KR101843109B1 - Stretchable conductivity film and manufacturing method thereof) - Google Patents

Stretchable conductivity film and manufacturing method thereof) Download PDF

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Publication number
KR101843109B1
KR101843109B1 KR1020160029483A KR20160029483A KR101843109B1 KR 101843109 B1 KR101843109 B1 KR 101843109B1 KR 1020160029483 A KR1020160029483 A KR 1020160029483A KR 20160029483 A KR20160029483 A KR 20160029483A KR 101843109 B1 KR101843109 B1 KR 101843109B1
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conductive layer
elastic substrate
elastic
conductive
layer
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KR1020160029483A
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KR20170105987A (en
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김민기
이상훈
손정환
이창헌
박종호
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(주)알킨스
주식회사 팬시스템
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B5/00—Non-insulated conductors or conductive bodies characterised by their form
    • H01B5/14—Non-insulated conductors or conductive bodies characterised by their form comprising conductive layers or films on insulating-supports
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
    • H01B1/02—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of metals or alloys
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
    • H01B1/04—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of carbon-silicon compounds, carbon or silicon
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B13/00—Apparatus or processes specially adapted for manufacturing conductors or cables
    • H01B13/0026—Apparatus for manufacturing conducting or semi-conducting layers, e.g. deposition of metal

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  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Laminated Bodies (AREA)

Abstract

The present invention relates to a stretchable electrically conductive film and a method of manufacturing the same. More particularly, the present invention relates to a method of manufacturing an electrically conductive film having stretchability, which comprises applying an external force to an elastic substrate to elongate the elastic substrate, Forming a conductive layer on one side or both sides of the elastic substrate in the stretched state and releasing an external force applied to the elastic substrate on which the conductive layer is formed to restore the elastic substrate in the stretched state .
According to the present invention, there is an advantage that it has an excellent elastic modulus and a restoration ratio and has excellent electric conductivity even in a stretched state. In addition, due to such characteristics, there is an advantage that it can be applied to various wearable and flexible electronic devices.

Description

TECHNICAL FIELD [0001] The present invention relates to an electroconductive film having stretchability and a manufacturing method thereof.

TECHNICAL FIELD The present invention relates to an electrically conductive film having elasticity and a method of manufacturing the same, and more particularly, to an electrically conductive film having stretchability capable of exhibiting excellent electrical conductivity even in a stretched state, and a method of manufacturing the same.

BACKGROUND ART [0002] Recently, computers, various home appliances and communication devices have been digitized and rapidly improved in performance.

In recent years, as wearable devices have come into widespread use, such wearable devices are generally operated in cooperation with smartphones or independently without a smartphone.

In accordance with this tendency, the number of users using the wearable device has been explosively increased, and the users are hoping to further improve the mobility or convenience, which is an advantage of the wearable device, I hope to use it more and more closely.

In order to meet such a demand, the conductive film or tape applied to the wearable device must be flexible as well as stretchable. That is, if sufficient conductivity is secured even in the elongated state, the body adhesion can be enhanced.

In addition, other electronic devices other than wearable devices have also been downsized and have become complicated in structure, so that flexible printed circuit boards (FPCB) have been applied, and flexible and stretchable flexible printed circuit boards Is desired.

However, conventional conductive films or tapes have disadvantages in that they are not stretchable by using a substrate made of a non-oriented metal material such as a copper foil or a plated polyester yarn. That is, even if the substrate is made in the form of a thin film and given some flexibility, there is a disadvantage that it is not possible to stretch.

Accordingly, there is a demand for the development of conductive films and tapes having not only flexibility but also stretchability and excellent electrical conductivity even in a stretched state.

KR 10-1462864 B1

SUMMARY OF THE INVENTION Accordingly, it is an object of the present invention to solve the problems of conventional conductive films, and it is an object of the present invention to provide a conductive film which has excellent elasticity and recovery rate by using an elastic substrate and forming a conductive layer in a state where the elastic substrate is elongated , And to provide an electrically conductive film having stretchability having excellent electrical conductivity even in a stretched state.

In order to accomplish the above object, the present invention provides a stretchable electroconductive film comprising: an elastic substrate; and a conductive layer formed on one side or both sides of the elastic substrate in a state where the elastic substrate is stretched.

The elastic substrate includes a polyurethane or a modified urethane, and the adhesive layer or adhesive layer is formed on the conductive layer, and a release layer is formed on the adhesive or adhesive layer.

