CN102762083A - Electromagnetic wave shielding material for FPC - Google Patents
Electromagnetic wave shielding material for FPC Download PDFInfo
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- CN102762083A CN102762083A CN2012101264474A CN201210126447A CN102762083A CN 102762083 A CN102762083 A CN 102762083A CN 2012101264474 A CN2012101264474 A CN 2012101264474A CN 201210126447 A CN201210126447 A CN 201210126447A CN 102762083 A CN102762083 A CN 102762083A
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- Prior art keywords
- electromagnetic shielding
- fpc
- shielding material
- film
- conductive paste
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- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K9/00—Screening of apparatus or components against electric or magnetic fields
- H05K9/0073—Shielding materials
- H05K9/0081—Electromagnetic shielding materials, e.g. EMI, RFI shielding
- H05K9/0086—Electromagnetic shielding materials, e.g. EMI, RFI shielding comprising a single discontinuous metallic layer on an electrically insulating supporting structure, e.g. metal grid, perforated metal foil, film, aggregated flakes, sintering
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
- B32B27/08—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/28—Layered products comprising a layer of synthetic resin comprising synthetic resins not wholly covered by any one of the sub-groups B32B27/30 - B32B27/42
- B32B27/281—Layered products comprising a layer of synthetic resin comprising synthetic resins not wholly covered by any one of the sub-groups B32B27/30 - B32B27/42 comprising polyimides
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
- B32B7/04—Interconnection of layers
- B32B7/12—Interconnection of layers using interposed adhesives or interposed materials with bonding properties
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2307/00—Properties of the layers or laminate
- B32B2307/20—Properties of the layers or laminate having particular electrical or magnetic properties, e.g. piezoelectric
- B32B2307/212—Electromagnetic interference shielding
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Physics & Mathematics (AREA)
- Electromagnetism (AREA)
- Engineering & Computer Science (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Shielding Devices Or Components To Electric Or Magnetic Fields (AREA)
Abstract
The invention provides an electromagnetic wave shielding material for FPC. The electromagnetic wave shielding material is flexible and thin. Even the electromagnetic wave shielding material is bent repeatedly and severely, the electromagnetic wave shielding performance does not degrade and thus the bending property is excellent. The electromagnetic wave shielding material (5) for FPC is characterized in that a base material (1) formed by coated dielectric thin resin film, a filmy adhesive layer (2), and an electrical conductivity layer (3) are laminated on a single face of a support body film (6), wherein the base material (1) is made of polyimide film formed by polyimide which is soluble through a solvent and is 1-9 microns thick.
Description
Technical field
The present invention relates to a kind of FPC and use electromagnetic shielding material, it covers the flexible printed circuit substrate receive flexure operation repeatedly (below be called FPC), is used for electromagnetic wave shielding.
Background technology
In portable phone etc. carries with e-machine,, electronic unit is integrated on the tellite in order the overall dimension of casing to be dwindled control to be easy to carry about with one carrying.In addition, a plurality of in order to dwindle the overall dimension of casing through tellite is divided into, and use has flexual FPC on the connection distribution between divided tellite, can fold tellite, and it is slided.
In addition; In recent years; Cause e-machine to carry out malfunction for the influence that prevents to receive the electromagnetic interference that receives each other between the electromagnetic interference that receives from the outside or the inner electronic unit, use electromagnetic shielding material to cover important electron parts and FPC.
Since previous, as the electromagnetic shielding material that uses from the purpose of this kind electromagnetic shielding, the surface of the metal forming of use rolled copper foil, soft aluminium foil etc. is provided with the material of pressure-sensitive bond layer.Come overlay masking object (for example, with reference to patent documentation 1,2) through the electromagnetic shielding material that constitutes by this metal forming.
Particularly, in order to cover the important electron parts, utilize metal forming or metallic plate to make the closed box shape and cover to prevent electromagnetic wave.In addition, for the distribution that covers crooked FPC to prevent electromagnetic wave, on the single face of metal forming, bond layer is set, fit through this pressure-sensitive bond layer.
In recent years, as the e-machine that carries at one's side, portable phone is popularized rapidly.Portable phone is preferably, and can dwindle whole size when being accommodated in the pocket etc. not using as far as possible, can the size of integral body be become big in use.Need seek improvement with portable phone miniaturization and operability.As the method that solves these problems, employing is divided into two parts with portable phone and folds the mode that opens and closes or slide the body structure of the mode of switching.
In addition, fold the mode that opens and closes or slide in any body structure of mode of switching portable phone being divided into two parts, need carry out the switching (operation that starts, stops) of operation screen continually.The switching number of times of operation screen carries out with the frequency in tens of times/days perhaps hundreds of times/skies.
That is to say, be used in the FPC of portable phone and cover FPC that FPC carries out electromagnetic shielding and compare with existing portable e-machine with the frequency more than very with electromagnetic shielding material and receive flexure operation repeatedly.Therefore, realize that the FPC of the electromagnetic shielding effect of FPC receives the alternate stress of harshness with electromagnetic shielding material.In case be unable to bear this alternate stress, final, constitute FPC and can receive fracture, peel off equivalent damage with the shielding material of the base material of electromagnetic shielding material and metal forming etc.Its result worries that FPC descends or disappearance with the electromagnetic shielding function of electromagnetic shielding material.
Therefore, also known being useful on dealt with the electromagnetic shielding material (for example, with reference to patent documentation 3) that receives this repeated bending action.
