CN107613628A - Electromagnetic shielding material - Google Patents
Electromagnetic shielding material Download PDFInfo
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- CN107613628A CN107613628A CN201710531323.7A CN201710531323A CN107613628A CN 107613628 A CN107613628 A CN 107613628A CN 201710531323 A CN201710531323 A CN 201710531323A CN 107613628 A CN107613628 A CN 107613628A
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- Prior art keywords
- electromagnetic shielding
- shielding material
- base material
- film
- conductive
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Classifications
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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
- H05K9/0084—Electromagnetic shielding materials, e.g. EMI, RFI shielding comprising a single continuous metallic layer on an electrically insulating supporting structure, e.g. metal foil, film, plating coating, electro-deposition, vapour-deposition
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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
- B32B15/00—Layered products comprising a layer of metal
- B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
- B32B15/08—Layered products comprising a layer of metal comprising metal 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
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- Physics & Mathematics (AREA)
- Electromagnetism (AREA)
- Engineering & Computer Science (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Shielding Devices Or Components To Electric Or Magnetic Fields (AREA)
- Laminated Bodies (AREA)
Abstract
The invention reside in provide a kind of tracing ability for high rank height also excellent electromagnetic shielding material.The present invention provides a kind of electromagnetic shielding material, it is characterized in that, it is laminated with the conductive paste bed of material (13) and conductive adhesive layer (14) successively on the one side for the base material (11) being made up of dielectric resin film in the thickness direction of base material (11), and the tensile elongation of base material (11) is more than 100%.
Description
Technical field
The present invention relates to the electromagnetic shielding material for the electromagnetic wave shielding that can be used in printed base plate etc..
Background technology
In the portable electric appts such as mobile phone, it is widely used for being integrated with the printed base plate of electronic unit.In addition,
In order to prevent the operating of the electronic equipment caused by the influence of electromagnetic wave noise from slipping up, electromagnetic shielding material has been used.
For example, having recorded a kind of electromagnetic wave shielding sheet in patent document 1, it is to include insulating barrier, conductive layer and bonding agent
The electromagnetic wave shielding sheet of layer, conductive layer contain resin and electroconductive stuffing, and sheet resistance is 100m Ω/below, electrical conductivity 1
×106More than S/m.
In addition, recorded a kind of electromagnetic shielding film in patent document 2, its using lamination state possess thickness as 0.5 μm~
12 μm of metal level and electric conductivity anisotropy bond layer.
Prior art literature
Patent document
Patent document 1：Japanese Unexamined Patent Publication 2015-138813 publications
Patent document 2：Japanese Unexamined Patent Publication 2015-109449 publications
The content of the invention
Invent problem to be solved
As printed base plate, it is known to the flexible base that insulated substrate is the rigid substrates of hard, insulated substrate is flexibility
Plate including part with flexibility and the rigid and flexible substrate (rigid flexible system substrate) of the part of hard etc..In substrate thickness
In the case that different portion boundary portion etc. has high rank height, when electromagnetic shielding material is affixed into printed base plate,
If electromagnetic shielding material for printed base plate rank it is high follow deficiency, can rank eminence produce gap, have electromagnetic wave
Intrusion or leakage, the intrusion of moisture, the attachment of dust the problems such as.If limpingly making electromagnetic shielding material follow rank height,
Fracture or damage of the conductive layer of electromagnetic shielding material etc. are formed, thus deteriorates electromagnetic wave shielding characteristic sometimes.
The present invention is to carry out in view of the foregoing, and its problem is to provide a kind of tracing ability for high rank height
Also excellent electromagnetic shielding material.
For solving the scheme of problem
In order to solve above-mentioned problem, the present invention provides a kind of electromagnetic shielding material, it is characterised in that by dielectric tree
On the one side for the base material that adipose membrane is formed, the thickness direction of above-mentioned base material is laminated with the conductive paste bed of material and conductive adhesive successively
Layer, the tensile elongation of above-mentioned base material is more than 100%.
The above-mentioned conductive paste bed of material preferably comprises the silver nano-grain that particle diameter is less than 1 μm.
The tensile elongation of above-mentioned base material is preferably less than more than 100% 300%.
Above-mentioned base material is preferably made up of solvent-soluble polyimide film.
Above-mentioned base material is preferably made up of polyimide film, and the polyimide film use has carbon atom between aromatic unit
Number is formed for the polyimide material of the aliphatic unit of more than 3.
The thickness of above-mentioned conductive adhesive layer is preferably less than 15 μm.
Above-mentioned conductive adhesive layer is preferably electric conductivity anisotropy bond layer.
Above-mentioned conductive adhesive layer preferably comprises polyurethane.
It it is preferably 6 μm~20 μm from gross thickness of the above-mentioned base material untill above-mentioned conductive adhesive layer.
Above-mentioned base material is preferably opposite in the side with being laminated with the above-mentioned conductive paste bed of material and above-mentioned conductive adhesive layer
Face by can from above-mentioned base material peel off supporting mass film supported.
In addition, the present invention provides a kind of mobile phone, it possesses above-mentioned electromagnetic shielding material.
In addition, the present invention provides a kind of electronic equipment, it possesses above-mentioned electromagnetic shielding material.
Invention effect
According to the electromagnetic shielding material of the present invention, using the teaching of the invention it is possible to provide a kind of tracing ability for high rank height is also excellent
Electromagnetic shielding material.
