JP2015179849A - Method for manufacturing electromagnetic wave shield material for fpc - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method for manufacturing an electromagnetic wave shield material for FPC, which is well flexible and slim in thickness, and is has a flexural property enough to avoid the worsening of an electromagnetic wave shielding performance even if repeatedly suffering a severe bending.SOLUTION: A method for manufacturing an electromagnetic wave shield material 10 for FPC comprises the steps of: preparing a laminate by laminating at least a base 1 composed of a dielectric thin film resin film, an adhesive layer 2 composed of a thin film, a before-sintering conductive paste layer 3, and a conducting adhesive layer 4 in turn, provided that the adhesive layer 2 includes a light absorption material including at least one black pigment or color pigment, which is selected from a group consisting of carbon black, graphite, aniline black, cyanine black, titanium black, black iron oxide, chromium oxide and manganese oxide; bonding the laminate, through the conducting adhesive layer 4, to FPC or a peel film 7 subjected to a treatment to facilitate peeling; and heating and pressing them and concurrently, sintering the conductive paste layer 3.

Description

  The present invention relates to a method of manufacturing an electromagnetic wave shielding material for FPC, which is used to shield an electromagnetic wave by covering a flexible printed circuit board (hereinafter referred to as FPC) that repeatedly receives a bending operation.

In portable electronic devices such as mobile phones, electronic components are integrated on a printed circuit board in order to keep the outer dimensions of the casing small and facilitate carrying. Furthermore, in order to reduce the outer dimensions of the housing, the printed circuit board is divided into a plurality of parts, and the printed circuit board is folded by using a flexible FPC for connection wiring between the divided printed circuit boards, or It is done to slide.
In recent years, in order to prevent malfunction of electronic devices due to the effects of electromagnetic wave noise received from outside or electromagnetic wave noise mutually received between internal electronic components, important electronic components and FPCs can be prevented. Is covered with an electromagnetic shielding material.

Conventionally, as an electromagnetic shielding material used for the purpose of such electromagnetic shielding, what provided the adhesive layer on the surface of metal foil, such as rolled copper foil and soft aluminum foil, was used. Covering an object to be shielded using an electromagnetic shielding material made of such a metal foil has been performed (see, for example, Patent Documents 1 and 2).
Specifically, in order to shield an important electronic component from electromagnetic waves, a metal box or metal plate is used to form a sealed box and cover it. Further, in order to shield the bent FPC wiring from electromagnetic waves, a metal foil provided with an adhesive layer on one side is used and bonded through an adhesive layer.

In recent years, mobile phones have rapidly spread as electronic devices that are carried around. In a cellular phone, it is preferable that the overall dimensions be as small as possible when stored in a pocket or the like without being used, and the overall dimensions can be increased when used. There is a need to reduce the size and thickness of mobile phones and to improve operability. In mobile phones, as a method of solving these problems, a folding / opening / sliding / opening / closing type housing structure is employed.
Moreover, in the case of a cellular phone, in both the folding open / close method and the slide open / close type housing structure, the operation screen is frequently opened and closed (start and stop operations) on a daily basis. It is performed at a frequency of several tens of times / day or several hundred times / day.

As a result, the FPC used in mobile phones and the electromagnetic wave shielding material for FPC that covers and shields the electromagnetic waves are repeatedly bent at a frequency exceeding the common sense of conventional portable electronic devices. Therefore, the electromagnetic shielding material for FPC which plays the role of electromagnetic shielding of FPC receives the severe repeated stress. If it becomes impossible to withstand the repeated stress, the base material constituting the FPC electromagnetic shielding material and the shielding material such as metal foil will eventually be damaged, such as rupture and peeling. There is a concern that the function as a shield material may be degraded or lost.
Therefore, an electromagnetic wave shielding material that copes with such repeated bending operations is also known (see, for example, Patent Document 3).

Japanese Utility Model Publication No. 56-084221 Japanese Patent Laid-Open No. 61-222299 Japanese Patent Laid-Open No. 7-122883

  In the electromagnetic wave shielding material provided with an adhesive layer on the surface of a metal foil such as rolled copper foil or soft aluminum foil as disclosed in the above-mentioned Patent Documents 1 and 2, the number of bending operations is small and it is used. There is no problem in shielding performance when the period is short. However, when the period of use is long from 5 to 10 years and the number of bending operations increases, there is a problem that the bending characteristics are lacking. Such an electromagnetic shielding material does not have an excellent bending characteristic that passes a bending test of 1 million times or more required for an electromagnetic shielding material for FPC used in recent mobile phones.

  In addition, the electromagnetic wave shielding material disclosed in Patent Document 3, in which a metal thin film such as metal vapor deposition is provided on one side of a flexible film and a conductive adhesive is laminated thereon, covers the wires that are repeatedly bent. And can be used. According to the example of Patent Document 3, a conductive film in which a conductive coating material containing silver powder having a thickness of 0.5 μm is provided on one side of a polyester film having a thickness of 12 μm and a polyester adhesive and nickel powder are mixed thereon is provided. The adhesive is heated and dried to provide a conductive adhesive layer having a thickness of 30 μm. In addition, it is said that it was confirmed that there was no damage by conducting a bending test with one cycle of bending at an angle of 180 ° along the outer periphery of a mandrel having an outer diameter of 10 mmφ and returning it to a straight line for one cycle.

  However, recent mobile phones are required to be as thin as possible by reducing the thickness of the outer dimensions of the casing in units of 0.1 mm. An electromagnetic wave shielding material for FPC having bending performance that can be used in such a thin casing is, for example, bent at an angle of 180 ° along the outer periphery of a mandrel having an outer diameter of 2 mmφ and returned to a straight line as one cycle. It is required that the bending test is not damaged even if it is carried out 1 million times or more. There is a need for an electromagnetic wave shielding material for FPC that can overcome a bending test under harsh conditions as compared with the prior art.