The prior art document
Patent documentation
Patent documentation 1: Japan opens clear 56-084221 communique in fact
Patent documentation 2: japanese kokai publication sho 61-222299 communique
Patent documentation 3: japanese kokai publication hei 7-122883 communique
Summary of the invention
(problem that invention will solve)
As above-mentioned patent documentation 1,2 is disclosed; On the surface of metal formings such as rolled copper foil, soft aluminium foil, be provided with in the electromagnetic shielding material of pressure-sensitive bond layer; Under the situation that number of times at the flexure operation time few, that be used lacks, the shielding properties fault-free.But, reach 5 years to 10 years, the number of times of flexure operation between in use and become under the many situation, there is the not enough problem of durability of flexural property.This existing electromagnetic shielding material do not have the FPC that is used in nearest portable phone necessary with electromagnetic shielding material, in the bend test more than 1,000,000 times qualified flexural property.
In addition, patent documentation 3 discloses a kind of electromagnetic shielding material, the metallic film of metal evaporation etc. is set, range upon range of conductive adhesive on flexible membrane's single face above that.According to record, this electromagnetic shielding material can be covered in the electric wire class that receives alternating bending and use.Embodiment according to patent documentation 3; Be that the coated film of conductive coating paint that thickness is the adding silver powder of 0.5 μ m is set on the single face of polyester film of 12 μ m at thickness, being provided with above that and making the conductive adhesive heat drying and the thickness that are mixed with polyesters bonding agent and nickel by powder is the conductive adhesive layer of 30 μ m.In addition; According to record; Carrying out 500,000 times will be the bend test of 1 circulation along the action that the periphery of the axle (mandrel) of external diameter
reverts to straight line after with 180 ° angular bend, and the result is not damage.
But, in nearest portable phone,,, seek slim as much as possible with the thickness that 0.1mm unit cuts down casing because the overall dimension of casing is diminished.The FPC that can on this slim casing, use needs outstanding bending property with electromagnetic shielding material.For example, will be the also not damage of bend test of 1 circulation along the action that the periphery of the axle (mandrel) of external diameter
reverts to straight line after with 180 ° angular bend even seek to carry out more than 1,000,000 times.Compared with prior art, need a kind of FPC that can overcome the bend test of carrying out under the exacting terms to use electromagnetic shielding material.
In addition, the electromagnetic shielding material that embodiment put down in writing of patent documentation 3 is that the resin film laminated thickness of 12 μ m is that the coated film and the thickness of the conductive coating paint of 0.5 μ m is the conductive adhesive layer of 30 μ m at thickness.The whole thickness of this electromagnetic shielding material has surpassed 40 μ m.
As stated, for overall dimension attenuation as much as possible, so require FPC to be as thin as below the 30 μ m with the integral thickness of electromagnetic shielding material with the casing of portable phone.That is, compare with electromagnetic shielding material, seek the thinner and solid FPC that stand severeer bend test of whole thickness and use electromagnetic shielding material with FPC of the prior art.
In addition, in order to let the pressure-sensitive bond layer have conductivity, being used in FPC need suitable volume ground interpolation electroconductive powder (metal microparticle or carbon particulate) with the conductivity pressure-sensitive bonding agent of electromagnetic shielding material.But if make the interpolation quantitative change of electroconductive powder many, the bonding force of pressure-sensitive bond layer can descend so.
In addition, the FPC on portable phone is with in electromagnetic shielding material etc., because carry out flexure operation repeatedly, so the bonding interface on each layer between base material and conductive paste layer and conductive paste layer and the FPC partly is stripped from interlayer.Worry ruptures at this local conductive paste layer of being stripped from, and As time goes on the electromagnetic shielding performance can descend.
In addition, also to stand the bending operation that carries out repeatedly (for example 1,000,000 times bend test) of e-machine length of life in order to make FPC with the base material of electromagnetic shielding material, so need outstanding flexural property.
Even the object of the present invention is to provide a kind of for being rich in the slim of flexibility and carrying out the outstanding FPC of flexural property that harsh flexure operation electromagnetic shielding performance also can not descend repeatedly and use electromagnetic shielding material.
(technical scheme of technical solution problem)
In order to stand burning till of harsh flexure operation and the conductive paste through heat, use the base material that constitutes by the heat-resistant resin film among the present invention.In the present invention, through on the base material that constitutes by the dielectric thin resin film that is applied, stacking gradually the thin layer of bond layer, conductive paste layer, seek to improve the power of connecting airtight of base material and conductive paste layer.Thus, technological thought of the present invention is to guarantee also can to improve bending property when FPC is with the electromagnetic wave shielding properties.
In addition, in the present invention, the base material that is made up of the heat-resistant resin film is considered flexibility and thermal endurance and is used the dielectric thin resin film that is applied.Thus, can the FPC that remove supporter film 6 and stripping film 7 be as thin as below the 25 μ m with the integral thickness of electromagnetic shielding material.
In addition, in the present invention, thin resin film that constitutes for the polyimide film that forms by using the solvent soluble polyimides that increases as base material and conductive paste connect airtight power, between base material and conductive paste layer, bond layer is set.
Therefore, in order to address the above problem, the present invention provides a kind of FPC to use electromagnetic shielding material, on the single face of supporter film, stacks gradually the base material, the bond layer of film, the conductive paste layer that are made up of the dielectric thin resin film that is applied.
In addition, the polyimide film that said base material forms by using the solvent soluble polyimides constitutes, and thickness is preferably 1～9 μ m.
In addition, the bond layer of said film is through making crosslinked formation of polyester resin constituent with epoxy radicals, and thickness is preferably 0.05～1 μ m.