Brief description of the drawings
Fig. 1 is the schematic sectional view of one for showing the electromagnetic shielding material of the present invention.
Fig. 2 is the schematic sectional view illustrated to the evaluation method of the high tracing ability of rank in embodiment.
Embodiment
Below, the preferred embodiment of the present invention is illustrated.
Figure 1 illustrates the schematic sectional view of the electromagnetic shielding material of present embodiment.The electromagnetic shielding material
10 have following compositions：On the one side for the base material 11 being made up of dielectric resin film, the thickness direction of above-mentioned base material layer successively
The conductive paste layers 13 of product and conductive adhesive layer 14.Electromagnetic shielding material 10 is being affixed to the print as adherend
During brush substrate etc., because outer surface is dielectric substrate 11, thus further in its outer surface electric insulation need not be set coated
Material.
(base material)
Base material 11 is the insulating barrier being made up of dielectric resin film.As the resin film for forming base material 11, can enumerate poly-
Imide resin film, polyester resin film, polyamide resin etc..In the case where base material 11 is made up of polyimide resin film,
Feature with polyimide resin, i.e., high mechanical strength, heat resistance, insulating properties, solvent resistance, it is considered that reaching
Chemical property is stable before 260 DEG C of degree, thus is suitable.
Polyimides has in the thermohardening type polyamides generated by heating in dehydration condensation caused by polyamic acid
Imines；With the solvent-soluble polyimide for dissolving in solvent of non-dehydrating condensation type.As the manufacture method of polyimide film,
The method being usually known is as follows：By making diamines and carboxylic acid dianhydride be reacted in polar solvent, so as to synthesize conduct
The polyamic acid of imide precursor, cyclodehydration is carried out to polyamic acid using heat or catalyst, so as to which corresponding polyamides be made
Imines.But, it is considered that the heat treatment temperature in the process of the imidizate is preferably 200 DEG C~300 DEG C of temperature model
Enclose.In the case where heating-up temperature is less than the temperature, imidizate is possible to without thus being not preferred.In heating temperature
In the case that degree is higher than said temperature, it is possible to the thermal decomposition of compound occurs, thus is not preferred.
In order to further improve the flexibility of base material 11, preferred thickness is less than 10 μm of very thin polyimide film.If propping up
Hold the polyimide film that lamination is thin on the one side of body film 21 and form base material 11, even if the then mechanical strength of polyimide film in itself
It is low, continuous transport also is carried out readily along length direction, thus be preferable.As supporting mass film 21, from taking into account price and resistance to
The aspect of stability energy is set out, the resin film of preferred generic, such as polyethylene terephthalate (PET) resin film.But
It is that PET heat resisting temperature is high not as polyimides, thus can not use the coating that imide precursor is carried out on PET
With the method for the imidizate of polyamic acid.
For solvent-soluble polyimide, because the imidizate of its polyimides is completed, and dissolve in molten
Agent, thus be coated with it is dissolved in solvent obtained from after coating fluid, solvent can be made in a low temperature of less than 200 DEG C
Volatilization carrys out film forming.Therefore, in the case where base material 11 is made up of solvent-soluble polyimide film, following method shapes can be utilized
Into the film resin film of polyimide film, this method is that coating is the solvent of non-dehydrating condensation type on the one side of supporting mass film 21
After the coating fluid of soluble polyimide, its drying is made with heating-up temperature of the temperature less than 200 DEG C.Furthermore it is possible to while along
Length direction carries identical supporting mass film 21, while continue to be continuously formed on the one side of supporting mass film 21 anchor layer 12,
The conductive paste bed of material 13, conductive adhesive layer 14 etc..Thus, electromagnetic shielding material can be also produced in a manner of volume to volume
10, processability, productivity are excellent.
It is not particularly limited, can uses for the solvent-soluble polyimide of the non-dehydrating condensation type for base material 11
The coating fluid of commercially available solvent-soluble polyimide.As the coating fluid of commercially available solvent-soluble polyimide, specifically may be used
To enumerate Solpit 6,6-PI (Solpit Industries, Ltd.), Q-IP-0895D (PI R＆D CO., LTD), PIQ (days
Vertical chemical conversion industry), SPI-200N (Nippon Steel's chemistry), RIKACOAT SN-20, RIKACOAT PN-20 (new Japan Chemical) etc..
For the method on the coating solution of solvent soluble polyamide to supporting mass film 21 is not particularly limited, example can be utilized
Such as die coating machine, scraper coating machine, lip coating machine coating machine are coated.
The thickness (such as thickness of polyimide film) of base material 11 is preferably 1 μm~9 μm.Thickness is being made in polyimide film
When degree is less than 0.8 μm of film, the mechanical strength of manufactured film is weak thus technically difficult.In addition, if the thickness of base material 11 surpasses
10 μm are crossed, then is difficult to obtain electromagnetic shielding material 10 slim and with the excellent high tracing ability of rank.In addition, in base material 11
Thickness is thinner than in the case of about 7 μm, it is difficult to which tension force when roller is batched in adjustment.It is therefore preferable that on the one side of supporting mass film 21
Lamination thin polyimide film forms base material 11.Or conductive adhesive layer is preferably formd on stripping film 22 in advance
14th, the conductive paste bed of material 13, anchor layer 12 etc., base material 11 is further formed afterwards.