In addition, the electromagnetic wave shielding material described in the example of Patent Document 3 has a resin film having a thickness of 12 μm, a coating film of a conductive paint having a thickness of 0.5 μm, and a conductive adhesive layer having a thickness of 30 μm. The total thickness of the electromagnetic shielding material exceeds 40 μm.
As described above, in order to make the outer dimensions of the casing of the mobile phone as thin as possible, the electromagnetic shielding material for FPC is required to have a total thickness of 30 μm or less. That is, there is a demand for a strong FPC electromagnetic shielding material that is thinner than the conventional FPC electromagnetic shielding material and that can withstand severer bending tests.

Moreover, in the conductive adhesive used for the electromagnetic wave shielding material for FPC, in order to make the adhesive layer conductive, it is necessary to add a considerable amount of conductive powder (metal fine particles or carbon fine particles). Then, conversely, the adhesive strength of the adhesive layer is reduced.
In addition, in an electromagnetic wave shielding material for FPC in a mobile phone, the bending operation is repeated, so that the adhesive interface between the base material and the conductive paste layer and between the conductive paste layer and the FPC is partially delaminated. Then, there is a concern that the conductive paste layer breaks at the peeled portion, and the electromagnetic wave shielding performance deteriorates with time.
In addition, the base material itself is required to have excellent bending characteristics enough to withstand repeated bending operations (for example, one million bending tests) during the lifetime of the electronic device.

  An object of the present invention is an efficient production of an electromagnetic wave shielding material for FPC excellent in bending characteristics, which is thin and flexible and does not cause deterioration in electromagnetic wave shielding performance even when severe bending operations are repeated. It is to provide a method.

In the present invention, a base material made of a thin film of a heat resistant resin is used in order to withstand a severe bending operation and to withstand firing of a conductive paste by heating at a high temperature. In the present invention, a laminate in which an adhesive layer, a conductive paste layer, and a conductive adhesive layer before firing are sequentially laminated on a substrate composed of at least a dielectric thin film resin film is used as the conductive adhesive. The step of reducing the resistance of the conductive paste layer by baking the conductive paste layer at the same time as applying to the FPC or the release film that has been subjected to the release treatment and heating and pressure bonding through the agent layer is omitted. The technical idea is to efficiently manufacture an electromagnetic shielding material for FPC.
Also, in the present invention, a coated dielectric thin film resin film is used as a substrate made of a heat resistant resin thin film in consideration of flexibility and heat resistance, and the support film and the release film are removed. In addition, the entire thickness of the electromagnetic shielding material for FPC can be reduced to 25 μm or less.
Moreover, in this invention, in order to increase the adhesive force of the thin film resin film of the polyimide film which is a base material, and an electroconductive paste, the adhesive bond layer is provided between the base material and the electroconductive paste layer.

  Therefore, in the present invention, in order to solve the above-described problems, at least a base material composed of a dielectric thin film resin film, a thin film adhesive layer, a conductive paste layer before firing, and a conductive adhesive layer are sequentially formed. The laminated layered product is bonded to an FPC or a peeled release film through the conductive adhesive layer and heated and pressure-bonded, and at the same time, the conductive paste layer is fired. A method for producing an electromagnetic wave shielding material for FPC is provided.

  Further, in the present invention, in order to solve the above-described problems, a substrate made of a thin film resin film of a dielectric material applied on one side of a support film, an adhesive layer of a thin film, and conductivity before firing. A laminate in which a paste layer and a conductive adhesive layer are sequentially laminated is bonded to an FPC or a release film that has been subjected to a release treatment through the conductive adhesive layer, and heated and pressed simultaneously. The manufacturing method of the electromagnetic wave shielding material for FPC characterized by baking an adhesive paste layer is provided.

  Moreover, it is preferable that the said base material consists of a polyimide film and thickness is 1-9 micrometers.

  Moreover, it is preferable that the adhesive layer of the said thin film bridge | crosslinks the polyester-type resin composition which has an epoxy group, and thickness is 0.05-1 micrometer.

  Further, the adhesive layer is further one or more black pigments or colored pigments selected from the group consisting of carbon black, graphite, aniline black, cyanine black, titanium black, black iron oxide, chromium oxide, and manganese oxide. It is preferable that the light absorption material which consists of 1 or more types of these is included.

  In addition, after the conductive paste layer is applied with a conductive paste containing silver nanoparticles having an average particle diameter of 1 to 120 nm and a binder resin composition, the conductive paste layer is heated and pressure-bonded to the adherend. The final thickness is preferably 0.1 to 2 μm.

Moreover, it is preferable that the volume resistivity after baking of the electrically conductive paste which comprises the said electrically conductive paste layer is 1.5 * 10 <^-5> ohm * cm or less.

  In addition, the present invention provides a mobile phone in which the electromagnetic wave shielding material for FPC produced by the above manufacturing method is used as an electromagnetic wave shielding member.

  In addition, the present invention provides an electronic device in which the FPC electromagnetic shielding material produced by the above production method is used as an electromagnetic shielding member.

According to the electromagnetic wave shielding material for FPC of the present invention described above, by using a thin film resin film (thickness of 1 to 9 μm) of a polyimide film having high temperature heat resistance, by conducting baking of the conductive paste, conductivity is improved. In addition to being able to increase, it is possible to have excellent bending characteristics that can withstand severe bending operations.
Also, a laminate in which at least a base material composed of a dielectric thin film resin film, a thin film adhesive layer, a conductive paste layer before firing, and a conductive adhesive layer are sequentially laminated is used as the conductive adhesive layer. Then, the electromagnetic wave shielding material for FPC can be efficiently manufactured by baking the conductive paste layer at the same time as bonding to the FPC or the release film subjected to the release treatment and heating and pressure bonding.
Moreover, by using a thin film resin film (thickness: 1 to 9 μm) of a polyimide film and a conductive paste layer, the electromagnetic wave shielding performance can be obtained while suppressing the thickness.
By this, the whole thickness of the electromagnetic wave shielding material for FPC excluding the support film and the release film can be suppressed to 25 μm or less, which can contribute to reducing the overall thickness of the mobile phone and the electronic device.
By mixing a light absorbing material composed of one or more kinds of black pigments or colored pigments in the adhesive layer, specific coloring can be performed on one side of the shield film.
As described above, according to the present invention, the electromagnetic wave shielding material for FPCs is excellent in bending characteristics, which is flexible and thin, and does not deteriorate the electromagnetic wave shielding performance even when severe bending operation is repeated. It is possible to provide an efficient manufacturing method.