In addition; Said bond layer preferably further contains light absorbing material, and more than one of the black pigment of more than one of the crowd that said light absorbing material is black by carbon black, graphite, nigrosine, cyanines by being selected from, titanium is black, black iron oxide, chromium oxide, manganese oxide constitute or colored pigment constitute.
In addition, the conductive paste that constitutes said conductive paste layer preferably contain be selected among the conductive filler crowd who constitutes by conductive metal particulate, CNT, carbon nano-fiber more than one and the resin glue constituent.
In addition, said conductive paste layer is burnt till for 150～250 ℃ with temperature by the Nano silver grain that will contain averaged particles footpath 1～100nm and the conductive paste of resin glue constituent, and thickness is preferably 0.1～2 μ m.
In addition, the dried specific insulation of conductive paste that constitutes said conductive paste layer is preferably 1.5 * 10
-5Below the Ω cm.
In addition, preferred further range upon range of conductive adhesive layer on said conductive paste layer.
In addition, preferred further the applying is stripped from the stripping film of processing on said conductive adhesive layer.
In addition, the present invention provides a kind of portable phone, in this portable phone, and parts that above-mentioned FPC uses as electromagnetic shielding with electromagnetic shielding material and using.
In addition, the present invention provides a kind of e-machine, in this e-machine, and parts that above-mentioned FPC uses as electromagnetic shielding with electromagnetic shielding material and using.
(effect of invention)
Above-mentioned FPC of the present invention uses by use with electromagnetic shielding material has the solvent soluble polyimides of high-temperature heat-resistance property and thin resin film (thickness is 1～9 μ m) that the polyimide film that forms constitutes.FPC of the present invention can improve conductivity with electromagnetic shielding material through carrying out burning till of conductive paste, can access the outstanding flexural property of standing harsh flexure operation simultaneously.
In addition, through using the thin resin film (thickness is 1～9 μ m) and conductive paste layer that constitutes by the polyimide film that uses the solvent soluble polyimides to form, can suppress thickness, and can access the electromagnetic wave shielding performance ability.
Thus, can the FPC that remove supporter film 6 and stripping film 7 be suppressed at below the 25 μ m with the integral thickness of electromagnetic shielding material, can the thinning portable phone and the integral thickness of e-machine.
Through in bond layer, mixing the light absorbing material that is made up of more than one black pigment or colored pigment, the single face side of electromagnetic wave shield film can be painted into specific color.
As stated, according to the present invention, even can provide be rich in flexibility, slim and carry out the outstanding FPC of flexural property that harsh flexure operation electromagnetic shielding performance also can not descend repeatedly and use electromagnetic shielding material.
Description of drawings
Fig. 1 shows that the FPC that the present invention relates to is with one of electromagnetic shielding material routine general profile chart.
Fig. 2 shows the FPC that the present invention relates to another routine general profile chart with electromagnetic shielding material.
Fig. 3 is the general profile chart that shows the state that uses with removing supporter film and stripping film the electromagnetic shielding material from the FPC of Fig. 2.
Symbol description
1 base material
2 bond layers
3 conductive paste layers
4 conductive adhesive layers
5,10,11FPC uses electromagnetic shielding material
6 supporter films
7 stripping films.
Embodiment
Below, suitable execution mode of the present invention is described.
FPC of the present invention is fitting in as by the FPC of convered structure etc. the time with electromagnetic shielding material, and outer surface is a dielectric, need be at this FPC insulation film of fitting on the electromagnetic shielding material outer surface.In addition, FPC of the present invention improves the bending property to flexure operation with the whole thickness attenuation of electromagnetic shielding material.
As shown in Figure 1, the base material 1 that FPC of the present invention uses electromagnetic shielding material 5 is for having flexual thin resin film, and this thin resin film is that the polyimide film that the solvent soluble polyimides of 1～9 μ m forms constitutes by used thickness.At the range upon range of supporter film 6 of the one side of base material 1, stack gradually to make at the another side of base material 1 and connect airtight the bond layer 2 that power improves, the conductive paste layer 3 that contains conductive particle between conductive paste layer 3 and the base material 1.As shown in Figure 2, the FPC of the present invention that another example relates to further stacks gradually conductive adhesive layer 4, stripping film 7 with electromagnetic shielding material 10 on conductive paste layer 3.This FPC is as shown in Figure 3 with electromagnetic shielding material 10, can use with electromagnetic shielding material 11 as the FPC that removes 2 stripping films 6,7.
(polyimide film)
The thin resin film that the FPC that the present invention relates to constitutes with the polyimide film that forms by using solvent soluble polyimides electromagnetic shielding material 5,10,11, that become base material 1; Have high mechanical properties, thermal endurance, insulating properties, solvent resistance as the characteristic of polyimide resin, 260 ℃ of its chemical states of degree are also very stable until reaching.
As polyimides, Thermocurable polyimide that dehydration condensation generated that carries out through the heating polyamic acid and the solvent soluble polyamic acid that dissolves in the solvent of non-dehydrating condensation type are arranged.
Usually the manufacture method of the Kapton of being known does; By in polar solvent, making diamines (ジ ア ミ Application) and carboxylic diacid acid anhydride (カ Le ボ Application acid two anhydrides) reaction; After the synthetic polyamic acid as the imines precursor; To the polyamic acid heating, perhaps, obtain the method for corresponding polyimides by using catalyst to make its dehydration ring-typeization.But the temperature of the heat treated in this imidization operation is preferably 200 ℃～300 ℃ temperature range.Heating-up temperature than the low situation of this temperature under, the possibility that can not carry out imidization is arranged, thus not preferred, under the heating-up temperature situation higher, the danger of the thermal decomposition that produces compound is arranged, so also not preferred than said temperature.