In the case where using the base material 11 for not utilizing supporting mass film 21 and being only made up of thin polyimide film, thickness is excellent
Elect about 1 μm~9 μm as.
In addition, in order to improve for the high tracing ability of the rank of the printed base plate as adherend, the base material of present embodiment
11 preferred tensile elongations are high.The tensile elongation of base material 11 is preferably more than 100%.In addition, the stretching for base material 11 is stretched
The upper limit of long rate is not particularly limited, and can exemplify less than 300%.The modulus of elasticity of base material 11 is preferably more than 1.0GPa
It is 2.5GPa following.In the case where being made up of the high base material 11 of tensile elongation polyimide film, for example, it is preferable to using in fragrance
There is the polyimide film that carbon number is formed by the polyimide material of the aliphatic unit of more than 3 between race's unit.Enter
And aliphatic unit preferably comprises the polyalkylene oxide base of the alkylidene with the degree that carbon number is 1~10.
In addition, the moisture-vapor transmission of the polyimide film used in the base material 11 of present embodiment is preferably 500g/
m2More than it.It is less than 500g/m in moisture-vapor transmission2In the case of it, the coated printing of electromagnetic shielding material 10 is utilized
After substrate in heating process as solder backflow, due in residual solvent or the outgassing of bonding agent, film from each layer
Moisture is drastically heated and caused vapor, and each interlayer is likely to occur stripping.Do not set especially for moisture-vapor transmission
The upper limit, but as long as using identical material, then moisture-vapor transmission is inversely proportional to the thickness, thus is steamed in thickness thinning, raising water
In the case of vapor permeability, preferably in above-mentioned thickness range.
(supporting mass film)
Supporting mass film 21 can be peeled off in the use of electromagnetic shielding material 10 from base material 11.As supporting mass film 21
Base material, for example, polyethylene terephthalate, polybutylene terephthalate (PBT), PEN
Deng polyester film；The polyolefin films such as polypropylene, polyethylene.The thickness of supporting mass film 21, which is not included in, to be coated on printed base plate and uses
When electromagnetic shielding material 10 integral thickness in, thus there is no particular limitation as to it, usually 12 μm~150 μm of journey
Degree.
There is certain in itself for the base material such as polyethylene terephthalate (PET) in the base material of supporting mass film 21
In the case of the fissility of degree, lift-off processing can not be implemented on supporting mass film 21, direct lamination is situated between by the electricity being coated with
The base material 11 that matter film resin film is formed, it can also implement on the surface of supporting mass film 21 in order that the more easily peelable stripping of base material 11
From processing.In addition, in the case where the base material of supporting mass film 21 does not have fissility, can be by coating amino-alkyd resin
Or it is thermally dried after the remover such as silicone resin and implements lift-off processing.It is applied to the remover of supporting mass film 21 preferably not
Use silicone resin.If using silicone resin as remover, a part for silicone resin can be transferred to and supporting mass film 21
Surface contact base material 11 surface, and then silicone resin is transferred to electric conductivity by the inside of electromagnetic shielding material 10
The surface of bond layer 14, it is possible to the bonding force of conductive adhesive layer 14 can be weakened.
(anchor layer)
In the electromagnetic shielding material 10 of present embodiment, in order to realize the closely sealed of base material 11 and the conductive paste bed of material 13
The raising of power, anchor layer 12 can be used.Anchor layer 12 is by the bonding of the film be bonded with the conductive paste bed of material 13 of base material 11
Oxidant layer.In the case of the adaptation of the conductive paste bed of material 13 and base material 11 is sufficient, anchor layer 12 can also be omitted.In anchor layer
Carry out the coating of conductive paste on 12 and heating is fired and, it is necessary to using heat resistance in the case of forming the conductive paste bed of material 13
Material of the excellent adhesive resin as anchor layer 12.
As the adhesive resin for anchor layer 12, polyester resin, polyurethane resin, (methyl) third can be preferably enumerated
The thermoplastic resins such as olefin(e) acid resinoid, polyvinyl resin, polystyrene resin, polyamide；Epoxy resin, amino resins,
The thermohardening type resins such as polyimide resin, (methyl) acrylic resin.It is especially excellent as the adhesive resin of anchor layer 12
Choosing, make the adhesive resin composition of polyester resin composition crosslinking with epoxy radicals；In polyurethane series resin
It is mixed with the adhesive resin composition of the epoxy resin as curing agent.Therefore, anchor layer 12 with by the thin of polyimide film
The base material 11 that film is formed, which is compared, has harder physical property.Do not limited especially for the polyester resin composition with epoxy radicals
It is fixed, for example, can by the epoxy resin (its uncured resin) in 1 molecule with more than 2 epoxy radicals with 1 molecule with 2
Reaction of polybasic carboxylic acid of individual above carboxyl etc. and obtain.The crosslinking of polyester resin composition with epoxy radicals can use
With the crosslinking agent of the epoxy resin of epoxy reaction.
The thickness of anchor layer 12 is preferably 0.05 μm~1 μm of degree.If the thickness of the degree, then can obtain and conduction
The sufficient closing force of property paste layers 13.In the case where the thickness of anchor layer 12 is less than 0.05 μm, base material 11 and electric conductivity
The closing force of paste layers 13 is possible to reduce.In addition, if the thickness of anchor layer 12 is more than 1 μm, cost increase, because rather than
Preferably.