The elastic substrate may have a thickness of 5 to 100 탆 and may be formed of conductive powder such as nickel, gold, silver, copper, carbon, carbon nanotube (CNT), graphite graphite, graphene, and ferrite. The present invention is further characterized in that:

The method for manufacturing an electrically conductive film having stretchability according to the present invention includes the steps of elongating the elastic substrate by applying an external force to the elastic substrate and forming a conductive layer on one side or both sides of the elastic substrate in the stretched state And releasing the external force applied to the elastic base material on which the conductive layer is formed to restore the elastic base material in the stretched state.

Forming an adhesive or pressure-sensitive adhesive layer on the releasing layer, and bonding the adhesive or pressure-sensitive adhesive layer on which the releasing layer is formed to the conductive layer, wherein the elastic substrate comprises a polyurethane or a modified urethane do.

The stretchable electrically conductive film according to the present invention has an advantage that it has excellent elastic modulus and recovery rate and has excellent electric conductivity even in a stretched state.

In addition, due to the characteristics of elastic modulus, restoration ratio and electric conductivity, it has an advantage that it can be applied to various wearable and flexible electronic devices.

1 is a cross-sectional view showing a state in which a conductive layer is formed on one surface of an elastic substrate according to the present invention.
2 is a cross-sectional view showing a state in which a conductive layer is formed on both surfaces of an elastic substrate according to the present invention.
Fig. 3 is a cross-sectional view showing a state in which the conductive layer of Fig. 1 is adhered or an adhesive layer and a release layer are formed. Fig.
4 is a cross-sectional view showing a state in which the conductive layer of FIG. 2 is adhered or an adhesive layer and a release layer are formed.

Hereinafter, the present invention will be described in detail.

First, the conventional electroconductive film showed a slight flexibility, but had no disadvantage of being stretchable. Therefore, there is a limitation in application to wearable and flexible devices, which are the mainstream of the electric and electronic market.

Accordingly, it is an object of the present invention to provide an electrically conductive film which exhibits not only flexibility but also excellent stretchability, excellent electrical conductivity even in a stretched state, and excellent restoration ratio.

Hereinafter, the electroconductive film of the present invention will be described in detail with reference to the accompanying drawings.

First, as shown in Fig. 1, the electroconductive film of the present invention comprises an elastic substrate 1 and a conductive layer 2 formed on one surface of the elastic substrate 1. As shown in Fig.

Here, the elastic substrate 1 is made of a polyurethane or a modified urethane resin having high flexibility and high elasticity. As the modified urethane, various types of modification may be used depending on the functional requirements such as acrylic urethane, amide urethane, epoxy urethane, polyester urethane, and polyether urethane, and the kind thereof is not limited. The elastic substrate 1 composed of the polyurethane or the modified urethane resin is capable of elongation of 200% or more, and its thickness can be made 5 to 100 탆.

The conductive layer 2 formed on one side of the elastic substrate 1 may be formed of a metal such as gold, silver, copper, nickel, titanium, molybdenum, And at least one kind of high-conductivity metal selected from the alloys of these metals, and may be formed by various methods such as plating, vapor deposition, and coating. At this time, the thickness of the conductive layer 2 is preferably about 10 to 5000 ANGSTROM.

The methods of plating, vapor deposition, coating and the like are well known in the field of the present invention, so that a detailed description thereof will be omitted.

The most characteristic feature of the present invention is that the conductive layer 2 is formed in a state in which the elastic substrate 1 is stretched. More specifically, the elastic substrate 1 is stretched at an elongation rate of 50% or more, the elastic substrate 1 is stretched, the conductive layer 2 is formed, or the elastic substrate 1 is stretched, The formation of the conductive layer 2 may also be completed when the formation of the layer 2 is started and finally the extension of the elastic substrate 1 is completed.

That is, the conductive layer 2 may start to form the conductive layer 2 in a state where the elastic substrate 1 is elongated (regardless of the elongation ratio, and may also start to form the conductive layer 2, , So that it is possible to have a sufficient electric conductivity even if the produced film is stretched. In addition, since the elastic substrate 1 is made of polyurethane or modified urethane resin, the elastic substrate 1 has a characteristic of being restored to its original size when an external force applied for elongation after forming the conductive layer 2 is removed.

On the other hand, the conductive layer 2 may be formed of one layer using one metal, but may be formed of a multilayer structure, and its implementation is not limited.

For example, a primary conductive layer is formed of titanium (Ti), molybdenum (Mo), nickel (Ni), or nickel-copper alloy on the surface of the elastic base material 1, The conductive layer, and finally the copper or nickel-copper alloy to form the third conductive layer. At this time, the primary conductive layer made of titanium (Ti), molybdenum (Mo), nickel (Ni) or nickel-copper alloy is intended to improve adhesion with the elastic substrate 1, , And silver is intended to increase the electrical conductivity. The thickness of the secondary conductive layer is preferably 50 to 2000 Å. The tertiary conductive layer made of copper or a nickel-copper alloy prevents oxidation of silver, And the thickness thereof is preferably 10 to 500 angstroms.