In order to improve the pliability of base material more, FPC of the present invention is with as thin as a wafer the polyimide film of electromagnetic shielding material used thickness less than 10 μ m.
Therefore, on the single face of the supporter film 6 that uses as the reinforcing material on the intensity, the polyimide film that range upon range of formation is thin.But; Polyimide film itself is for having thermal endurance with 200 ℃～250 ℃ heat treated of carrying out of heating-up temperature; And supporter film 6 is owing to take into account price and heat resisting temperature performance; Use general heat-resistant resin film, for example therefore PET (PET) resin film can not adopt of the prior art from form the method for polyimides as the polyamic acid of imines precursor.
The solvent soluble polyimides does, the imidization of its polyimides finishes, and, dissolve in solvent.Therefore, coating through under less than 200 ℃ low temperature, making solvent evaporates, can be carried out film forming by behind the coating fluid of dissolution with solvents.It is the thin resin film of polyimides that FPC of the present invention uses in the electromagnetic shielding material employed base material 1; The thin resin film of this polyimides is behind the coating fluid of the solvent soluble polyimides of the non-dehydrating condensation type of coating on the single face of supporter film 6; Make its drying with temperature less than 200 ℃ heating-up temperature, use the solvent soluble polyimides and form.Through as above operation, can at the single face laminated thickness of the supporter film 6 that forms by general heat-resistant resin film the polyimide film as thin as a wafer of 1～9 μ m.Can be on one side with supporter film 6 along its length direction conveyance, on one side on this supporter film 6, form base material 1, bond layer 2, conductive paste layer 3 etc. continuously.Can produce FPC of the present invention through the production method of volume to volume (roll to roll) and use electromagnetic shielding material.
The solvent soluble polyimides of the non-dehydrating condensation type that uses among the present invention does not have special qualification, can use the coating fluid of the common solvent soluble polyimides of selling.The coating fluid of the common solvent soluble polyimides of selling; Specifically can enumerate ソ Le ピ 1,6-PI (ソ Le ピ one industry), Q-IP-0895D (ピ one ア イ skill is ground), PIQ (Hitachi changes into industry), SPI-200N (Nippon Steel's chemistry), リ カ コ one ト SN-20, リ カ コ one ト PN-20 (new Japanese physics and chemistry) etc.The method that the coating fluid of solvent soluble polyimides is coated on the supporter film does not have special qualification, for example, can be coated with through the coating machine of metal mold coating machine, scraper type coating machine, lip formula coating machine etc.
The thickness of the polyimide film that uses among the present invention is preferably 1～9 μ m.If the thickness of polyimide film is processed less than 0.8 μ m, so since the mechanicalness intensity of the film that is made into a little less than, thereby be difficult technically.In addition, if the thickness of polyimide film surpasses 10 μ m, that FPC that just can not obtain having outstanding bending property is with electromagnetic shielding material 5,11.
(supporter film)
The base material of the supporter film 6 that uses among the present invention for example can be enumerated the polyolefin film of polyester film, polypropylene and the polyethylene etc. of PETG, polybutylene terephthalate (PBT), PEN etc.
The base material of supporter film 6 is for example PETG etc.; When base material has fissility to a certain degree; Can on supporter film 6, not implement lift-off processing, but the directly range upon range of base material that forms by the dielectric thin resin film that is applied.In addition, also can on supporter film 6, implement the lift-off processing that is easy to peel off.
In addition, the base film that uses as above-mentioned supporter film 6, when not having fissility, the coating amino-alkyd resin or gather the remover of silica resin etc. after, implement lift-off processing through heat drying.Because FPC of the present invention is fitted in FPC with electromagnetic shielding material 10,11, gathers silica resin so hope not use in this remover.Reason is; If will gather silica resin uses as remover; Have so on the surface of the base material 1 on the surface of contact supporter film 6; A part of gathering silica resin is moved, further through FPC with the inside of electromagnetic shielding material 11, the danger of moving from the electrical bond layer 4 of base material 1 guide.Has the danger that silica resin weakens the bonding force of conductive adhesive layer 4 that gathers of on the surface of this conductive adhesive layer 4, moving.Be used in the thickness of supporter film 6 of the present invention,,, be generally the thickness of 12～150 μ m degree so there be not special the qualification because from be pasted on the thickness of FPC with the integral body of electromagnetic shielding material 11 of FPC when using, remove.
(bond layer)
Be used in the bond layer 2 of FPC of the present invention, film that constitutes for the polyimide film that forms by using the solvent soluble polyimides that improves as base material 1 and the connecting airtight power of conductive paste layer 3 and be set up with electromagnetic shielding material 5,10,11.
For bond layer 2, it is 150～250 ℃ because the firing temperature of conductive paste layer 3 on it is set, so need to use the outstanding bonding agent of thermal endurance.In addition, bond layer 2 needs for as the use solvent soluble polyimides of base material 1 and the outstanding bonding force of the polyimide film that forms and conductive paste layer 3.
As the adhesive resin constituent that is used for bond layer 2, preferably use thermoplastic resins such as mylar, polyurethane resin, (methyl) acrylic resin, polyvinyl resin, polystyrene resin, polyamide.Also can be thermosetting resins such as epoxy resin, amino resins, polyimide resin, (methyl) acrylic resin in addition.