(the conductive paste bed of material)
Filled out in the formation of the conductive paste bed of material 13 using being mixed into electric conductivity in the resin combination as binding agent
Expect the conductive paste formed.As conductive paste, preferably comprise to be selected from and received by conductive metallic particles, CNT, carbon
More than a kind and adhesive resin composition in the electroconductive stuffing group that rice fiber is formed.As conductive metallic particles, use
The metal fine powders such as copper, silver, nickel, aluminium end, but from electric conductivity is high, low-cost aspect, preferably using the micro mist of copper or silver,
Or particle diameter is less than 1 μm of nano particle (copper nano particles, silver nano-grain etc.).It is conductive as having alternatively, it is also possible to use
CNT, the carbon nano-fiber of the carbon nano-particle of property.Specific insulation after the firing of the conductive paste bed of material 13 is preferably
1.5×10-5Below Ω cm.In addition, the surface resistivity after the firing of the conductive paste bed of material 13 is preferably 0.3 Ω/below.
In order to the firing temperature of conductive paste is suppressed to 150 DEG C~250 DEG C temperature range low temperature, metal particle
Average grain diameter be preferably 1nm~120nm scope, more preferably 1nm~100nm scope.By making the conductive paste bed of material
Containing such metal particle in 13, filming can not only be carried out, and particulate occur each other it is hot sticky, additionally it is possible to realize simultaneously
The raising of electrical conductivity.In addition, the surface by using molecule organic layer coated metal particulate, it is possible to increase the dispersiveness in solvent
Energy.In the heating ablating work procedure of conductive paste, metal particle mutually contacts surface, so as to which the conductive paste bed of material 13 shows
Go out electric conductivity.
The heating of conductive paste is fired for example by being heated to 150 DEG C~250 DEG C of degree, and makes coated metal particulate
The molecule organic layer on surface depart from, remove its evaporation, therefore preferably make firing temperature in the boiling spread of molecule organic layer.
In the firing of conductive paste, in the case where using supporting mass film 21 or stripping film 22, in order to suppress these
The heat deterioration of resin film, firing temperature is preferably set to be lower temperature, preferably 150 DEG C~180 DEG C.
As the adhesive resin composition being used in mixed way in conductive paste with electroconductive stuffing, can preferably enumerate
The thermoplastic resins such as polyester resin, (methyl) acrylic resin, polyvinyl resin, polystyrene resin, polyamide；Ring
The heat-curing resins such as oxygen tree fat, amino resins, polyimide resin, (methyl) acrylic resin.
For conductive paste, conductive metallic particles, carbon nanometer are mixed into these adhesive resin compositions
After the electroconductive stuffings such as pipe, carbon nano-fiber, the organic solvent such as alcohol or ether is added as needed and carries out viscosity regulation.Viscosity is adjusted
It can be carried out by the addition (mix ratio) of organic solvent.Combined by being mixed into resin glue into conductive paste
Thing, make FPC followed with electromagnetic shielding material rank it is high and in the case of being attached, even if being elongated can also prevent
It is cracked, prevents from damaging electric conductivity.
Thickness after the firing of the conductive paste bed of material 13 is preferably 0.1 μm~2 μm of degree, is more preferably 0.3 μm~1 μm
Degree.Thickness after the firing of the conductive paste bed of material 13 is thinner than in the case of 0.1 μm, it is difficult to obtains high electromagnetic wave shielding
Performance.On the other hand, if the thickness after the firing of the conductive paste bed of material 13 is thicker than 2 μm, cost increases, thus is not preferred
's.
(conductive adhesive layer)
Conductive adhesive layer 14 is the bonding for electromagnetic shielding material 10 to be pasted on to the adherends such as printed base plate
Oxidant layer.As conductive adhesive layer 14, the Thermocurable bond layer of heating pressurization is preferably based on, rather than is shown at normal temperatures
The adhering agent layer of pressure-sensitive adhesive is shown.Thus, even if in the case where printed base plate is by alternating bending, bonding force is not easy to drop
It is low.
As the Thermocurable bonding agent for conductive adhesive layer 14, acrylic acid series bonding agent, poly- ammonia can be enumerated
The usually used heat curable adhesives such as ester system bonding agent, epoxy bonding agent, rubber series bonding agent, silicone-based bonding agent.
Furthermore it is preferred that there is the Thermocurable bonding agent of anti-flammability using fire retardants such as phosphorus system, bromine system etc. are mixed with, to it without spy
Do not limit.Thermocurable bonding agent can also be used as using polyurethane resin, the polyurethane resin uses phosphorous compound
Contain as polyol compound or the polyisocyanate compound of the raw material as polyurethane in the molecular structure of resin
Phosphorus.The conductive adhesive layer 14 of Thermocurable preferably comprises phosphorous polyurethane resin composition and epoxy resin.
It is not particularly limited, can applies existing known for electrically conductive microparticle of the mixture in conductive adhesive layer 14
Electrically conductive microparticle.For example,：Carbon black；The metal particle being made up of metals such as silver, nickel, copper, aluminium；And in these gold
The surface of category particulate has been coated to the composition metal particulates of other metals, and can suitably select in these one kind or two or more makes
With.
