part is the state of the nickel plated glass fiber after the heat treatment.

Next, a process of fusing the interface between the glass fiber and the nickel plating layer through the heat treatment process will be described with reference to FIGS. 4 to 5. FIG.

As shown in Fig. 4, the nickel plated layer and the glass fiber interface in the state of performing the heat treatment are changed into the fused state. That is, the interface between the nickel plated layer and the glass fiber can be more firmly bonded due to the heat treatment process. The fusion state shown in Fig. 4 is made at 600 degrees Celsius.

As shown in FIG. 5, the fusion bonding is performed by heat treatment, and deformation occurs in the interface layer of the nickel plated layer and the glass fiber, and the nickel plated layer and the glass fiber can be more firmly bonded due to such deformation.

7 is a flowchart showing a method of manufacturing a metal-coated glass fiber SMC for electromagnetic wave shielding according to an embodiment of the present invention.

Referring to FIG. 7, a method for fabricating a metal-coated glass fiber SMC for electromagnetic wave shielding according to an embodiment of the present invention includes the steps of preparing an electroless plating solution and glass fiber (S10), forming a metal plating layer (S20) A fiber heat treatment step (S30), a sizing treatment step (S40) for performing a silane coating treatment on the heat treated metal plated glass fiber, and a metal-coated glass fiber SMC manufacturing step (S50) for shielding electromagnetic waves.

Specifically, step (S10) of preparing the electroless plating solution and the glass fiber may be a step of preparing an electroless plating solution and a glass fiber including a metal salt, a reducing agent and a complexing agent.

The glass fiber pre-treatment such as desizing (picking), pickling treatment, and activation treatment can be performed in preparation step S10 of preparing the electroless plating solution and the glass fiber.

For reference, the activation treatment is a process of adsorbing Sn / Pd catalyst metal on the glass fiber surface by using SnCl ₂ and PdCl ₂ , and the Sn / Pd adsorbed on the glass fiber surface promotes the deposition of the metal to be plated.

The glass fibers can be prepared in the form of continuous fibers in which the filaments are bundled together without kinking. Further, the filament diameter of the glass fiber may be 5 탆 to 50 탆. More specifically, it is preferably 10 占 퐉 to 30 占 퐉.

Also, the linear density (tex) of the glass fiber may be 200 tex to 10,000 tex. More preferably 1,000 tex to 5,000 tex. For reference, tex is a unit for indicating the thickness of a fiber or yarn, and is an odd number. The length of a kilometer is expressed as weight (g), and the weight of 1 kilometer is called 1 tex. 1 text corresponds to 9D (denier: D / d).

The metal salt may be at least one selected from the group consisting of a nickel salt, a copper salt, a tin salt, a zinc salt, a gold salt, a silver salt, a lead salt, an aluminum salt, Cobalt (Co) salt and chromium (Cr) salt.

The pH of the electroless metal plating solution is preferably in the range of 2 to 11 although it depends on the kind of metal to be plated.

When the pH of the electroless metal plating solution is more than 11, the solution may self-decompose and the plating may not be performed well. Further, when the pH of the electroless metal plating solution is less than 2, the quality of the plating layer may be deteriorated.

The reducing agent is a reactive substance capable of causing a reduction reaction. Sodium hypophosphite may be used as the reducing agent. The reducing agent may also include at least one of hydrazine (N ₂ H ₄ ), sodium borohydride (NaBH ₄ ), formaldehyde, an amine compound, a glycol compound, glycerol, dimethylformamide, tannic acid, citric acid salt and glucose .

The complexing agent can generate complex ions around the metal ions. The complexing agent may be a cyanide salt. In addition, the complexing agent may include at least one of pyrophosphoric acid, glycine, citric acid,? -Carbonyl-based acetylacetone, alkanolamine-based mono-ethanolamine, and dimethylamine.

The metal plating layer forming step (S20) may be a step of forming a metal plating layer on the glass fiber surface through a chemical reduction reaction using an electroless plating solution.

More specifically an embodiment of a metal-plated layer formation step (S20), the case of forming a nickel plating layer on the glass fiber _{surface, NiCl 2 6H 2 O, NaH} 2 PO 2 H 2 0, NaC 6 H 5 O 7 2H 2 0 , The nickel-plated layer can be formed as shown in Table 1, provided that the activated glass fiber passes through the nickel-electroless plating solution having a composition of 60% by weight in 30 seconds to 5 minutes.