As another example, a primary conductive layer made of a nickel-copper alloy may be formed on the surface of the elastic substrate 1, and a secondary conductive layer made of copper may be formed thereon. At this time, the primary conductive layer made of the nickel-copper alloy is for the purpose of improving adhesion and ease of etching. The thickness of the primary conductive layer is preferably 10 to 500 angstroms. The secondary conductive layer made of copper is for ease of etching, Preferably from 50 to 2000 Angstroms.

In addition, it is a matter of course that various metal layers can be formed in multiple layers in addition to these examples. However, if the thickness of the conductive layer 2 is too small, the thickness of the entire conductive layer 2 is not sufficient. If the thickness of the conductive layer 2 is too thick, (2) may adversely affect the elongation and restoration of the film.

The electrically conductive film of the present invention constituted as described above has a horizontal resistance and exhibits excellent stretchability, that is, elongation and resilience, and exhibits sufficient electrical conductivity even in a stretched state.

2, the conductive layer 2 may be formed on both sides of the elastic substrate 1 as well as on one side of the elastic substrate 1. The constitution and the formation method of the conductive layer 2 are not limited thereto 1.

However, when an electrically conductive film having conductive layers 2 on both sides is to be produced, conductive material such as nickel, gold, copper, or the like is added to the elastic substrate 1 in order to secure not only horizontal resistance but also vertical resistance. And may further include at least one of silver, copper, carbon, carbon nanotube (CNT), graphite, graphene, and ferrite. At this time, the content of the conductive powder may be 5 to 60% by weight based on 100% by weight of the elastic base material, but the content thereof is not limited. That is, it is constituted by mixing 40 to 95% by weight of a polyurethane or a modified urethane resin and 5 to 60% by weight of a conductive powder.

It is needless to say that the conductive base material 2 may not include the conductive powder in the elastic base material 1 so that the film formed with the conductive layer 2 on both sides may have only a horizontal resistance.

The conductive powder preferably has a particle size of 1 to 15 탆. If the size is less than 1 탆, the conductive powder is easily scattered to deteriorate the workability. If it is too large, it can not be uniformly dispersed in the polyurethane or modified urethane resin. It is preferable to have the above-mentioned particle size.

As shown in FIGS. 3 and 4, the film of the present invention can also be realized as an adhesive or an adhesive tape for electromagnetic shielding. FIG. 3 is a cross-sectional view of the film of FIG. The adhesive layer 3 and the release layer 4 are formed on the film on which the conductive layer 2 is formed on both sides.

The adhesive or pressure-sensitive adhesive layer 3 is formed on the conductive layer 2 to a thickness of about 3 to 25 탆. The adhesive or adhesive layer 3 adheres or adheres to the conductive layer 2 and is electrically conductive. And also suppresses the generation of electromagnetic waves.

The adhesive or adhesive layer 3 may be formed using a variety of known adhesive or adhesive compositions, but the most preferred form includes a polymer; At least one conductive powder selected from the group consisting of carbon, graphite, graphene, carbon nanotube (CNT), copper, silver, nickel, silver coated copper, and silver coated nickel; And a hardening agent. The polymer may be one or more of a modified polyurethane, a modified polyester, an acrylic copolymer and a copolyamide. Examples of the curing agent include epoxy resin, isocyanate, aziridine Or more can be used. The mixing ratio of the polymer is preferably 40 to 90% by weight, the conductive powder is 5 to 60% by weight, and the curing agent is 0.1 to 5% by weight.

If the size of the conductive powder is less than 1 mu m, the conductive powder may easily scatter and degrade the workability. When the conductive powder is too large, the conductive powder may not be uniformly dispersed in the polymer, It is preferable to have one particle size.

The release layer 4 may be formed of a polyester film or the like having a thickness of about 23 to 100 탆. The release layer 4 may be formed of the adhesive or the adhesive layer 3 It is removed before application to electronic products. In addition to the above-mentioned types, various types of release layers commonly used in the field to which this technology belongs may be used.

In addition to the film having the above-described structure, it is possible to constitute the film in various other known types. If the elastic substrate 1 and the conductive layer 2 formed in the elongated state of the elastic substrate 1 are included, There is no restriction on structure.

The electrically conductive film having such elasticity has an advantage that it can be applied to various wearable and flexible electronic devices such as medical, sports, leisure, and flexible storage devices.