As the adhesive resin constituent of bond layer 2, be preferably especially and make the crosslinked adhesive resin constituent of polyester resin constituent, or epoxy resin is mixed in the resinoid adhesive resin constituent of polyurethane as curing agent with epoxy radicals.Therefore, bond layer 2 is than coating solvent soluble polyimide and base material 1 range upon range of, that be made up of the film film of polyimides has hard rerum natura.Polyester resin constituent with epoxy radicals is not specially limited, and the reaction etc. that has the polybasic carboxylic acid of the carboxyl more than 2 in epoxy resin (unhardened resin) that for example can be through having the epoxy radicals more than 2 in 1 molecule and 1 molecule obtains.Polyester resin constituent crosslinked with epoxy radicals uses the crosslinking agent with the used for epoxy resin of epoxy reaction to carry out.
In addition; Bond layer 2 can comprise light absorbing material, and the black pigment or the coloring pigment of more than one of the crowd that this light absorbing material is black by carbon black, graphite, nigrosine, cyanines black (シ ア ニ Application Block ラ Star Network), titanium by being selected from, black iron oxide, chromium oxide, manganese oxide constitute constitute.
Preferably sneak into the black pigment of carbon black etc. in the bond layer 2.The light absorbing material that is made up of black pigment or coloring pigment is preferably contained with 0.1～30 weight % in bond layer 2.The average grain diameter of the primary particle that black pigment or coloring pigment are preferably observed according to SEM is 0.02～0.1 μ m degree.
In addition, as black pigment, have silicon dioxide granule etc. is immersed in the dyestuff of black only to make skin section become the situation of black, perhaps the pigmentary resin from black forms, and integral body becomes the situation of black.In addition, the black pigment in addition to the case of black outside, but also includes gray, black, brown (black つ ぽ Kei brown) or dark green (black つ ぽ Kei green) and so was similar to black color particles, as long as it is not easy to reflected light dark to be used.
The thickness of adhesive linkage 2 is preferably 0.05～1 μ m degree, if the film thickness of this degree, what just can access conductive paste layer 3 connects airtight power fully.Thickness at bond layer 2 is under the situation below the 0.05 μ m; Exist the particulate of light absorbing material to expose, base material 1 and conductive paste layer 3 connect airtight the danger that power descends; In addition; Even the thickness of bond layer 2 has surpassed 1 μ m, the increase of the base material 1 that constitutes for the polyimide film that forms by using the solvent soluble polyimides or the bonding force of conductive paste layer 3 does not have effect.Therefore, if the thickness of bond layer 2 surpasses 1 μ m, manufacturing cost increases, so not preferred.
(conductive paste layer)
Be used for conductive paste layer 3 use of the present invention conductive filler is sneaked into the conductive paste as the resin combination of binding agent (binder).
As conductive paste, preferably comprise be selected among the conductive filler crowd who constitutes by conductive metal particulate, CNT, carbon nano-fiber more than one and the resin glue constituent.As the conductive metal particulate, can use the metal fine powder end of copper, silver, nickel, aluminium etc., preferably use the micropowder or the nano particle of electric conductivity height, low-cost copper or silver.In addition, also can use as CNT, carbon nano-fiber with carbon nano-particles of conductivity.
For the firing temperature with conductive paste is suppressed at the low temperature of 150～250 ℃ temperature range, the averaged particles of metal microparticle directly is preferably the scope of 1～100nm, more preferably the scope of 1～60nm.
Hope that conductive paste layer 3 dried specific insulation are 1.5 * 10
-5Below the Ω cm.
The FPC that the present invention relates to is with the conductive paste layer 3 of electromagnetic shielding material 5,10,11, through containing this metal microparticle, not only can corresponding filmization, and also it is sticking that heat takes place between the particulate, also can realize the raising of conductance simultaneously.The conductive paste that the present invention uses is preferably, and for for example averaged particles directly is that the metal microparticle of the scope of 1～100nm is evenly dispersed in the dispersion solvent, covers this metal particle sub-surface through molecule organic layer, and the dispersive property in solvent is improved.Finally, in the heating firing process of conductive paste, make metal microparticle surface contact each other, can access the conductivity of conductive paste layer 3.The heating of conductive paste is burnt till and is preferably firing temperature in the boiling spread of molecule organic layer, and reason is, for example breaks away from, evapotranspires and remove through under the temperature of 150～250 ℃ of degree, heating the molecule organic layer that makes the surface that covers metal microparticle.
In conductive paste,, preferably use thermoplastic resins such as mylar, (methyl) acrylic resin, polyvinyl resin, polystyrene resin, polyamide as mix the resin glue constituent that uses with conductive filler.In addition, also can use thermosetting resins such as epoxy resin, amino resins, polyimide resin, (methyl) acrylic resin.
Conductive paste, in these resin glue constituents, sneak into the conductive filler of conductive metal particulate, CNT, carbon nano-fiber etc. after, add the organic solvent of ethanol or ether etc. as required, carry out the adjustment of viscosity.In addition, the adjustment of the viscosity of conductive paste is carried out according to the increase and decrease of the addition (mix proportion) of organic solvent.
Burn till conductive paste layer 3 thickness afterwards and be preferably 0.1～2 μ m degree, be more preferably the thickness of 0.3～1 μ m degree.If the thickness that burns till after the conductive paste layer 3 is thinner than 0.1 μ m, obtain high electromagnetic wave shielding performance difficulty.On the other hand, if the thickness that burns till after the conductive paste layer 3 is thicker than 2 μ m, can not with the FPC that removes supporter film 6 and stripping film 7 with the THICKNESS CONTROL of the integral body of electromagnetic shielding material 11 below 25 μ m.