[Table 1] Electroless Nickel Plating Conditions and Glass Fiber Surface Nickel Plating Thickness

As shown in Table 1, it can be seen that the nickel plating thickness is increased by increasing the plating time at 60 degrees Celsius.

The thickness of the metal plating layer in the metal plating layer formation step (S20) is preferably 0.1 to 2.0 占 퐉.

When the thickness of the metal plating layer is less than 0.1 탆, the metal film (metal layer) is formed too thin and it may be difficult to measure the electric conductivity. If the thickness of the metal plating layer is more than 2.0 占 퐉, the metal layer becomes too thick to cause a phenomenon in which a yarn-to-fiber yarn combination (two or more yarn-binding yarns are merged) and workability is poor.

The metal-plated glass fiber heat treatment step (S30) improves the interfacial bonding force by making fusion between the surface of the glass fiber on which the metal plating layer is formed and the metal plating layer, with respect to the glass fiber having the metal plating layer formed through the metal plating layer forming step, And performing heat treatment to remove impurities existing in the metal plating layer.

In the metal-plated glass fiber heat treatment step (S30), impurities in the metal plating layer are removed from the glass fiber having the metal plating layer formed through the metal plating layer formation step to improve the interfacial adhesion between the surface of the glass fiber and the metal plating layer, And performing a predetermined heat treatment to form an embossed structure on the surface of the metal plating layer.

In the metal-plated glass fiber heat treatment step (S30), the heat treatment temperature may be in the range of 300 to 800 degrees Celsius under active or inactive conditions.

When the temperature of the metal plating glass fiber heat treatment is less than 300 degrees, an increase in bonding strength between the glass fiber and the metal plating layer may be low. In addition, when the temperature of the heat treatment of the metal-plated glass fiber exceeds 800 ° C, damage of the glass fiber may occur.

Therefore, it is preferable that the temperature of the heat treatment of the metal-plated glass fiber is between 300 and 800 degrees. More specifically, in the case of nickel plating, it is preferably about 600 deg.

Further, in the metal-plated glass fiber heat treatment step (S30), the heat treatment time may be within 5 to 60 minutes.

Metal Plating If the glass fiber heat treatment time is less than 5 minutes or too short, removal of impurities such as phosphorus (P) or boron (B) present in the metal plating plated layer may not be sufficient. As a result, the bonding force between the metal plating layer and the glass fiber can not be maintained.

In addition, when the heat treatment time of the metal-plated glass fiber exceeds 60 minutes, the heat treatment of more than 60 minutes does not cause any additional effect, resulting in economical and time-wasting.

The metal-plated glass fiber heat treatment step S30 may form an embossed surface while removing impurities such as phosphorus (P) and boron (B) components present in the metal plating layer.

In addition, impurities (such as phosphorus and boron components) on the metal-plated glass fiber subjected to the metal-plating glass fiber heat treatment step (S30) may be 5% by weight or less.

That is, the metal content in the metal plating layer plated on the glass fiber may be 95 wt% or more. As a result, a metal plating layer of high purity can be obtained.

Further, the metal-plated glass fiber subjected to the metal-plating glass fiber heat treatment step (S30) may have an electrical conductivity of 1 x 10 ³ (S / cm) to 6 x 10 ⁵ (S / cm).

Table 2 shows the results of measuring the electrical conductivity of the glass fiber treated with nickel for 2 minutes in the sample of Table 1 while setting the heat treatment time to 30 minutes and changing the heat treatment temperature condition within 300 to 800 degrees Celsius .

As shown in Table 2, it was found that the electric conductivity generally increased with increasing the heat treatment temperature. This can be understood as a result of increasing the purity of the plated nickel by removing impurities (such as phosphorus and boron components) on the nickel plated glass fiber in the heat treatment step.

[Table 2] Heat treatment temperature condition and electric conductivity of nickel plated glass fiber plated for 2 minutes

As shown in Table 2, the electrical conductivity of the plated glass fibers was measured while changing the temperature condition within the range of 300 ° C. to 800 ° C. for 2 minutes in Table 1, and the heat treatment time was 30 minutes. As a result, it was found that the electric conductivity increased as the heat treatment temperature increased.