It is a schematic sectional drawing which shows an example of the electromagnetic wave shielding material for FPC concerning this invention. It is a schematic sectional drawing which shows the state which removes a support body film and a peeling film from FIG. 1, and uses it.

Hereinafter, preferred embodiments of the present invention will be described.
When the FPC electromagnetic shielding material of the present invention is bonded to an FPC, which is an adherend, the outer surface is a dielectric, and there is no need to bond an insulating film to the outer surface of the FPC electromagnetic shielding material. . In addition, the electromagnetic shielding material for FPC of the present invention has a reduced overall thickness in order to improve the bending characteristics with respect to the bending operation.

  The electromagnetic wave shielding material 10 for FPC of the present invention shown in FIG. 1 is a thin film resin film of a polyimide film formed using a solvent-soluble polyimide having a base material 1 having a thickness of 1 to 9 μm. A support film 6 is laminated on one surface of the material 1, and an adhesive layer 2 for improving the adhesion between the conductive paste layer 3 and the substrate 1 and conductive fine particles are coated on the other surface of the substrate 1. The contained conductive paste layer 3 is sequentially laminated, and further, the conductive adhesive layer 4 and the release film 7 are sequentially laminated on the conductive paste layer 3. This FPC electromagnetic shielding material 10 can be used as an FPC electromagnetic shielding material 11 from which the support film 6 and the release film 7 are removed as shown in FIG.

The manufacturing method of the electromagnetic wave shielding material 10 for FPC of the present invention includes a substrate 1 made of at least a dielectric thin film resin film, a thin adhesive layer 2, a conductive paste layer 3 before firing, a conductive adhesive layer 4, Are laminated together on the FPC or the release film 7 that has been subjected to the release treatment, and heated and pressed together with the conductive adhesive layer 4, and at the same time, the conductive paste layer 3 is baked.
In addition, the method for producing an electromagnetic wave shielding material for FPC of the present invention comprises a base material 1 made of a dielectric thin film resin film coated on one side of a support film 6, a thin adhesive layer 2, and before firing. When the laminate in which the conductive paste layer 3 and the conductive adhesive layer 4 are sequentially laminated is bonded to the FPC or the release film that has been subjected to the release treatment via the conductive adhesive layer 4 and heated and pressed. At the same time, the conductive paste layer 3 is fired.
This eliminates the step of reducing the resistance of the conductive paste layer that has been made before the conductive adhesive layer 4 of the laminate is bonded to the FPC or the release film 7 that has been subjected to the release treatment. An electromagnetic shielding material can be produced efficiently.
In the laminate before being bonded to the FPC or the release film 7 that has been subjected to the release treatment, the conductive paste layer 3 before firing (unfired) is laminated via the conductive adhesive layer 4. The conductive paste layer 3 before firing (unfired) is preferably sufficiently dried before the conductive adhesive layer 4 is applied.
When the conductive adhesive layer 4 of the laminate is bonded to the release film 7 that has been subjected to the release treatment, the release film 7 can be peeled and removed and bonded to the FPC after heating and pressure bonding.
When the conductive adhesive layer 4 of the laminate is bonded to the FPC, the release film 7 is not necessary, and the FPC provided with the FPC electromagnetic shielding material 11 is obtained by heating and pressure bonding the electromagnetic shielding material and the FPC. Can be obtained.
When the support film 6 is present in the laminate, the support film 6 can be peeled off after being attached to the FPC. After the support film 6 is peeled and removed (or while being peeled off), the conductive adhesive is used. It can also be attached to the FPC via the layer 4.

(Polyimide film)
A thin film resin film of a polyimide film formed using a solvent-soluble polyimide, which becomes the base material 1 of the electromagnetic wave shielding materials 10 and 11 for FPC according to the present invention, has high mechanical strength, heat resistance, It has insulating properties and solvent resistance, and is chemically stable up to about 260 ° C.
Examples of polyimide include thermosetting polyimide that is generated by a dehydration condensation reaction by heating polyamic acid, and solvent-soluble polyimide that is soluble in a non-dehydration condensation type solvent.
A generally known method for producing a polyimide film is to synthesize polyamic acid, which is an imide precursor, by reacting diamine and carboxylic dianhydride in a polar solvent, and heat the polyamic acid. Alternatively, a corresponding polyimide is formed by dehydration cyclization by using a catalyst. However, the temperature of the heat treatment in this imidization step is preferably a temperature range of 200 ° C. to 300 ° C., and if the heating temperature is lower than this temperature, imidization may not proceed, which is not preferable. If the heating temperature is higher than the above temperature, the compound may be thermally decomposed, which is not preferable.

The electromagnetic wave shielding material for FPC of the present invention uses a very thin polyimide film having a thickness of less than 10 μm with the intention of further improving the flexibility of the substrate.
In the present invention, a base material formed by laminating a thin polyimide film on one side of a support film 6 used as a reinforcing material for strength, or a base made of only a thin polyimide film without using the support film 6. Any of the materials can be used.
When the thickness of the polyimide film to be used is thinner than about 7 μm, it is preferable to form a thin polyimide film on one surface of the support film 6 used as a reinforcing material for strength.