In addition, in above-mentioned conductive adhesive, by the mutual contact of conductive particle and the conductive particle with
The contact of the conductive paste bed of material and the printed base plate as adherend, so as to show electric conductivity.Therefore, led if containing in large quantities
Conductive substances, then excellent electric conductivity can be obtained, but bonding force reduces, if reducing the content of conductive material, bonding force
Improve, but electric conductivity reduces, and the problem of this opposite be present.Accordingly, with respect to the parts by weight of bonding agent (solid constituent) 100, lead
The blend amount of electrical particulate is usually the degree of the parts by weight of 10 parts by weight~100, the parts by weight of more preferably 30 parts by weight~80.
In addition, as the conductive adhesive for forming conductive adhesive layer 14, the conduction of electrically conductive microparticle is preferably comprised
Property anisotropy bonding agent.As the electric conductivity anisotropy bonding agent, known material can be used, it is, for example, possible to use
Using the heat-curing resin of the insulating properties such as epoxy resin as main component and it is dispersed with the bonding agent of electrically conductive microparticle.As with
In the electrically conductive microparticle of electric conductivity anisotropy bonding agent, for example,：The metal particle of gold, silver, zinc, tin, solder etc.
In it is one kind or two or more；Or metal-coated resin particle.On the shape of electrically conductive microparticle, preferably with branch
Shape or needle-like.If such shape, when carrying out heating pressurized treatments to adherend printed base plate using welded part,
Electrically conductive microparticle can be made to bite the conductor wirings of printed base plate with low plus-pressure, electric conductivity anisotropy bonding can be reduced
Resistance between oxidant layer and conductor wirings.
It is not particularly limited for the bonding force of conductive adhesive, its assay method is based on described in JIS Z 0237
Test method.Peeled off, under conditions of peeling rate 300mm/ minutes in peel angle 180 degree, to the bonding force on adherend surface
The scope of preferably 5N/ inches~30N/ inches.When bonding force is less than 5N/ inches, for example, being pasted on the electromagnetic wave of printed base plate
Shielding material 10 is peeled off or floated sometimes.The condition of heating pressurization bonding for printed base plate is not particularly limited, such as
It is preferred that temperature is set to 160 DEG C, plus-pressure is set to 4.5MPa progress hot pressing in 60 minutes.
The thickness of conductive adhesive layer 14 is preferably less than 15 μm.Thus, the thickness of conductive adhesive layer 14 is included
The gross thickness of electromagnetic shielding material 10 inside is thinning, and the high tracing ability of rank improves.If the thickness of conductive adhesive layer 14 is thick
In 15 μm, then the slimming of information terminal in recent years, and cost increase can not be tackled, thus be not preferred.
(light absorber)
, can be in the composition electricity in addition to supporting mass film 21 and stripping film 22 in order to assign the light-proofness of electromagnetic shielding material 10
Light absorber is included in any layer of magnetic wave shielding material 10.Example can be enumerated with the layer that the purpose includes light absorber
Such as：1 layer in base material 11, anchor layer 12, the conductive paste bed of material 13, conductive adhesive layer 14 or more than 2 layers.As light absorbs
Agent, can enumerate selected from by non-conductive carbon black, graphite, nigrosine, Cyanine Black, titanium be black, black iron oxide, chromium oxide, oxidation
More than a kind of black pigment or coloring pigment in the group of manganese composition.Electromagnetic shielding material 10 is pasted on print in order to improve
Outward appearance in the state of the adherends such as brush substrate, preferably as electromagnetic shielding material 10 outside base material 11 or anchor layer 12
In any one or both include light absorber.
The light transmittance for eliminating the electromagnetic shielding material 10 after supporting mass film 21 and stripping film 22 is preferably less than 5%.
As light transmittance, visible light transmissivity, total light transmittance etc. can be enumerated.In base material 11 by solvent-soluble polyimide film
In the case of composition, base material 11 can contain light absorber.
In order to be effectively reduced light transmittance, in light absorber, the preferred black pigment such as carbon black.By black pigment or coloring
The light absorber that pigment is formed is contained preferably in any layer with the weight % of 0.1 weight %~30.Black pigment or coloring pigment
It is preferred that the degree for being 0.02 μm~0.1 μm by the average grain diameter of the primary particle of SEM observations.The thickness of layer containing light absorber
Degree is preferably greater than the particle diameter of light absorber, so that the particulate of light absorber does not expose.In addition, as black pigment, can make
Silica dioxide granule etc. is impregnated in black pigment and only makes skin section be black, can also be formed by pigmentary resin of black etc.
And entirety is set to be made up of black.In addition, for black pigment, in addition to black, can also include show grey black,
The particle of the color of dark brown or the approximate black of blackish green grade, as long as the dead color for being difficult to reflected light can be used.
(stripping film)
In order to protect conductive adhesive layer 14, stripping film 22 can be set on the surface of conductive adhesive layer 14.Stripping
It can be peeled off from film 22 in the use of electromagnetic shielding material 10 from conductive adhesive layer 14.Base as stripping film 22
Material, for example, polyethylene terephthalate, polybutylene terephthalate (PBT), PEN etc.
Polyester film；The polyolefin films such as polypropylene, polyethylene.By being coated with amino-alkyd resin or silicone resin etc. on these base material films
It is thermally dried after remover and implements lift-off processing.The remover of stripping film 22 is applied to preferably without using silicone resin.
If it is used as remover using silicone resin, it is likely that the bonding force of conductive adhesive layer 14 can be weakened.The thickness of stripping film 22
Degree is not included in the integral thickness of the electromagnetic shielding material 10 when being pasted on printed base plate and using, thus to it without spy
Do not limit, usually 12 μm~150 μm of degree.