Further, as shown in FIG. 2, it can be seen that the surface shape of the nickel-plated glass fiber subjected to the heat treatment as compared with that before the heat treatment changed into the embossed form.

Through the embossed surface shape of the heat-treated nickel-plated glass fiber, it is possible to provide the effect that the bonding force is improved more than before the heat treatment when bonded to the resin in the future.

For reference, the mechanism of chemical fusion at the nickel-glass fiber interface after nickel plating is as follows.

After the heat treatment of the nickel plated glass fiber, the Si-O structure on the surface and the Ni chemically bond to form a Si-O-Ni bond.

In addition, the phosphorus (P) molecules contained in the metal layer may absorb thermal energy due to the heat treatment, so that the phosphorus (P) molecules may be vaporized. Accordingly, the content of phosphorus (P) molecules contained in the metal layer can be reduced.

In the present invention, P is removed from the physical bonding form of Ni-P: SiO ₂ to form a chemical bond of Ni-O-Si, and a strong metal bonding force can be imparted.

The present invention is characterized by controlling the shape and size of the embossing morphology and the electric conductivity / electromagnetic wave shielding property on the surface of the metal plating layer by controlling the content of boron (B) or phosphorus (P) in the metal plating layer in the heat treatment step .

The electromagnetic shielding ability of a composite material produced by using plated and heat-treated metal-plated glass fibers and a polymer resin according to an embodiment of the present invention will be described in detail with reference to Tables 3 and 6 below.

An epoxy resin is used as the polymer resin, but various types of polymer resins can be used without being limited to the epoxy resin.

Table 3 shows the electromagnetic shielding performance of the composite material produced by using the nickel-plated glass fiber and the epoxy resin heat-treated at each heat treatment temperature according to the heat treatment temperature of the nickel plated glass fiber, and Fig. 6 shows the heat- (DB) according to the frequency (abscissa) of the electromagnetic shielding ability pattern of a composite material produced by using a plated glass fiber and an epoxy resin.

As shown in Table 3, the composites produced by using the nickel-plated glass fiber and epoxy resin subjected to the heat treatment process have the electromagnetic shielding ability of 60 dB or more and the shielding strength of the electromagnetic wave is generally increased as the heat treatment temperature is increased Could know.

The left side of FIG. 6 shows the electromagnetic wave shielding intensity in the entire frequency band, and the right side shows the electromagnetic wave shielding intensity in the low frequency band in detail.

[Table 3] EMI shielding ability of heat-treated nickel-plated glass fiber and epoxy resin composite material

As a result, the step of preparing the electroless plating solution and the glass fiber (S10), the step of forming the metal plating layer (S20) and the step of heat-treating the metal-plated glass fiber (S30) Can be produced.

Further, the method may further include a second plating step of performing metal plating on the metal-plated glass fibers subjected to the metal-plating glass fiber heat treatment step (S30) through an electrolytic plating method.

The second plating step may include a step of performing a second plating step of depositing nickel (Ni), copper (Cu), tin (Sn), zinc (Zn) At least one metal selected from silver (Ag), gold (Au), aluminum (Al), cobalt (Co), and chromium (Cr) is further plated.

The surface of the heat-treated metal-plated glass fiber is hydrophilic and has a low interfacial affinity with the hydrophobic surface of the polymer resin used for preparing the metal-coated glass fiber SMC. Therefore, a sizing treatment step (S40) for performing a silane coating treatment on the surface of the heat-treated metal-plated glass fiber for enhancing the hydrophilic-hydrophobic interface bonding strength can be performed.

The sizing treatment step S40 may be performed after the heat treatment is performed with a dilute solution using at least one silane selected from the group consisting of Amino-silane, Epoxy-silane, Methacrylate-silane, Vinyl-silane, Alkyl- It is the process of coating the surface of the metal plating plies.

The sizing treatment step (S40) is a surface treatment process of the metal-plated glass fiber for enhancing the bonding force between the hydrophilic interface of the metal-plated glass fiber and the hydrophobic interface of the polymer resin in the production of the fiber-reinforced composite material.