Hereinafter, a method for producing a film according to the present invention will be described in detail.

A step of producing the elastic substrate (1).

First, the elastic substrate 1 is made conductive or non-conductive, depending on the required characteristics. In the case of producing the non-conductive elastic substrate 1, the conductive layer 2 is formed only on one side so as to have a horizontal resistance. In the case of producing the conductive elastic substrate 1, 2) so as to have both the horizontal and vertical resistances.

At this time, the application of the conductivity is achieved by mixing the conductive metal described above with the polyurethane or the modified urethane resin.

Applying an external force to the elastic base material (1) to elongate the elastic base material (1).

Next, an external force is applied to the elastic substrate 1 to stretch it. At this time, the elongation of the elastic substrate 1 is elongated to be 50% or more, more preferably about 50 to 200%.

Forming a conductive layer (2) on one side or both sides of the elastic substrate (1) in the stretched state.

Then, the conductive layer 2 is formed on one side or both sides of the elastic substrate 1 in the stretched state by vapor deposition, coating or plating.

Here, the formation of the conductive layer 2 may be performed in a state in which the extension is completed, that is, in order to extend the final extension to 100%, the conductive layer 2 may be formed with 100% extension completed, The formation of the conductive layer 2 may be completed at the time point (100%) at which the formation of the conductive layer 2 is started and the extension is completed from the time point when the extension of the conductive layer 2 is started (0%). Do not.
That is, it is a matter of course that an external force is continuously applied to the elastic base 1 at this stage.

Releasing the external force applied to the elastic substrate having the conductive layer and restoring the elastic substrate in the stretched state.
The external force applied to the elastic base 1 is released to restore the elastic base 1. At this time, since the elastic substrate 1 is made of a modified urethane or polyurethane having excellent elasticity, it can be restored to its original state simply by releasing the external force.

delete

(3) to the release layer (4).

If the adhesive or adhesive layer 3 and the release layer 4 are required on the film, that is, if they are to be manufactured as a tape, the release layer 4, that is, the surface of the release film, The adhesive layer 3 is formed and dried at 80 to 160 DEG C for about 1 to 3 minutes.

Here, since the adhesive or pressure-sensitive adhesive composition has been described in detail in the description of the adhesive or pressure-sensitive adhesive layer 3, detailed description thereof will be omitted.

Bonding the adhesive or adhesive layer (3) on which the release layer (4) is formed to the conductive layer (2).

Next, the adhesive or pressure-sensitive adhesive layer (3) and the release layer (4) are thermally joined to the conductive layer (2). The thermal lamination proceeds at a pressure of 3 kg / cm 2, a temperature of 60 to 120 ° C, a rate of 5 to 15 M / min, and aging at about 50 ° C for more than 24 hours to complete the final product.

Hereinafter, the present invention will be described in more detail with reference to specific examples.

(Example 1)

An elastic substrate having a width, a length, and a thickness of 100 mm x 50 mm x 20 m was produced using a polyurethane resin. Then, a conductive layer of nickel and copper alloy (500 Å), silver (2000 Å) and copper (500 Å) was formed in this order by vapor deposition. At this time, the conductive layer is formed in a state in which the elastic base material is stretched by 100%. More specifically, the elastic base material is stretched so as to have an elongation percentage of 100% by applying a tensile force to the elastic base material. . When the formation of the conductive layer is completed, the tensile force applied to the elastic substrate is released to restore the elastic substrate to its original length.
(Example 2)

delete

A polyurethane resin was used to produce an elastic substrate having a width, a length, and a thickness of 100 mm x 50 mm x 60 m. Then, a conductive layer made of nickel, copper alloy (500 Å), and copper (2000 Å) was formed in this order by vapor deposition. At this time, the conductive layer was formed in a state where the elastic base was stretched 100%.

(Test Example 1)

Resistance and resistance after restoration according to elongation ratios of Examples 1 and 2 were measured, and the results are shown in Tables 1 and 2 below. Here, in the MD direction, a conductive layer is formed in a state in which the elastic base material is stretched in the MD direction, and the resistance is measured by extending in the MD direction. In the TD direction, a conductive layer is formed in a state in which the elastic base material is stretched in the TD direction , And the resistance was measured by stretching in the TD direction

Results of resistance measurement of Example 1. kidney%
MD direction TD direction Elongation State Resistance (Ω) Resistance after restoration (Ω) Elongation State Resistance (Ω) Resistance after restoration (Ω) 0 0.183 0.165 10 0.236 0.189 0.24 0.171 20 0.62 0.243 0.431 0.248 30 0.968 0.323 0.714 0.366 40 1.399 0.486 1.002 0.449 50 2.107 1.02 1.242 0.548 60 2.32 1.216 1.549 0.742

