CN208891128U

CN208891128U - Electromagnetic shielding film and printed circuit board with electromagnetic shielding film

Info

Publication number: CN208891128U
Application number: CN201821261692.5U
Authority: CN
Inventors: 吉田一义; 权田贵司
Original assignee: Shin Etsu Polymer Co Ltd
Current assignee: Shin Etsu Polymer Co Ltd; Shin Etsu Chemical Co Ltd
Priority date: 2017-09-01
Filing date: 2018-08-07
Publication date: 2019-05-21
Anticipated expiration: 2028-08-07
Also published as: JP2019046980A

Abstract

The utility model provides a kind of bonding force that can sufficiently improve insulating resin layer and conductive layer and the low electromagnetic shielding film of dielectric constant and the printed circuit board with electromagnetic shielding film.The electromagnetic shielding film (1) of the utility model has insulating resin layer (10) and the conductive layer (20) adjacent with insulating resin layer (10), insulating resin layer (10) is the foaming layer containing aromatic polyether ketone, and conductive layer (20), which at least has, wraps metalliferous conductive adhesive layer.The aromatic polyether ketone can be at least one party in polyether-ether-ketone and polyether ketone ketone.

Description

Electromagnetic shielding film and printed circuit board with electromagnetic shielding film

Technical field

The utility model relates to electromagnetic shielding film and with the printed circuit board of electromagnetic shielding film.

Background technique

In order to shield from external electromagnetic noise, and prevent electromagnetic noise caused by printed circuit board from leaking, sometimes Via insulating film (cover lay film, cover film), on the surface of printed circuit board, setting has insulating resin layer and conductive layer Electromagnetic shielding film (for example, with reference to patent document 1).

For example, it includes thermosetting property tree that electromagnetic shielding film, which is by the one side coating in carrier film (carrier film), The coating of rouge, curing agent and solvent, makes it dry to form insulating resin layer, and conductive layer is arranged on the surface of insulating resin layer and makes It makes.As conductive layer, sometimes using in the metal film layer and conductive adhesive layer having for shielding electromagnetic wave extremely The conductive layer of a few side.

Existing technical literature

Patent document

Patent document 1: Japanese Unexamined Patent Publication 2016-86120 bulletin

Utility model content

Utility model project to be solved

In the existing insulating resin layer formed by thermosetting resin, relative to the cementability for wrapping metalliferous conductive layer It is low.Especially in the case where conductive layer has metal film layer and metal film layer and insulating resin layer are in contact, cementability It is especially low.Therefore, in existing electromagnetic shielding film, the bonding force of insulating resin layer and conductive layer is weak sometimes, and there are electromagnetism There is a situation where splittings during use for wave screened film.For example, there is insulation when removing carrier film from insulating resin layer The case where resin layer is removed together with carrier film from conductive layer.

In addition, in the printed circuit boards, the signal velocity of preferred circuit is very fast.The signal of printed circuit board propagates speed Degree is by formula k × C × ε_r ^1/2Acquire (k: constant, C: the light velocity [m/s], ε in vacuum_r: the opposite dielectric of printed circuit board is normal Number).Therefore, in order to improve signal velocity, the dielectric constant of printed circuit board is reduced.

Due to the reason identical as printed circuit board, the electromagnetic shielding film being arranged on printed circuit board is it is also preferred that low dielectric Constant.

But so far there are no can sufficiently improve the bonding force of conductive layer and insulating resin layer, simultaneously dielectric constant it is low Electromagnetic shielding film.

The purpose of this utility model is to provide can sufficiently improve the viscous of the metalliferous conductive layer of packet and insulating resin layer Relay and the low electromagnetic shielding film of dielectric constant.In addition, the purpose of this utility model is to provide wrap metalliferous conductive layer The fast printed circuit board with electromagnetic shielding film of and signal velocity sufficiently high with the bonding force of insulating resin layer.

A technical solution to solve project

The first method of the utility model is electromagnetic shielding film,

Its conductive layer with insulating resin layer and with insulating resin layer adjoining,

The insulating resin layer is foaming layer, at least conductive adhesive layer of the conductive layer.