Aminopropyl trimethoxysilane (APS) can be used as a representative silane of the amino-silane system.

Representative silanes of epoxy-silane system can use glycidoxy propyl trimethoxy silane (GPS).

Typical examples of methacrylate-silane silanes are 3- (trimethoxysilyl) propylmethacrylate (MPS).

Metal Plating for Electromagnetic Wave Shielding The glass fiber SMC manufacturing step (S50) is a step of manufacturing a metal-plated glass fiber SMC for electromagnetic wave shielding by using a metal-plated glass fiber having enhanced purity and metal bonding strength through a metal-plated glass fiber heat treatment step .

Metal-plating for electromagnetic wave shielding The glass fiber SMC manufacturing step (S50) is a step of manufacturing a sheet molding compound (SMC), which is a kind of molding material for producing a fiber-reinforced plastic part.

The metal-plated glass fiber SMC for electromagnetic wave shielding is manufactured by cutting the metal-plated glass fiber subjected to the metal-plating glass fiber heat treatment step (S30) and the sizing treatment step (S40) into a short fiber form, , A water reducing agent, a filler, a releasing agent, a coloring agent, and the like to prepare a sheet.

The metal-plated glass fiber SMC for electromagnetic wave shielding (S50) is formed by applying a resin composition comprising a thermosetting resin, a curing agent, a thickener, a water-reducing agent, a filler, a releasing agent and a coloring agent onto the lower side carrier film The composition may be prepared including a coating step.

Further, the metal-coated glass fiber SMC for electromagnetic wave shielding (S50) may be manufactured by including a metal-coated glass fiber applying step of dispersing and applying the metal-plated glass fibers cut into short fibers on the applied lower resin composition have.

In addition, the metal-coated glass fiber SMC for electromagnetic wave shielding step (S50) may be manufactured by including an upper resin composition application step of applying the resin composition on the upper side carrier film continuously supplied and transported.

In addition, the metal-coated glass fiber SMC for electromagnetic wave shielding step (S50) may be manufactured by laminating the upper side carrier film coated with the resin composition on the coated metal-plated glass fiber.

The metal-coated glass fiber SMC for electromagnetic shielding (S50) may be prepared by impregnating the coated metal-plated glass fiber with the resin composition so that the resin composition is impregnated into a sheet form, .

In addition, the metal-coated glass fiber SMC for electromagnetic shielding (S50) may further include a step of dispersing and applying a short carbon fiber between the lower carrier film and the upper carrier film.

In addition, the metal-coated glass fiber SMC for electromagnetic wave shielding (S50) may include a conductive fiber such as a carbon fiber fabric, a metal-plated glass fiber fabric, a metal-plated polyester fabric, or the like between the lower carrier film and the upper carrier film The method may further include the step of laminating the conductive fabric.

In addition, the metal-coated glass fiber SMC for electromagnetic wave shielding step (S50) may be manufactured by applying the resin composition at least once between the lower carrier film and the upper carrier film.

Further, the metal-coated glass fiber SMC for electromagnetic wave shielding is made of a material such as Milled Carbon Fiber, Chopped Carbon Fiber, Carbon Nano Tube, Graphite Powder and Carbon Black (Carbon Black) to the carbon-based conductive material. The carbon-based conductive material absorbs electromagnetic waves and converts the electromagnetic waves into heat.

For reference, the principle that a fiber-reinforced plastic product manufactured using a metal-coated glass fiber SMC for shielding electromagnetic waves has high electromagnetic wave shielding ability is as follows.

Reflection occurs when an electromagnetic wave touches a metallic substance. In addition, the electromagnetic wave shielding rate can be further improved if it comes in contact with a metal material having a mesh size that matches the length of the electromagnetic wave wavelength.

The present invention can reflect or block electromagnetic waves by forming a metal plating layer on the surface of the glass fiber.

When the electromagnetic waves are transmitted through the air and then meet with the surface of another medium, a part of the electromagnetic waves is reflected, and the electromagnetic waves other than the reflected electromagnetic waves are refracted and transmitted. At this time, the conductive material is encountered inside the new medium, and multiple reflections occur or absorption occurs, and the intensity of the electromagnetic waves weakens or disappears. That is, in the metal-plated glass fiber SMC for shielding electromagnetic waves, the electromagnetic wave can be destroyed by multiple reflection by the metal plating layer of the metal-plated glass fiber or absorption of electromagnetic wave by the carbon-based conductive filler material.