The resistance measurement result of Example 2. kidney%
MD direction TD direction Elongation State Resistance (Ω) Resistance after restoration (Ω) Elongation State Resistance (Ω) Resistance after restoration (Ω) 0 0.463 0.46 10 0.496 0.471 0.684 0.552 20 0.609 0.563 1.275 0.609 30 1.233 0.643 1.951 0.885 40 1.819 0.693 2.659 1.267 50 2.384 0.787 3.052 1.507 60 3.183 0.938 4.15 1.665

As can be seen from Tables 1 and 2, the electrically conductive film according to the present invention was found to have excellent electrical conductivity even in the elongated state, and it was confirmed that it exhibited excellent electrical conductivity characteristics even after the restoration.

Although the present invention has been described and illustrated in detail, it should be understood by those skilled in the art that various changes and modifications may be made without departing from the scope of the present invention as defined by the appended claims. It will be understood that various modifications and changes may be made in the present invention.

1: elastic substrate 2: conductive layer
3: Adhesion or adhesive layer 4: Release layer

Claims (5)

Applying an external force to the elastic substrate (1) to elongate the elastic substrate (1) so that the elastic substrate (1) has an elongation of 50 to 200%
Forming a conductive layer (2) on both sides of the elastic substrate (1) in the stretched state,
And releasing the external force applied to the elastic substrate (1) on which the conductive layer (2) is formed to restore the elastic substrate (1) in the stretched state,
The elastic substrate 1 comprises a polyurethane or a modified urethane and has a thickness of 5 to 100 탆 and is made of conductive powder such as nickel, gold, silver, copper, carbon ), Carbon nanotubes (CNTs), graphite, graphene, and ferrites,
The step of forming the conductive layer (2) on both sides of the elastic base material (1) in the elongated state comprises the steps of: forming a primary conductive layer on both sides of the elastic base material (1) in the elongated state by nickel- Forming a second conductive layer with silver (Ag) on the first conductive layer, and forming a tertiary conductive layer with copper on the secondary conductive layer,
Wherein the thickness of the conductive layer (2) is 10 to 5000 ANGSTROM.
delete An electrically conductive film having elasticity, which is produced by the method of claim 1. delete delete
KR1020160029483A 2016-03-11 2016-03-11 Stretchable conductivity film and manufacturing method thereof) KR101843109B1 (en)

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KR101948537B1 (en) 2016-12-13 2019-02-15 주식회사 아모그린텍 Flexible EMI shielding materials for electronic device, EMI shielding type circuit module comprising the same and Electronic device comprising the same
US10945358B2 (en) 2016-12-12 2021-03-09 Amogreentech Co., Ltd. Flexible electromagnetic wave shielding material, electromagnetic wave shielding type circuit module comprising same and electronic device furnished with same
CN108274865A (en) * 2018-02-12 2018-07-13 北京梦之墨科技有限公司 Conducting connecting part and its manufacturing method
CN110379544A (en) * 2019-07-31 2019-10-25 广东南海启明光大科技有限公司 A kind of retractable and flexible conductive film and preparation method thereof
KR102367243B1 (en) * 2020-02-10 2022-03-02 연세대학교 산학협력단 Method for Manufacturing Piezoelectric Energy Harvesting Structures and Piezoelectric Energy Structures Manufactured by the Same
WO2021200518A1 (en) * 2020-03-31 2021-10-07 日東電工株式会社 Stretchable, electrically conductive film, sensor, radio wave absorber, and reflector

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JP2015074678A (en) * 2013-10-07 2015-04-20 株式会社ブリヂストン Flexible electrode, and electro-device therewith
JP2015210927A (en) * 2014-04-25 2015-11-24 住友理工株式会社 Conductive film and conductive tape member and electronic part using the same
KR101577212B1 (en) * 2014-06-16 2015-12-14 인하대학교 산학협력단 A Piezoresistive Carbon Nanotube-Polymer Composite and the Manufacturing Method Thereof

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Publication number Priority date Publication date Assignee Title
JP2015074678A (en) * 2013-10-07 2015-04-20 株式会社ブリヂストン Flexible electrode, and electro-device therewith
JP2015210927A (en) * 2014-04-25 2015-11-24 住友理工株式会社 Conductive film and conductive tape member and electronic part using the same
KR101577212B1 (en) * 2014-06-16 2015-12-14 인하대학교 산학협력단 A Piezoresistive Carbon Nanotube-Polymer Composite and the Manufacturing Method Thereof

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