However, although the polyimide film itself has heat resistance against heat treatment at a heating temperature of 200 ° C. to 250 ° C., the support film 6 is a general-purpose heat resistance because of the balance between price and heat resistance temperature performance. Since a resin film, for example, a polyethylene terephthalate (PET) resin film is used, a method of forming polyimide from polyamic acid which is a conventional imide precursor cannot be employed.
The solvent-soluble polyimide is complete in imidization of the polyimide and is soluble in the solvent. After applying the coating solution dissolved in the solvent, the solvent is volatilized at a low temperature of less than 200 ° C. A film can be formed. For this reason, the base material 1 used for the electromagnetic wave shielding material for FPC of the present invention is coated with a non-dehydration-condensation solvent-soluble polyimide coating solution on one surface of the support film 6, and then the temperature is 200. It is preferable to dry at a heating temperature of less than 0 ° C. to form a thin film resin film of a polyimide film formed using a solvent-soluble polyimide. By carrying out like this, the very thin polyimide film whose thickness is 1-9 micrometers can be laminated | stacked on the single side | surface of the support body film 6 which consists of a general purpose heat resistant resin film. Since the substrate 1, the adhesive layer 2, the conductive paste layer 3 and the like can be continuously formed on the support film 6 along its longitudinal direction, production on a roll-to-roll basis is possible. Is also possible.
The solvent-soluble polyimide that is a non-dehydrating condensation type used in the present invention is not particularly limited, but a commercially available coating solution for solvent-soluble polyimide can be used. Specific examples of commercially available solvent-soluble polyimide coating solutions include Solpy 6,6-PI (Solpy Industry), Q-IP-0895D (PI Engineering), PIQ (Hitachi Chemical Industry), SPI-200N (Nippon Steel Chemical). ), Rika Coat SN-20, Rika Coat PN-20 (New Nippon Rika) and the like. The method for applying the solvent-soluble polyimide coating solution on the support film 6 is not particularly limited, and can be applied by a coater such as a die coater, a knife coater, or a lip coater.

The thickness of the polyimide film used in the present invention is preferably 1 to 9 μm. Forming a polyimide film with a thickness of less than 0.8 μm is technically difficult because the mechanical strength of the formed film is weak. Moreover, when the thickness of a polyimide film exceeds 10 micrometers, it will become difficult to obtain the electromagnetic wave shielding material 11 for FPC which has the outstanding bending | flexion performance.
Further, when the thickness of the polyimide film to be used is thinner than about 7 μm, it is difficult to adjust the tension at the time of winding on a roll. Therefore, a thin polyimide film is formed on one side of the support film 6 used as a reinforcing material for strength. It is preferably formed by laminating films.
The thickness in the case of using a substrate made of only a thin polyimide film without using the support film 6 is preferably about 7 to 9 μm.

(Support film)
Examples of the substrate of the support film 6 used in the present invention include polyester films such as polyethylene terephthalate, polybutylene terephthalate, and polyethylene naphthalate, and polyolefin films such as polypropylene and polyethylene.
When the base material of the support film 6 has a certain degree of peelability on the base material itself, such as polyethylene terephthalate, for example, it is directly applied to the support film 6 without performing a peeling treatment. The base material 1 made of an applied dielectric thin film resin film may be laminated, or the surface of the support film 6 may be subjected to a peeling treatment for making the base material 1 easier to peel off.
Moreover, when the base film used as the support film 6 does not have releasability, a release treatment such as amino alkyd resin or silicone resin is applied and then dried by heating. Applied. Since the electromagnetic wave shielding materials 10 and 11 for FPC of the present invention are bonded to the FPC, it is desirable not to use a silicone resin for this release agent. This is because when a silicone resin is used as a release agent, a part of the silicone resin is transferred to the surface of the substrate 1 that is in contact with the surface of the support film 6, and further conductive from the substrate 1 through the inside of the electromagnetic shielding material 11 for FPC. The adhesive adhesive layer 4 may be transferred. This is because the silicone resin transferred to the surface of the conductive adhesive layer 4 may weaken the adhesive force of the conductive adhesive layer 4. The thickness of the support film 6 used in the present invention is not particularly limited because it is excluded from the overall thickness of the electromagnetic wave shielding material 11 for FPC when used by being attached to an FPC, but usually 12 to 150 μm. Degree.

(Adhesive layer)
The adhesive layer 2 used for the electromagnetic wave shielding materials 10 and 11 for FPC of the present invention is provided in order to improve the adhesion between the polyimide film thin film as the base material 1 and the conductive paste layer 3. .
Since the firing temperature of the conductive paste layer 3 laminated on the adhesive layer 2 is 150 to 250 ° C., it is necessary to use an adhesive having excellent heat resistance. Moreover, it is necessary to be excellent in the adhesive force with respect to the polyimide film used as the base material 1 and the conductive paste layer 3.
As the adhesive resin composition used for the adhesive layer 2, a thermoplastic resin such as a polyester resin, a polyurethane resin, a (meth) acrylic resin, a polyethylene resin, a polystyrene resin, or a polyamide resin is preferably used. Moreover, thermosetting types, such as an epoxy resin, an amino resin, a polyimide resin, (meth) acrylic resin, may be sufficient.
Particularly preferred as the adhesive resin composition for the adhesive layer 2 is an adhesive resin composition for crosslinking a polyester resin composition having an epoxy group, or an adhesive resin in which an epoxy resin is mixed as a curing agent with a polyurethane resin. It is a composition. For this reason, the adhesive bond layer 2 has a harder physical property than the base material 1 which consists of a thin film of a polyimide film. The polyester-based resin composition having an epoxy group is not particularly limited. For example, an epoxy resin having two or more epoxy groups per molecule (its uncured resin) and two or more carboxyls per molecule. It can be obtained by reaction with a polyvalent carboxylic acid having a group. For crosslinking of the polyester-based resin composition having an epoxy group, a crosslinking agent for epoxy resin that reacts with the epoxy group can be used.