Specifically, the metal-coated glass fiber SMC for electromagnetic wave shielding (S50) is a step of preparing a metal-coated glass fiber SMC, which is a kind of molding material for producing a fiber-reinforced plastic part, And a sizing process step (S40) are performed on the metal-plated glass fibers using a thermosetting resin to fabricate metal-coated glass fiber SMCs (Sheet Moldings Compound) for shielding electromagnetic waves.

In addition, the metal-coated glass fiber SMC for shielding electromagnetic waves is made of unsaturated polyester resin, epoxy resin, phenol resin, polyurethane resin, urea resin, A melamine resin, a mixture thereof, a melamine resin, and a mixture thereof.

The epoxy resin is not particularly limited. Examples of the epoxy resin include bisphenol A type epoxy resin, bisphenol F type epoxy resin, biphenyl type epoxy resin, tetramethylbiphenyl type epoxy resin, novolak type epoxy resin, rubber modified epoxy resin, Bisphenol A type epoxy resin, bisphenol A type phenoxy resin, bisphenol F type phenoxy resin, fluorene type phenoxy resin, and the like can be used in combination. have.

The unsaturated polyester resin is a colorless transparent thermosetting resin which can be produced by reacting a polybasic acid such as isophthalic acid, maleic anhydride, or fumaric acid and a polyhydric alcohol such as propylene glycol or diethylene glycol. The unsaturated polyester resin is a resin having excellent heat resistance and corrosion resistance.

Further, the metal-coated glass fiber SMC for shielding electromagnetic waves can be produced by using metal-plated glass fibers cut to a predetermined length. It is preferable that the length of the cut metal-plated glass fiber has a length of 1 mm to 100 mm.

Further, the metal-coated glass fiber SMC for electromagnetic wave shielding may be manufactured to contain 5.0 wt% to 80 wt% of the metal-plated glass fiber.

When the metal-plated glass fiber is less than 5% by weight, the electromagnetic shielding ability of the electromagnetic wave-shielding fiber-reinforced plastic part manufactured by using the metal-plated glass fiber SMC is insufficient and the mechanical properties such as tensile strength, . When the metal-plated glass fiber is more than 80% by weight, the moldability of the fiber-reinforced plastic part may not be good.

The metal-coated glass fiber SMC for shielding electromagnetic waves can also be produced by adding a metal oxide containing at least one of titanium oxide (TiO2), tungsten oxide (WO3) and niobium oxide (Nb2O5).

Metal oxide fillers such as titanium oxide (TiO2), tungsten oxide (WO3) and niobium oxide (Nb2O5) used in the present invention can improve the heat resistance, durability and strength of the composite material to be produced.

In addition, metal oxide fillers such as titanium oxide (TiO2), tungsten oxide (WO3), and niobium oxide (Nb2O5) increase the thermal stability of the composite material by lowering the thermal expansion coefficient.

The blending amount of the metal oxide filler such as titanium oxide (TiO2), tungsten oxide (WO3) and niobium oxide (Nb2O5) is 0.1 to 5.0 parts by weight per 100 parts by weight of the thermosetting resin. When the blending amount of the metal oxide filler is less than 0.1 part by weight, the effect of improving the heat resistance and strength of the composite material may be insignificant. If the compounding amount of the metal oxide filler is more than 5.0 parts by weight, the amount of components not mixed with the thermosetting resin increases, and the physical properties of the composite material may be deteriorated.

Further, the metal-plated glass fiber SMC for shielding electromagnetic waves can be generally used for improving the function of the metal-plated glass fiber or the thermosetting resin, improving the mutual affinity of the metal-plated glass fiber or the thermosetting resin, and improving the dispersibility of the metal- A colorant such as a dispersant, an organic-inorganic interfacial binder, a hardener, a heat stabilizer, an antioxidant, a hydrolysis stabilizer, a peroxide, a lubricant, an interfacial auxiliary agent, a UV stabilizer, a light stabilizer, a lubricant, Flame retardants, low specific gravity agents, fillers, and mixtures thereof can be used as auxiliary agents.