As the gross thickness of electromagnetic shielding material 10, in the range of preferably 6 μm~20 μm, more preferably 8 μm~15 μ
m.Herein, the gross thickness of electromagnetic shielding material 10 refers to the gross thickness untill conductive adhesive layer 14 from base material 11, bag
Include the thickness of base material 11 and the thickness of conductive adhesive layer 14.
(printed base plate)
As the printed base plate of the electromagnetic wave shielding using the present invention, the rigid base that insulated substrate is hard can be enumerated
Plate, the flexible base board including the part with flexibility and the rigid and flexible substrate of the part of hard that insulated substrate is flexibility
(rigid flexible system substrate) etc..It is high as rank, such as more than 50 μm can be exemplified and then be more than 300 μm.
One of supporting mass film 21 or stripping film 22 or two are laminated with the single or double of electromagnetic shielding material 10
Even if the gross thickness of the electromagnetic shielding material 10 of electromagnetic shielding material laminate 20 of person is thin, operability is also excellent.By electricity
When magnetic wave shielding material 10 is pasted on adherend printed base plate, after stripping film 22 at least is peeled off into removal, make conductive adhesive
The surface of layer 14 is opposed with adherend.In the case where needing the high tracing ability of rank, after supporting mass film 21 and stripping film 22 is removed
Gross thickness it is thin in the state of, overlap electromagnetic shielding material 10 and adherend.Afterwards, preferably conduction is made by heating pressurization
The property heat cure of bond layer 14, adherend is adhered to by electromagnetic shielding material 10.
As the electronic equipment of the electromagnetic wave shielding using the present invention, it is not particularly limited, mobile phone, pen can be enumerated
Remember this type PC, portable terminal device, tablet terminal etc..These electronic equipments can possess the electromagnetism wave screen for being pasted with the present invention
The printed base plate covered.
Embodiment
Below, the present invention is illustrated by embodiment.
(embodiment 1)
The thickness that one side is implemented to lift-off processing is used as supporting for 50 μm polyethylene terephthalate (PET) film
Body film.On the one side of the supporting mass film, the cast coat solvent-soluble polyimide in a manner of dried thickness is 4 μm
Coating fluid and make its drying, and lamination goes out the base material being made up of thin dielectric film resin film, the solvent-soluble polyimide
Coating fluid be relative to dried tensile elongation be 140% solvent-soluble polyimide solid constituent mixture
1 weight % non-conductive carbon black is as obtained from the black pigment of light absorber.It should be noted that in order to determine base material
Tensile elongation, the base of the measure of tensile elongation is made in the same manner as the base material of the manufacture of electromagnetic shielding material
Material, base material is peeled off from supporting mass film, tensile elongation is determined according to IPC-TM-650 2.4.19 method, is as a result 140%.
In lamination on the base material on the one side of supporting mass film, using using as the particle diameter of electroconductive stuffing be 10nm~
The conductive paste that 40nm Argent grain is mixed and prepared with resin glue is coated, and it is 0.25 μ to make dried thickness
M, afterwards with temperature 150 DEG C be fired, form the conductive paste bed of material.Determine the volume electricity of the dried conductive paste bed of material
Resistance rate, its value are 1.5 × 10-5Below Ω cm.
Additionally, relative to phosphorous polyurethane resin 40% solution (Japan spinning make：UR3575) 100 parts by weight, according to
Secondary addition polyfunctional epoxy resin 70% solution (make by Japan's spinning：HY-30) 3.9 parts by weight, the gas phase that average grain diameter is 16nm
(NIPPON AEROSIL Co., Ltd. manufactures method silica：R972) 2.1 parts by weight, the silane coupler as additive
(SHIN-ETSU HANTOTAI's chemical industry manufacture：KBM-403) 0.42 parts by weight, mix silver-bearing copper (family field industry manufacture：RD-MS3) 26 parts by weight, first is used
Base ethyl ketone and toluene are diluted, and stirring is kneaded, and obtains conductive adhesive solution.Relative to by phosphorous polyurethane resin and
The parts by weight of bonding agent (solid constituent) 100 that polyfunctional epoxy resin is combined, the ratio for mixing silver-bearing copper are about 60.8 parts by weight.
For resulting conductive adhesive solution, accumulated in the way of dried thickness is 4 μm on conductive paste bed of material upper strata
Conductive adhesive layer, obtain the electromagnetic shielding material of embodiment 1.
(embodiment 2)
Tensile elongation after the drying is added non-conductive in the coating fluid for 120% solvent-soluble polyimide
Carbon black, base material is formed, in addition, obtains the electromagnetic shielding material of embodiment 2 similarly to Example 1.
(embodiment 3)
Dried tensile elongation is not added non-conductive in the coating fluid for 170% solvent-soluble polyimide
Carbon black, base material is formed in the way of dried thickness is 4 μm, on the base material formed, using for forming anchor layer
Coating fluid, by dried thickness be 0.5 μm in a manner of be coated, lamination goes out anchor layer, and this is used to form anchor layer
The non-conductive carbon black and heat resisting temperature that coating fluid is mixed with the black pigment as light absorber are 260 DEG C~280 DEG C poly-
Ester based resin composition, the conductive paste bed of material and conductive adhesive layer are formed in anchor layer afterwards, in addition, with implementation
Example 1 similarly obtains the electromagnetic shielding material of embodiment 3.