The adhesive layer 2 is a light composed of one or more black pigments or colored pigments selected from the group consisting of carbon black, graphite, aniline black, cyanine black, titanium black, black iron oxide, chromium oxide, and manganese oxide. An absorbent material may be included.
It is preferable to mix a black pigment such as carbon black. The light absorbing material made of a black pigment or a colored pigment is preferably contained in the adhesive layer 2 at 0.1 to 30% by weight. The black pigment or the colored pigment preferably has an average primary particle size of about 0.02 to 0.1 μm by SEM observation.
Moreover, as a black pigment, a silica particle etc. may be immersed in a black color material, and only a surface layer part may be made black, and it may be formed from a black colored resin etc. and may become black over the whole. Further, the black pigment includes particles exhibiting a color similar to black, such as gray, dark brown, or dark green, in addition to true black, and can be used as long as it is a dark color that hardly reflects light.
The thickness of the adhesive layer 2 is preferably about 0.05 to 1 μm, and if the thickness is about this level, sufficient adhesion with the conductive paste layer 3 can be obtained. When the thickness of the adhesive layer 2 is 0.05 μm or less, fine particles of the light absorbing material are exposed, and the adhesion between the substrate 1 and the conductive paste layer 3 may be reduced. Moreover, even if the thickness of the adhesive layer 2 exceeds 1 μm, there is no effect in increasing the adhesive force to the substrate 1 made of a polyimide film or the conductive paste layer 3, so the thickness of the adhesive layer 2 exceeds 1 μm. This is not preferable because the cost increases.

(Conductive paste layer)
As the conductive paste layer 3 used in the present invention, a conductive paste in which a conductive filler is mixed in a resin composition serving as a binder is used.
The conductive paste preferably contains one or more selected from the group of conductive fillers composed of conductive metal fine particles, carbon nanotubes, and carbon nanofibers, and a binder resin composition. As the conductive metal fine particles, fine metal powders such as copper, silver, nickel, and aluminum are used, but it is preferable to use fine powders or nanoparticles of copper or silver because of their high conductive performance and low price. . In addition, carbon nanotubes and carbon nanofibers, which are carbon nanoparticles having conductivity, can also be used.
The volume resistivity of the conductive paste layer 3 after firing is desirably 1.5 × 10 ⁻⁵ Ω · cm or less. Further, the surface resistivity after firing of the conductive paste layer 3 is desirably 0.2Ω / □ or less.

In order to suppress the firing temperature of the conductive paste to a low temperature in the temperature range of 150 to 250 ° C., the average particle diameter of the metal fine particles is preferably in the range of 1 to 120 nm, and more preferably in the range of 1 to 100 nm.
The conductive paste layer 3 of the electromagnetic wave shielding materials 10 and 11 for FPC according to the present invention can not only cope with the thin film by containing such metal fine particles, but also the fine particles are fused. Thus, the conductivity can be improved at the same time. In the conductive paste used in the present invention, for example, in order to uniformly disperse metal fine particles having an average particle diameter of 1 to 120 nm in a dispersion solvent, the surface of the metal fine particles is coated with an organic molecular layer, It is preferable to improve the dispersion performance in a solvent. Finally, in the step of heating and baking the conductive paste, the metal fine particles can be brought into contact with each other to obtain the conductivity of the conductive paste layer 3.
The conductive paste is heated and fired, for example, by heating to about 150 to 250 ° C., the organic molecular layer covering the surface of the metal fine particles is separated and evaporated to remove the organic paste. Preferably, the boiling point is within the range.
In the present invention, the specific method for heating and baking the conductive paste includes at least a base material 1 made of a dielectric thin film resin film, a thin film adhesive layer 2, a conductive paste layer 3 before baking, and a conductive property. The laminate in which the adhesive layers 4 are sequentially laminated is bonded to the FPC or the release film 7 that has been subjected to the release treatment via the conductive adhesive layer 4 and is heated and pressure-bonded, and at the same time, the conductive paste layer 3 Is performed by firing. Also, on one side of the support film 6, a base material 1 made of a coated dielectric thin film resin film, a thin film adhesive layer 2, a conductive paste layer 3 before firing, a conductive adhesive layer 4, Are laminated by sequentially laminating the laminated body on the FPC or the release film subjected to the release treatment through the conductive adhesive layer 4 and heating and press-bonding, and simultaneously firing the conductive paste layer 3. .
As described above, the polyimide film itself serving as the base material 1 has heat resistance to heat treatment at a heating temperature of 200 ° C. to 250 ° C., but the support film 6 is inferior in heat resistance, and thus the support film. When 6 is used, it is preferable that the firing temperature is lower.
By suppressing the firing temperature of the conductive paste to 160 ° C. or less, it is possible to suppress appearance defects due to thermal deterioration of the support film 6.
In the heating and firing of the conductive paste, instead of setting the heating temperature to a relatively low temperature as described above, the conductive paste is pressurized at a pressure of, for example, 1 to 10 MPa from the stage before firing, and fired while being pressed, The mutual contact of the conductive fillers becomes dense, and a sufficiently low resistance can be achieved.

As the binder resin composition used by mixing the conductive paste with the conductive filler, a thermoplastic resin such as a polyester resin, a (meth) acrylic resin, a polyethylene resin, a polystyrene resin, or a polyamide resin is preferably used. Moreover, thermosetting resins, such as an epoxy resin, an amino resin, a polyimide resin, and a (meth) acrylic resin, may be sufficient.
The conductive paste is mixed with these binder resin compositions with conductive fillers such as conductive metal fine particles, carbon nanotubes, and carbon nanofibers, and then added with an organic solvent such as alcohol or ether as necessary. Make adjustments. Viscosity adjustment can be performed by the addition amount (blending ratio) of an organic solvent.
The thickness of the conductive paste layer 3 after firing is preferably about 0.1 to 2 μm. More preferably, the thickness is about 0.3 to 1 μm. When the thickness of the conductive paste layer 3 after firing is thinner than 0.1 μm, it is difficult to obtain high electromagnetic shielding performance. On the other hand, if the thickness of the conductive paste layer 3 after firing is greater than 2 μm, the entire thickness of the FPC electromagnetic wave shielding material 11 excluding the support film 6 and the release film 7 can be suppressed to 25 μm or less. It becomes difficult.