(S10) of preparing the electroless plating solution and the glass fiber of the present invention, a metal plating layer forming step (S20), a metal plating glass fiber heat treatment step (S30), a sizing through the heat treatment of the metal- The metal-plated glass fiber SMC for electromagnetic wave shielding manufactured by performing the processing step (S40) and the metal-coated glass fiber SMC manufacturing step (S50) for shielding electromagnetic waves can be applied to the production of fiber-reinforced plastic parts for shielding electromagnetic waves.

The fiber-reinforced plastic parts for electromagnetic wave shielding manufactured using the metal-plated glass fiber SMC for electromagnetic wave shielding according to the embodiments of the present invention are not particularly limited, but they may be used in DC converters, inverters, battery control systems, battery systems, Electronic parts such as a car controller, a body controller, a tire pneumatic alarm controller, an airbeck control device, a lane departure warning system, a mobile phone, a notebook computer, a TV, a microwave oven, Device parts, and the like.

Claims (10)

(a) preparing an electroless plating solution containing a metal salt, a reducing agent and a complexing agent, and a glass fiber;
(b) forming a metal plating layer on the surface of the glass fiber through a chemical reduction reaction using the electroless plating solution;
(c) fusion bonding is performed between the surface of the glass fiber on which the metal plating layer is formed and the metal plating layer with respect to the glass fiber on which the metal plating layer is formed through the metal plating layer formation step to improve the interfacial adhesion force, A metal-plated glass fiber heat treatment step of performing heat treatment so as to remove impurities present;
(d) a sizing treatment step of performing a silane coating treatment on the surface of the heat-treated metal-plated glass fiber; And
(e) fabricating a metal-coated glass fiber SMC for shielding electromagnetic waves using metal-plated glass fibers having enhanced purity and metal bonding strength through the steps (a) to (d)
The step (c)
Heat treatment is performed at a temperature of 300 to 800 degrees Celsius for 5 minutes to 60 minutes,
The content of impurities existing in the metal plating layer is controlled,
The step (b)
The thickness of the metal plating layer is 0.1 to 2.0 탆,
The step (e)
Titanium oxide (

), Tungsten oxide (

) And niobium oxide (

) Is added to the thermosetting resin in an amount of 0.1 to 5.0 parts by weight based on 100 parts by weight of the thermosetting resin, thereby producing a metal-coated glass fiber SMC for electromagnetic wave shielding.
The method according to claim 1,
The metal salt may be at least one selected from the group consisting of a nickel salt, a copper salt, a tin salt, a zinc salt, a gold salt, a silver salt, a lead salt, , A cobalt (Co) salt and a chromium (Cr) salt.
The method according to claim 1,
The electroless plating solution may contain,
and a pH of 2 to 11. A method of producing a metal-coated glass fiber SMC for electromagnetic wave shielding according to claim 1,
The method according to claim 1,
The metal-plated glass fiber SMC may be,
At least one of a unsaturated polyester resin, an epoxy resin, a phenol resin, a polyurethane resin, a urea resin, and a melamine resin. Wherein the metal-coated glass fiber SMC is formed of a metal.
delete The method according to claim 1,
After step (c)
Wherein the metal content in the metal plating layer plated on the glass fiber is 95 wt% or more.
The method according to claim 1,
After step (c)
Wherein the metal-plated glass fiber has an electrical conductivity of 1 x 10 ³ (S / cm) to 6 x 10 ⁵ (S / cm).
The method according to claim 1,
Wherein the sizing processing step comprises:
The surface of the heat-treated metal-plated glass fiber is coated with a dilute solution using at least one silane selected from the group consisting of Amino-silane, Epoxy-silane, Methacrylate-silane, Vinyl-silane, Alkyl-silane and Phenyl- Wherein the metal-coated glass fiber SMC is formed on the surface of the metal-coated glass fiber SMC.
A metal-coated glass fiber SMC for electromagnetic wave shielding produced by the manufacturing method according to any one of claims 1 to 4 and 6 to 8.
10. The method of claim 9,
The metal-plated glass fiber SMC for electromagnetic wave shielding comprises,
And the metal-plated glass fiber is contained in an amount of 5.0 wt% to 80 wt%.

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