(embodiment 4)
In addition to the thickness for making the conductive paste bed of material is 0.8 μm, the electromagnetism of embodiment 4 is obtained similarly to Example 1
Ripple shielding material.
(comparative example 1)
Tensile elongation after the drying is added non-conductive in the coating fluid for 50% solvent-soluble polyimide
Carbon black, base material is formed, in addition, obtains the electromagnetic shielding material of comparative example 1 similarly to Example 1.
(comparative example 2)
Instead of the lamination conductive paste bed of material, and the silver-colored evaporation film that thickness is 0.08 μm is set, in addition, with embodiment 1
Similarly obtain the electromagnetic shielding material of comparative example 2.
(comparative example 3)
The lamination conductive paste bed of material is replaced in anchor layer, and the electrolytic copper foil that thickness is 12 μm is set, in addition, with
Embodiment 3 similarly obtains the electromagnetic shielding material of comparative example 3.
(comparative example 4)
Without using supporting mass film, the thermohardening type polyimides institute structure that thickness is 10 μm, tensile elongation is 62% is used
Into polyimide film as base material, in addition, obtain the electromagnetic shielding material of comparative example 4 similarly to Example 3.
(evaluation method of the high tracing ability of rank)
As shown in Fig. 2 prepare to be provided with the detection base of hard substrate portion 33 and portion of terminal 31 on flexibility baseplate part 32
Plate 30, electromagnetic shielding material 10 is being stacked thereon.The length being formed between the portion of terminal 31 on the both ends of flexibility baseplate part 32
Spend for 50mm.Relative to flexibility baseplate part 32, the high height of the rank that is formed by hard substrate portion 33 is 0.3mm (300 μm), wide
Spend for 30mm.The length in hard substrate portion 33 is 30mm, the length of the opening portion 35 between portion of terminal 31 and hard substrate portion 33
For each 10mm in left and right.
The exposed division 34 for determining resistance between terminal is remained in portion of terminal 31, the end of electromagnetic shielding material 10 is covered
The part being placed in portion of terminal 31, covered according to opening portion 35 by the face of the conductive adhesive of electromagnetic shielding material 10
Mode be laid out, with 160 DEG C, 2.5MPa, 65 minutes condition carry out hot pressing, obtain the evaluation sample of tracing ability.Observation
The section of resulting sample, it is designated as " 〇 " in the case where electromagnetic shielding material follows the rank height in center；It will not follow, electricity
Magnetic wave shielding material generates gap from detection substrate floating, or is broken in the film of the high corner electromagnetic shielding material of rank
Situation be designated as "×".
(evaluation method of electric conductivity)
Utilize digital multimeter (manufacture of TFF Keithley Instruments companies, model：2100/100), in rank
Resistance is measured between the terminal at the both ends of the sample obtained by the evaluation method of high tracing ability, will be designated as " 〇 " less than 1 Ω,
1 Ω is designated as " △ " less than 2 Ω, 2 more than Ω are designated as "×".
(evaluation method of heat resistance)
160 DEG C, 2.5MPa, be 25 μ by resulting electromagnetic shielding material hot pressing to thickness under conditions of 65 minutes
M polyimide film, obtain the sample for evaluation of heat resistance.Test film is cut into 2.5cm × 5cm size, is impregnated in 290
DEG C solder bath in lift after 10 seconds.The outward appearance for observing the electromagnetic shielding material after immersion solder bath by visual observation whether there is deformation
Or contraction etc. is abnormal, without exception, good situation is designated as " 〇 ", it will be observed that abnormal situation is designated as "×".
(result of the test)
On embodiment 1~4 and comparative example 1~4, commenting for electromagnetic shielding material is carried out using above-mentioned evaluation method
Valency, resulting evaluation result is shown in table 1~2."None" has been charged in the column of thickness and has referred to do not have the layer.In addition, poly-
In the column of the polyimide material of acid imide base material, " PI1 ", " PI2 ", " PI3 ", " PI4 ", " PI5 " are referred respectively in embodiment
1st, the polyimides used in embodiment 2, embodiment 3, comparative example 1, comparative example 4.
【Table 1】
【Table 2】
It is more than 100% in the tensile elongation of base material it can be seen from the result of the experiment of the tracing ability shown in table 1~2
In the case of, tracing ability and electric conductivity become good.That is, can not in the case where the tensile elongation of base material is less than 100%
It is high that the rank of detection substrate is followed completely, in detection with producing gap between substrate, or the disconnected of the conductive paste bed of material occurs
Split, tracing ability and electric conductivity are deteriorated.
In addition, in the case of making evaporation film as comparative example 2 for conductive layer, because conductive layer lacks flexibility, thus
Even if the tensile elongation of base material is more than 100%, it is high also to follow the rank of detection substrate completely, with detection substrate
Between produce gap, or conductive layer produces cracking or is broken, tracing ability and electric conductivity variation.
In addition, in the case of making metal foil as comparative example 3 for conductive layer, because conductive layer lacks extensibility, thus
Even if the tensile elongation of base material is more than 100%, it is high also to follow the rank of detection substrate completely, with detection substrate
Between produce gap, or conductive layer produces cracking or is broken, tracing ability and electric conductivity variation.