(Conductive adhesive layer)
As the conductive adhesive laminated on the conductive paste layer 3 of the electromagnetic wave shielding materials 10 and 11 for FPC according to the present invention, acrylic adhesive, polyurethane adhesive, epoxy adhesive, rubber adhesive Add conductive fine particles, ionic compounds such as quaternary ammonium salts, conductive polymers, etc. to commonly used thermosetting adhesives such as adhesives and silicone adhesives to make them conductive. However, it is not particularly limited.
It is preferable that the conductive adhesive is not a pressure-sensitive adhesive exhibiting pressure-sensitive adhesiveness at room temperature but an adhesive by heating and pressurization because the adhesive force is unlikely to decrease with respect to repeated bending.
The electroconductive fine particles mix | blended with the electroconductive adhesive layer 4 are not specifically limited, A conventionally well-known thing can be applied. Examples thereof include metal fine particles made of metal such as carbon black, silver, nickel, copper, and aluminum, and composite metal fine particles obtained by coating the surface of the metal fine particles with other metals. Can be appropriately selected and used.
Further, in the above conductive adhesive, in order to obtain excellent conductivity, the contact between the conductive material particles and the contact between the particles, the conductive paste layer, and the FPC as the adherend are improved. In addition, if a large amount of conductive material is contained, the adhesive strength is reduced. On the other hand, when the content of the conductive material is reduced in order to increase the adhesive force, the contact between the conductive material and the conductive paste layer and the FPC that is the adherend becomes insufficient, and the conductivity decreases. There are conflicting problems. For this reason, the compounding quantity of electroconductive fine particles is about 0.5-50 weight part normally with respect to 100 weight part of adhesive agents (solid content), More preferably, it is 2-10 weight part.

Moreover, as a conductive adhesive which comprises the conductive adhesive layer 4 of this invention, the anisotropic conductive adhesive containing conductive fine particles is preferable, and a well-known thing can be used. As this anisotropic conductive adhesive, for example, an adhesive having an insulating thermosetting resin such as an epoxy resin as a main component and conductive fine particles dispersed therein can be used.
In addition, as the conductive fine particles used for the anisotropic conductive adhesive, for example, single or two or more kinds of metal fine particles such as gold, silver, zinc, tin, and solder may be combined. Further, as the conductive fine particles, resin particles plated with metal can be used. The shape of the conductive fine particles is preferably a shape in which fine particles are connected in a straight chain or a needle shape. If it is such a shape, when heat-pressing processing with respect to FPC by a crimping | compression-bonding member, it will become possible for electroconductive fine particles to bite into the conductor wiring of FPC with a low pressurizing force.
The anisotropic conductive adhesive preferably has a connection resistance value with the FPC of 5 Ω / cm or less.

The adhesive strength of the conductive adhesive is not particularly limited, but the measurement method is in accordance with the test method described in JIS Z 0237. A range of 5 to 30 N / inch is preferable under the condition that the adhesive strength to the adherend surface is a peeling angle of 180 ° peel and a peeling speed of 300 mm / min. When the adhesive force is less than 5 N / inch, for example, the electromagnetic wave shielding material bonded to the FPC may peel off or float.
The conditions for heat and pressure adhesion to the FPC are not particularly limited, but for example, it is preferable to heat-press for 30 minutes at a temperature of 160 ° C. and a pressure of 2.54 MPa.

(Peeling film)
Examples of the substrate of the release film 7 include polyester films such as polyethylene terephthalate, polybutylene terephthalate, and polyethylene naphthalate, and polyolefin films such as polypropylene and polyethylene. After applying a release agent such as amino alkyd resin or silicone resin to these base films, the release treatment is performed by drying by heating. Since the electromagnetic wave shielding materials 10 and 11 for FPC of the present invention are bonded to the FPC, it is desirable not to use a silicone resin for this release agent. This is because when a silicone resin is used as a release agent, a part of the silicone resin is transferred to the surface of the conductive adhesive layer 4 in contact with the surface of the release film 7 and further conductively bonded through the inside of the electromagnetic shielding material 11 for FPC. There is a risk of migration from the agent layer 4 to the substrate 1. This is because the silicone resin transferred to the surface of the conductive adhesive layer 4 may weaken the adhesive force of the conductive adhesive layer 4. The thickness of the release film 7 used in the present invention is not particularly limited because it is excluded from the total thickness of the electromagnetic wave shielding material 11 for FPC when used by being attached to an FPC, but is usually about 12 to 150 μm. It is.

  The electromagnetic wave shielding materials 10 and 11 for FPC of the present invention can be suitably used as an electromagnetic wave shielding material for FPC having excellent bending characteristics that can be used by being bonded to an FPC that undergoes repeated bending operations. Moreover, the electromagnetic wave shielding material for FPC of this invention can be used for a mobile telephone or an electronic device as an electromagnetic wave shielding member.

Hereinafter, the present invention will be described specifically by way of examples.
Example 1
A polyethylene terephthalate (PET) film (product number: E5100, manufactured by Toyobo Co., Ltd.) having a thickness of 50 μm was used as the support film 6. On one side of the support film 6, a solvent-soluble polyimide coating solution is casted and dried so that the thickness after drying is 4 μm, and a base material 1 made of a dielectric thin film resin film is laminated. did. Coating for forming an adhesive layer 2 in which carbon black as a light-absorbing material black pigment and a polyester resin composition having a heat-resistant temperature of 260 to 280 ° C. are mixed on the formed substrate 1. Using the solution, the adhesive layer 2 was laminated by coating so that the thickness after drying was 0.3 μm. On the adhesive layer 2, a conductive paste prepared by mixing silver particles having a primary average particle diameter of about 50 nm as a conductive filler was applied so that the thickness after drying was 0.3 μm. The measured value of the surface resistivity of the conductive paste layer 3 before firing was 0.8Ω / □. An electrically conductive adhesive layer 4 is formed by applying an epoxy thermosetting conductive adhesive on the conductive paste layer 3 before firing so that the thickness after drying becomes 12 to 18 μm. 1 electromagnetic shielding material was obtained. When the conductive adhesive layer and the release-treated polyimide film (Toray DuPont Kapton 100H) are opposed to each other and baked by heating and pressing at a temperature of 160 ° C. and a pressure of 4.5 MPa for about 60 minutes, The surface resistivity of the conductive paste layer 3 after firing was 0.12Ω / □.