(conductive adhesive layer)
The FPC that the present invention relates to electromagnetic shielding material 10,11 in; Be laminated in conductive adhesive on the conductive paste layer 3 and use acrylic-based adhesives, polyurethanes bonding agent, epoxies bonding agent, rubber-like bonding agent, silicone bonding agent etc. in normally used heat-curable adhesive, to sneak into the ionic compound of particulate or the quaternary ammonium salt etc. of conductivity, electroconductive polymer etc., do not have special qualification.
Conductive adhesive does not use the pressure-sensitive bonding agent that shows the pressure-sensitive cementability at normal temperatures.The bonding agent of conductive adhesive of the present invention for getting through heating and pressurizing is preferably for the very difficult bonding agent that descends of repeated bending bonding force.
Cooperate the particulate of the conductivity of conductive adhesive layer 4 not have special qualification, can be suitable for the particulate of conductivity commonly known in the art.For example, can enumerate metal microparticle that the metal by carbon black and silver, nickel, copper, aluminium etc. constitutes and at the composition metal particulate of other metals of surface coverage of these metal microparticles.Suitable select to use these conductivity atomic one or more.
In addition; In above-mentioned conductive adhesive layer 4, in order to obtain outstanding conductivity, for the mutual contact of the particulate of conductivity and this particle and conductive paste layer and as better by contacting between the FPC of convered structure; If contain the volume conductive material, then bonding force descends.On the other hand, if lower the amount of conductive particle in order to improve bonding force, conductive particle and conductive paste layer then can appear and as insufficient, the conductivity of being become by the contact between the FPC of the convered structure this opposite problem that descends.Therefore, the use level of conductive particle is generally 0.5～50 weight portion degree, more preferably 2～10 weight portions with respect to bonding agent (solid) 100 weight portions.
In addition,, preferably contain the anisotropic conductive bonding agent of conductive particle, can use known material as the conductive adhesive that constitutes conductive adhesive layer 4 of the present invention.As this anisotropic conductive bonding agent, can use as with the thermosetting resin of the insulating properties of epoxy resin etc. as principal component, be dispersed with the bonding agent of conductive particle.
In addition, as the conductive particle that is used in the anisotropic conductive bonding agent, for example can make up gold, silver, zinc, tin, scolding tin etc. metal microparticle monomer or more than 2 kinds.In addition, as conductive particle, can use by the resin particle of metal plating.The shape of conductive particle preferably has the shape that fine particle connects into the straight chain shape, perhaps the aciculiform shape.If this shape, when FPC being carried out the heating and pressurizing processing through welded part, the conductor wirings that conductive particle can get into FPC under low exerting pressure.
The resistance value that is connected of anisotropic conductive bonding agent and FPC is preferably 5 Ω/below the cm.
The bonding force of conductive adhesive does not have special restriction, and its assay method is as the criterion with the test method of record among the JIS Z 0237.Under the condition of peel off for being spent in peel angle 180, peeling rate 300mm/ dividing, be suitably the scope of 5～30N/ inch by the bonding force on convered structure surface.During less than the 5N/ inch, for example, the electromagnetic shielding material that fits in FPC can peel off from FPC, produces floating portion at bonding force.
FPC is carried out the bonding condition of heating and pressurizing be not particularly limited, preference such as temperature are that 160 ℃, plus-pressure are 2.54MPa, hot pressing 30 minutes.
(stripping film)
As the base material of stripping film 7, for example can enumerate the polyolefin film of polyester film, polypropylene or the polyethylene etc. of PETG, polybutylene terephthalate (PBT), PEN etc.After amino-alkyd resin or the remover that gathers silica resin etc. are coated these base films, implement lift-off processing through heat drying.FPC of the present invention owing to fit in FPC, does not gather silica resin so in this remover, preferably do not use with electromagnetic shielding material 10,11.Reason is; If will gather silica resin uses as remover; Have so on the surface of conductive adhesive layer 4 on the surface of contact stripping film 7; A part of gathering silica resin is moved, further through FPC with the inside of electromagnetic shielding material 11, the danger of moving to base material 1 from conductive adhesive layer 4.In addition, has the possibility that silica resin weakens the bonding force of conductive adhesive layer 4 of gathering that on the surface of this conductive adhesive layer 4, moves.Be used in the thickness of stripping film 7 of the present invention owing to be from fit in FPC the thickness with the integral body of electromagnetic shielding material 11 of FPC when using, to remove,, be generally the thickness of 12～150 μ m degree so there is not special qualification.
FPC of the present invention can fit in the FPC that receives flexure operation repeatedly with electromagnetic shielding material 5,10,11 and use, and suits to use with electromagnetic shielding material as the outstanding FPC of bending property.In addition, the parts used as electromagnetic shielding with electromagnetic shielding material of FPC of the present invention can be used in portable phone or e-machine.
Embodiment
Below, specify the present invention according to embodiment.
(embodiment 1)
With thickness is that (Co., Ltd.'s system, article number spin in Japan: E5100) use as supporter film 6 for PETG (PET) film of 50 μ m.Coating fluid with the solvent soluble polyimides on the single face of this supporter film 6 carries out the curtain coating coating with the mode that dried thickness becomes 4 μ m, makes its drying, the range upon range of base material 1 that is made up of dielectric thin resin film.On the base material that is formed 1; Use is used to form the coating of bond layer 2; So that being the mode of 0.3 μ m, dried thickness is coated with; Lamination adhesive layer 2, said coating is for will be as the carbon black of the black pigment of light absorbing material and the polyester resin constituent mixing that heat resisting temperature is 260～280 ℃.On bond layer 2; As conductive filler; Use directly is about the conductive paste that the silver particles hybrid modulation of 50nm becomes with averaged particles; After the mode that becomes 0.3 μ m with dried thickness is coated with, burn till and form conductive paste layer 3 with 150 ℃ of temperature, the FPC that obtains embodiment 1 uses electromagnetic shielding material.The value of measuring the specific insulation of dry conductive paste layer 3 is 1.5 * 10
-5Below the Ω cm.