In the case of embodiment 1~4, by making conductive layer use the conductive paste bed of material, due to nanometer after firing
The binding agent filled in the space of Argent grain, so as to produce flexibility, conductive layer follows rank height, even if thus base material polyamides
Imines film is elongated, and will not also lose conduction, can obtain the good electromagnetic shielding material of the high tracing ability of rank.
In addition, the feelings as comparative example 2,3 using the fine and close electrically conductive film of metal foil or evaporation film etc as conductive layer
Under condition, vapor caused by the moisture in the base material film generated when drastically being heated in solder bath etc. or unreacted reactant, low point
Outgassing caused by subconstiuent can not pass through, it may occur that the bad order such as foaming.That is, adopt conductive layer as embodiment 1~4
With conductive paste, in the conductive layer there is also space after as a result firing, thus above-mentioned moisture or outgassing can be by, even if
The bad orders such as foaming also do not occur in the case where drastically heating, the good electromagnetic shielding material of heat resistance can be obtained.
It should be noted that in the ratio using thickness is big, tensile elongation is less than 100% polyimide film as base material
Compared with example 4, heat resistance is also deteriorated, it is believed that because from the gas generated more of the big base material of thickness, and gas is saturating
The property crossed is low.
Symbol description
10 ... electromagnetic shielding materials, 11 ... base materials, 12 ... anchor layers, 13 ... the conductive paste bed of materials, 14 ... electric conductivity are glued
Connect oxidant layer, 20 ... electromagnetic shielding material laminates, 21 ... supporting mass films, 22 ... stripping films, 30 ... detection substrates, 31 ... ends
Sub-portion, 32 ... flexibility baseplate parts, 33 ... hard substrate portions.
Claims (12)
- A kind of 1. electromagnetic shielding material, it is characterised in that on the one side for the base material being made up of dielectric resin film, the base The thickness direction of material is laminated with the conductive paste bed of material and conductive adhesive layer successively, and the tensile elongation of the base material is More than 100%.
- 2. electromagnetic shielding material as claimed in claim 1, it is characterised in that the conductive paste bed of material is less than comprising particle diameter 1 μm of silver nano-grain.
- 3. electromagnetic shielding material as claimed in claim 1 or 2, it is characterised in that the tensile elongation of the base material is Less than more than 100% 300%.
- 4. such as electromagnetic shielding material according to any one of claims 1 to 3, it is characterised in that the base material can by solvent Dissolubility polyimide film is formed.
- 5. such as electromagnetic shielding material according to any one of claims 1 to 4, it is characterised in that the base material is sub- by polyamides Amine film is formed, and the polyimide film uses the gathering with the aliphatic unit that carbon number is more than 3 between aromatic unit Acid imide material is formed.
- 6. such as electromagnetic shielding material according to any one of claims 1 to 5, it is characterised in that the conductive adhesive The thickness of layer is less than 15 μm.
- 7. such as electromagnetic shielding material according to any one of claims 1 to 6, it is characterised in that the conductive adhesive Layer is electric conductivity anisotropy bond layer.
- 8. such as electromagnetic shielding material according to any one of claims 1 to 7, it is characterised in that the conductive adhesive Layer includes polyurethane.
- 9. such as electromagnetic shielding material according to any one of claims 1 to 8, it is characterised in that from the base material to described Gross thickness untill conductive adhesive layer is 6 μm~15 μm.
- 10. such as electromagnetic shielding material according to any one of claims 1 to 9, it is characterised in that the base material with lamination There is the branch that the opposite face in the side of the conductive paste layer and the conductive adhesive layer can be peeled off from the base material Body film is held to be supported.
- 11. a kind of mobile phone, it possesses electromagnetic shielding material according to any one of claims 1 to 10.
- 12. a kind of electronic equipment, it possesses electromagnetic shielding material according to any one of claims 1 to 10.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2016-136743 | 2016-07-11 | ||
| JP2016136743A JP2018010888A (en) | 2016-07-11 | 2016-07-11 | Electromagnetic wave shield material |
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| CN107613628A true CN107613628A (en) | 2018-01-19 |
| CN107613628B CN107613628B (en) | 2021-10-01 |
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| JP (1) | JP2018010888A (en) |
| KR (1) | KR101949143B1 (en) |
| CN (1) | CN107613628B (en) |
| TW (1) | TWI800485B (en) |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112888288A (en) * | 2021-01-18 | 2021-06-01 | 哈尔滨工业大学 | Electromagnetic shielding curved surface optical window based on ultrathin doped metal/medium composite structure |
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| JP6624331B1 (en) * | 2019-08-01 | 2019-12-25 | 東洋インキＳｃホールディングス株式会社 | Electromagnetic wave shielding sheet and electromagnetic wave shielding wiring circuit board |
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| JP2006245160A (en) * | 2005-03-02 | 2006-09-14 | Sharp Corp | Ferrite ring core housing case |
| CN102762083A (en) * | 2011-04-26 | 2012-10-31 | 藤森工业株式会社 | Electromagnetic wave shielding material for FPC |
| CN103140126A (en) * | 2011-11-24 | 2013-06-05 | 大自达电线股份有限公司 | Shield film, shielded printed wiring board, and method for manufacturing shield film |
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| TW201819183A (en) | 2018-06-01 |
| JP2018010888A (en) | 2018-01-18 |
| TWI800485B (en) | 2023-05-01 |
| KR101949143B1 (en) | 2019-02-18 |
| CN107613628B (en) | 2021-10-01 |
| KR20180006851A (en) | 2018-01-19 |
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