(Example 2)
An electromagnetic wave shielding material of Example 2 was obtained in the same manner as in Example 1 except that the heating press was performed at a temperature of 140 ° C. and a pressure of 4.5 MPa for 60 minutes. The measured value of the surface resistivity of the conductive paste layer 3 before firing was 0.8Ω / □. In the electromagnetic wave shielding material of Example 2, the surface resistivity of the fired conductive paste layer 3 was 0.12Ω / □.

(Example 3)
A solvent-soluble polyimide coating solution was casted and dried so that the thickness after drying was 8 μm, and the substrate 1 made of a dielectric thin film resin film was laminated. The electromagnetic shielding material of Example 3 was obtained. The measured value of the surface resistivity of the conductive paste layer 3 before firing was 0.8Ω / □. Moreover, in the electromagnetic wave shielding material of Example 3, the surface resistivity of the conductive paste layer 3 after firing was 0.12Ω / □.

Example 4
An electromagnetic wave shielding material of Example 4 was obtained in the same manner as in Example 1 except that the support film 6 was not used and a polyimide film made of a thermosetting polyimide having a thickness of 10 μm was used as the substrate 1. The measured value of the surface resistivity of the conductive paste layer 3 before firing was 0.8Ω / □. Moreover, in the electromagnetic wave shielding material of Example 4, the surface resistivity of the conductive paste layer 3 after firing was 0.11Ω / □.

(Comparative Example 1)
A polyethylene terephthalate (PET) film (product number: E5100, manufactured by Toyobo Co., Ltd.) having a thickness of 50 μm was used as the support film 6. On one side of the support film 6, a solvent-soluble polyimide coating solution is casted and dried so that the thickness after drying is 4 μm, and a base material 1 made of a dielectric thin film resin film is laminated. did. Coating for forming an adhesive layer 2 in which carbon black as a light-absorbing material black pigment and a polyester resin composition having a heat-resistant temperature of 260 to 280 ° C. are mixed on the formed substrate 1. Using the solution, the adhesive layer 2 was laminated by coating so that the thickness after drying was 0.3 μm. On the adhesive layer 2, a conductive paste prepared by mixing silver particles having a primary average particle diameter of about 50 nm as a conductive filler was applied so that the thickness after drying was 0.3 μm. The measured value of the surface resistivity of the conductive paste layer 3 before firing was 0.8Ω / □. Furthermore, after baking the conductive paste layer 3 at a temperature of 240 ° C. for about 7 minutes, the thickness after drying an epoxy thermosetting conductive adhesive on the fired conductive paste layer 3 is 12. The conductive adhesive layer 4 was formed by coating so as to be ˜18 μm, and the electromagnetic wave shielding material of Comparative Example 1 was obtained. The surface resistivity of the conductive paste layer 3 after firing was 0.13Ω / □. The conductive adhesive layer 4 and the peeled polyimide film (Toray DuPont Kapton 100H) were stacked to face each other and fired by heating and pressing at a temperature of 160 ° C. and a pressure of 4.5 MPa for about 60 minutes. However, the surface resistivity of the conductive paste layer 3 after firing was 0.13Ω / □ without change before and after the hot press.

(Measurement method of surface resistivity of conductive paste layer 3 before firing)
In accordance with JIS-K-7194 “Resistivity Test Method for Conductive Plastics by Four-Probe Method”, the resistivity meter Lorester GP T600 type manufactured by Mitsubishi Chemical Corporation is used to determine the surface resistivity of the conductive paste layer 3. It was measured.

(Measurement method of surface resistivity of conductive paste layer 3 after firing)
When the conductive paste layer 3 after firing is covered with the conductive adhesive layer 4, it cannot be measured with a resistivity meter Lorestar GP T600 type manufactured by Mitsubishi Chemical Corporation, so an eddy current resistance measuring device (( Surface resistivity was measured using EC-80P manufactured by Napson Corporation.

(Measurement method of bending test)
A test pattern was prepared by applying an epoxy thermosetting adhesive (manufactured by ThreeBond, product number: 33A-798) on the conductive paste layer 3 so that the thickness after drying was 12 μm. Is placed on the flexible printed circuit board with the conductive adhesive layer 4 side of the FPC electromagnetic wave shielding material facing each other, heat-pressed at 160 ° C. and 2.54 MPa for 30 minutes, and then 12.7 mm wide × 160 mm long A test piece was obtained by cutting into the following dimensions.
In accordance with IPC standard TM-650 “TEST METHODS MANUAL” (Reference 3 “Bend resistance” of JIS-C-6471), an IPC bend test is performed under the setting condition of R = 1.5 mm using a cut specimen. The bending performance was evaluated by measuring the number of bending tests when the resistance value of the conductive paste layer increased twice as much as the initial resistance value due to repeated bending of the conductive layer.
The determination of the bending test result is based on the bending test, when the resistance value of the conductive paste layer increases twice as much as the initial resistance value due to repeated bending operation of the conductive layer. The case where it exceeded 300,000 times was set to pass (◯), and the case where it was 300,000 times or less was set to fail (x).

(Measurement method of flexibility test)
Using the sample (width 17 mm x length 160 mm) used for the bending test, the sample was set on a loop stiffness tester manufactured by Toyo Seiki Seisakusyo Co., Ltd., and the measurement was started. The sample was bent into a loop shape, and the diameter of the loop The strength of the stiffness is evaluated by the load when the direction is crushed. Specifically, a ring with an outer circumference of 80 mm is formed so that the outer side of the sample used for the bending test is bent in a loop shape to be an electromagnetic shielding material, and the short axis of the sample portion is formed at a speed of 3.3 mm / sec from the upper side of the ring A force is applied until the distance becomes 1.5 mm, and the stress of the sample when measured for 5 seconds is measured.