(embodiment 2)
With thickness is that (Co., Ltd.'s system, article number spin in Japan: E5100) use as supporter film 6 for PETG (PET) film of 50 μ m.On the single face of this supporter film 6, the coating fluid of solvent soluble polyimides is carried out the curtain coating coating with the mode that dried thickness becomes 8 μ m, make its drying, the range upon range of base material 1 that constitutes by dielectric thin resin film.On the base material that is formed 1; Use is used to form the coating of bond layer 2; So that being the mode of 0.3 μ m, dried thickness is coated with; Lamination adhesive layer 2, said coating is for will be as the carbon black of the black pigment of light absorbing material and the polyester resin constituent mixing that heat resisting temperature is 260～280 ℃.On bond layer 2; As conductive filler; Use directly is about the conductive paste that the silver particles hybrid modulation of 50nm becomes with averaged particles; After the mode that becomes 0.3 μ m with dried thickness is coated with, burn till and form conductive paste layer 3 with 150 ℃ of temperature, the FPC that obtains embodiment 2 uses electromagnetic shielding material.The value of measuring the specific insulation of dry conductive paste layer 3 is 1.5 * 10
-5Below the Ω cm.
(comparative example 1)
Except not using supporter film 6, and to use by thickness as base material 1 be that the same with embodiment 1, the FPC that obtains comparative example 1 uses electromagnetic shielding material beyond the polyimide film that constitutes of the Thermocurable polyimide of 10 μ m.
(assay method of the surface resistivity of conductive paste layer 3)
According to the regulation that JIS-K-7194 " utilizes the resistivity test method of the four probe method of Markite ", measure the surface resistivity of conductive paste layer 3 through the resistrivity meter (ロ レ ス タ-GP T600 type) of Mitsubishi Chemical's (strain) manufacturing.
(assay method of bend test (1))
Use heat-curable adhesive (ス リ one ボ Application De system, article number: 33A-798); The mode that becomes 12 μ m with dried thickness is adjusted; It is coated on the conductive paste layer 3; (ス リ one ボ Application De system, article number: conductive paste layer 3 33A-798) overlaps on the flexible printed circuit substrate that is provided with specimen will to be coated with heat-curable adhesive; And make itself and FPC with conductive adhesive layer 4 side of electromagnetic shielding material relatively to, hot pressing after 30 minutes under 160 ℃, 2.54MPa, obtain test film according to the size severing of 12.7mm * 160mm.
According to IPC specification TM-650 " TEST METHODS MANUAL " (reference 3 " resistance to bend(ing) " of JIS-C-6471); Use the test film of severing under the imposing a condition of R=1.5mm, to carry out the IPC bend test; The resistance value of instrumentation conductive paste layer through conductive layer the repeated bending action and resistance value during with the initial stage is compared the number of times of the bend test when increasing to 2 times, estimate bending property.
Bend test result is judged to be; According to bend test, the situation that the number of times of the bend test when increasing to 2 times surpasses 300,000 times is regarded as qualified (zero), the situation below 300,000 times is regarded as defective (*) because the action of the repeated bending of conductive layer and resistance value during with the initial stage are compared with the resistance value of conductive paste layer.
(assay method of bend test (2))
Use heat-curable adhesive (ス リ one ボ Application De system, article number: 33A-798); The mode that becomes 12 μ m with dried thickness is adjusted; It is coated on the conductive paste layer 3; (ス リ one ボ Application De system, article number: conductive paste layer 3 33A-798) overlaps on the flexible printed circuit substrate that is provided with specimen will to be coated with heat-curable adhesive; And make itself and FPC with conductive adhesive layer 4 side of electromagnetic shielding material relatively to, hot pressing after 30 minutes under 160 ℃, 2.54MPa, obtain test film according to the size severing of 12.7mm * 160mm.
According to IPC specification TM-650 " TEST METHODS MANUAL " (reference 3 " resistance to bend(ing) " of JIS-C-6471); Use the test film of severing under the imposing a condition of R=1.0mm, to carry out the IPC bend test; The resistance value of instrumentation conductive paste layer is because bending property is estimated in the repeated bending of conductive layer action and resistance value during with the initial stage is compared the number of times of the bend test when increasing to 2 times.
Bend test result is judged to be; According to bend test, the situation that the number of times of the bend test when increasing to 2 times surpasses 300,000 times is regarded as qualified (zero), the situation below 300,000 times is regarded as defective (*) because the action of the repeated bending of conductive layer and resistance value during with the initial stage are compared with the resistance value of conductive paste layer.
(assay method of flexibility test)
Use is used for the sample (wide 17mm * long 160mm) of bend test; The last sample of installing of ring stiffness testing machine (Le one プ ス テ イ Off ネ ス テ ス タ) of doing manufacturing in the smart mechanism of (strain) Japan begins to measure; With the sample looped-shaped bending, the load when rolling according to the diametric(al) along this ring is estimated the power of elasticity (コ シ).Particularly; The mode that becomes electromagnetic shielding material with the outside of the sample looped-shaped bending that will be used for bend test is made the ring of periphery 80mm; Begin to apply power from the upside of ring with the speed of 3.3mm/sec; Distance until the minor axis of sample portion becomes 1.5mm, is determined at the stress of the sample when keeping for 5 times in second under this state.