(Appearance of the electromagnetic shielding material after firing)
The external appearance of the electromagnetic shielding material after firing is visually observed for abnormalities such as deformation and shrinkage. If there are no abnormalities and they are good, the result is good (○), and if abnormalities are found, X).

(Test results)
With respect to Examples 1 to 4 and Comparative Example 1, the surface resistivity, the bending test, and the flexibility test of the conductive paste layer before and after firing were performed by the above test method, and the obtained test results are shown in Table 1. Indicated.

According to the result of the firing test of the conductive paste layers 3 of Examples 1 to 4 shown in Table 1, the firing step of the conductive paste layer 3 that has been conventionally required can be omitted.
In Comparative Example 1, the process is performed in the same manner as in the prior art, and the conductive paste layer 3 is baked before the application of the conductive adhesive layer 4, but the heat resistance of the support film 6 is insufficient. Therefore, a good appearance cannot be obtained. However, in Examples 1 and 2 of the same configuration, the firing process that has been necessary so far is omitted, and the firing is performed in a hot press process in which heating and pressure bonding is performed at a lower temperature. The surface resistivity of the subsequent conductive paste layer 3 is not different from that of Comparative Example 1.
According to the present invention, a laminated body in which a base material composed of at least a dielectric thin film resin film, a thin film adhesive layer, a conductive paste layer before firing, and a conductive adhesive layer are sequentially laminated is formed by conductive bonding. It is bonded to the FPC or the release film that has been subjected to the release treatment through the agent layer, and is heated and pressure-bonded at a temperature lower than the firing temperature that has been required so far, and at the same time, the conductive paste layer is fired. An electromagnetic wave shielding material for FPC having no defects can be efficiently produced.
Further, according to the present invention, on one side of the support film, a base material composed of a coated dielectric thin film resin film, a thin film adhesive layer, a conductive paste layer before firing, a conductive adhesive layer At the same time, the laminated body in which is laminated in order is bonded to the FPC or the release film subjected to the release treatment through the conductive adhesive layer, and is heated and pressed at a temperature lower than the firing temperature required so far. By firing the conductive paste layer, it is possible to efficiently produce an electromagnetic shielding material for FPC having no appearance defect.

Furthermore, according to Examples 1 and 3, since the thickness of the base material which consists of a polyimide film is 1-9 micrometers, the more flexible electromagnetic shielding material for FPC was obtained, and it passed the bending test.
From these test results, it is necessary for the electromagnetic shielding material for FPC having excellent bending performance to make the base material made of a polyimide film a thin film having a thickness of 1 to 9 μm. However, as the thickness of the polyimide film made of thermosetting polyimide that is currently marketed in Japan, 7.5 μm is the thickness of the thinnest standard product. In the electromagnetic wave shielding material for FPC of the present invention, the thickness is as follows. It is necessary to use a thinner polyimide film as the substrate. Therefore, an electromagnetic shielding material for FPC having excellent bending performance can be obtained only by using a polyimide film having a thickness of 1 to 9 μm obtained by thinly casting a solvent-soluble polyimide coating solution as a base material. be able to.

  The electromagnetic wave shielding material for FPC of the present invention can be used as an electromagnetic wave shielding member in various electronic devices such as a mobile phone, a notebook computer, and a portable terminal.

DESCRIPTION OF SYMBOLS 1 ... Base material, 2 ... Adhesive layer, 3 ... Conductive paste layer, 4 ... Conductive adhesive layer, 6 ... Support film, 7 ... FPC or peeling film, 10, 11 ... Electromagnetic wave shielding material for FPC.

Claims (7)

  A substrate composed of at least a dielectric thin film resin film, a thin film adhesive layer, a conductive paste layer before firing, and a conductive adhesive layer are laminated in order, and the adhesive layer comprises carbon black, graphite, and aniline black. A laminate comprising a light absorbing material comprising at least one black pigment selected from the group consisting of cyanine black, titanium black, black iron oxide, chromium oxide, and manganese oxide, or at least one colored pigment. A method for producing an electromagnetic wave shielding material for FPC, wherein the conductive paste layer is fired at the same time as being bonded to an FPC or a release film that has been subjected to a release treatment through heating and pressure bonding via a conductive adhesive layer.   On one side of the support film, a substrate made of a coated dielectric thin film resin film, a thin film adhesive layer, a conductive paste layer before firing, and a conductive adhesive layer are laminated in order, and the adhesion The agent layer is composed of one or more black pigments selected from the group consisting of carbon black, graphite, aniline black, cyanine black, titanium black, black iron oxide, chromium oxide, and manganese oxide, or one or more of colored pigments. A laminate containing a light absorbing material is bonded to an FPC or a release film that has been subjected to a release treatment through the conductive adhesive layer, and heated and pressure-bonded, and at the same time, the conductive paste layer is fired. The manufacturing method of the electromagnetic wave shielding material for FPC.   The said base material consists of a polyimide film, and thickness is 1-9 micrometers, The manufacturing method of the electromagnetic wave shielding material for FPC of Claim 1 or 2 characterized by the above-mentioned.   The FPC according to any one of claims 1 to 3, wherein the thin-film adhesive layer is formed by crosslinking a polyester-based resin composition having an epoxy group and has a thickness of 0.05 to 1 µm. Manufacturing method of electromagnetic shielding material.   After the conductive paste layer is coated with a conductive paste containing silver nanoparticles having an average particle diameter of 1 to 120 nm and a binder resin composition, the conductive paste layer is finally heated and pressure-bonded to the adherend. 5. The method for producing an electromagnetic wave shielding material for FPC according to claim 1, wherein the thickness is 0.1 to 2 μm.   A mobile phone in which the electromagnetic shielding material for FPC produced by the production method according to claim 1 is used as an electromagnetic shielding member.   6. An electronic device in which the FPC electromagnetic shielding material produced by the manufacturing method according to claim 1 is used as an electromagnetic shielding member.

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