(result of the test)
About embodiment 1～2 and comparative example 1, carry out surface resistivity, bend test and the flexibility test of conductive paste layer according to above-mentioned test method, table 1 illustrates the result of the test that obtains.
(table 1)
Result according to the bend test shown in the table 1 can know, as the thickness of the polyimide film of base material 1 FPC had considerable influence with the result of the flexibility test of electromagnetic shielding material.
When the thickness of the polyimide film that forms using the solvent soluble polyimides is the film of 4 μ m because FPC is rich in flexibility with electromagnetic shielding material, even thereby bending radius little of R=1.0mm, also can access outstanding bending property.In addition, when the thickness of the polyimide film that forms using the solvent soluble polyimides was 8 μ m, if bending radius is R=1.5mm, bending property was better, if but bending radius is little of R=1.0mm, and then bending property is bad.
Can know that from these result of the tests the thickness of the base material that the polyimide film that the FPC with outstanding bending property needs to form by using the solvent soluble polyimides with electromagnetic shielding material constitutes forms the film of 1～9 μ m.But as the thickness of the polyimide film of selling in Japan now that is made up of Thermocurable polyimide, 7.5 μ m are the thickness of thin slab product.FPC of the present invention with electromagnetic shielding material in, need to use polyimide film in the base material than this thin thickness.Therefore, be the polyimide film of 1～9 μ m only through in base material, using the thickness that obtains through coating fluid than unfertile land curtain coating coating solvent soluble polyimide, the FPC that just can access outstanding bending property uses electromagnetic shielding material.
FPC of the present invention can be used in various e-machines such as portable phone, notebook computer, carried terminal as the electromagnetic shielding parts with electromagnetic shielding material.
Claims (10)
1. a FPC uses electromagnetic shielding material, it is characterized in that, on the single face of supporter film, stacks gradually the base material, the bond layer of film, the conductive paste layer that are made up of the dielectric thin resin film that is applied.
2. FPC according to claim 1 uses electromagnetic shielding material, it is characterized in that,
The polyimide film that said base material forms by using the solvent soluble polyimides constitutes, and thickness is 1～9 μ m.
3. FPC according to claim 1 and 2 uses electromagnetic shielding material, it is characterized in that,
The bond layer of said film is through making crosslinked formation of polyester resin constituent with epoxy radicals, and thickness is 0.05～1 μ m.
4. FPC according to claim 1 and 2 uses electromagnetic shielding material, it is characterized in that,
Said bond layer further contains light absorbing material, and more than one of the black pigment of more than one of the crowd that said light absorbing material is black by carbon black, graphite, nigrosine, cyanines by being selected from, titanium is black, black iron oxide, chromium oxide, manganese oxide constitute or colored pigment constitute.
5. FPC according to claim 1 and 2 uses electromagnetic shielding material, it is characterized in that,
Said conductive paste layer is burnt till for 150～250 ℃ with temperature by the Nano silver grain that will contain averaged particles footpath 1～100nm and the conductive paste of resin glue constituent, and thickness is 0.1～2 μ m.
6. FPC according to claim 1 and 2 uses electromagnetic shielding material, it is characterized in that,
The dried specific insulation of conductive paste that constitutes said conductive paste layer is 1.5 * 10
-5Below the Ω cm.
7. FPC according to claim 1 and 2 uses electromagnetic shielding material, it is characterized in that,
Further range upon range of conductive adhesive layer on said conductive paste layer.
8. FPC according to claim 7 uses electromagnetic shielding material, it is characterized in that,
On said conductive adhesive layer, further fit and be stripped from the stripping film of processing.
9. a portable phone is characterized in that, the parts that each described FPC in the claim 1 to 8 is used as electromagnetic shielding with electromagnetic shielding material use.
10. an e-machine is characterized in that, the parts that each described FPC in the claim 1 to 8 is used as electromagnetic shielding with electromagnetic shielding material use.
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| CN201510489727.5A CN105208843B (en) | 2011-04-26 | 2012-04-26 | FPC electromagnetic shielding materials |
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| JP2011098430A JP5707216B2 (en) | 2011-04-26 | 2011-04-26 | Electromagnetic wave shielding material for FPC |
| JP2011-098430 | 2011-04-26 |
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| CN110024503B (en) * | 2016-12-08 | 2021-04-20 | 杜邦帝人先进纸（日本）有限公司 | Electromagnetic wave suppressing sheet |
| CN106531344A (en) * | 2016-12-26 | 2017-03-22 | 南昌联能科技有限公司 | Electromagnetic shielding film for cable, manufacturing method for electromagnetic shielding film and manufacturing method for wire rod |
| CN108718518A (en) * | 2018-05-21 | 2018-10-30 | 深圳昌茂粘胶新材料有限公司 | A kind of electromagnetic wave shielding membrane material and preparation method thereof |
| CN108718518B (en) * | 2018-05-21 | 2020-02-07 | 深圳昌茂粘胶新材料有限公司 | Electromagnetic wave shielding film material and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2012231021A (en) | 2012-11-22 |
| KR101407684B1 (en) | 2014-06-17 |
| TWI468084B (en) | 2015-01-01 |
| CN105208843A (en) | 2015-12-30 |
| TW201309111A (en) | 2013-02-16 |
| KR20140063548A (en) | 2014-05-27 |
| KR20120121357A (en) | 2012-11-05 |
| CN105208843B (en) | 2018-04-24 |
| JP5707216B2 (en) | 2015-04-22 |
| KR101602214B1 (en) | 2016-03-10 |
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Application publication date: 20121031 |