Second method as the utility model, which is characterized in that in the electromagnetic shielding film of above-mentioned first method,

Foaming in the insulating resin layer is independent foaming or continuous foamed,

The expansion ratio of the insulating resin layer be greater than 1 times and 10 times hereinafter,

The mean air bubble diameter of bubble contained in the insulating resin layer be 0.1 μm or more and 30 μm hereinafter,

The bubble density of the insulating resin layer is 1.0 × 10⁷A/cm³Above and 1.0 × 10¹³A/cm³Hereinafter,

The insulating resin layer with a thickness of 3 μm or more and 100 μm hereinafter,

The relative dielectric constant of the insulating resin layer is 1.5 or more and 3.3 or less.

Third Way as the utility model, which is characterized in that in the electromagnetic shielding film of above-mentioned first method,

The expansion ratio of the insulating resin layer be 1.1 times or more and 5 times hereinafter,

The mean air bubble diameter of bubble contained in the insulating resin layer be 1 μm or more and 5 μm hereinafter,

The bubble density of the insulating resin layer is 1.0 × 10¹⁰A/cm³Above and 1.0 × 10¹¹A/cm³Hereinafter,

The insulating resin layer with a thickness of 5 μm or more and 20 μm hereinafter,

The relative dielectric constant of the insulating resin layer be 1.8 or more and 3.0 hereinafter,

The sheet resistance of the insulating resin layer 10 is 1 × 10⁶Ω or more and 1 × 10¹⁹Ω or less.

Fourth way as the utility model, which is characterized in that in the electromagnetic shielding film of above-mentioned first method,

The insulating resin layer is the foaming layer containing aromatic polyether ketone, and the conductive layer at least has packet metalliferous Conductive adhesive layer.

The 5th mode as the utility model, which is characterized in that in the electromagnetic shielding film of above-mentioned fourth way,

The aromatic polyether ketone is at least one party in polyether-ether-ketone and polyether ketone ketone.

The 6th mode as the utility model, which is characterized in that in the electromagnetic shielding film of above-mentioned first method,

The conductive adhesive layer is anisotropic conductive adhesive layer, includes Thermocurable bonding agent and electric conductivity Particle,

Ratio of the conductive particle in the anisotropic conductive adhesive layer are as follows: led in the anisotropy In 100 volume % of electrical adhesive layer, account for 1 volume % or more and 30 volume % hereinafter,

The average grain diameter of the conductive particle be 2 μm or more and 26 μm hereinafter,

The anisotropic conductive adhesive layer with a thickness of 3 μm or more and 25 μm hereinafter,

Storage modulus of the anisotropic conductive adhesive layer at 180 DEG C is 1 × 10³Pa or more and 5 × 10⁷Pa Hereinafter,

The sheet resistance of the anisotropic conductive adhesive layer is 1 × 10⁴Ω or more and 1 × 10¹⁶Ω or less.

The 7th mode as the utility model, which is characterized in that in the electromagnetic shielding film of above-mentioned first method,

Ratio of the conductive particle in the anisotropic conductive adhesive layer are as follows: led in the anisotropy In 100 volume % of electrical adhesive layer, account for 2 volume % or more and 15 volume % hereinafter,

The average grain diameter of the conductive particle be 4 μm or more and 16 μm hereinafter,

The anisotropic conductive adhesive layer with a thickness of 5 μm or more and 15 μm hereinafter,

Storage modulus of the anisotropic conductive adhesive layer at 180 DEG C is 5 × 10³Pa or more and 1 × 10⁷Pa Hereinafter,

The sheet resistance of the anisotropic conductive adhesive layer is 1 × 10⁶Ω or more and 1 × 10¹⁴Ω or less.

Eighth mode as the utility model, which is characterized in that in the electromagnetic shielding film of above-mentioned first method,

The conductive adhesive layer is isotropic conductivity adhesive layer, includes Thermocurable bonding agent and electric conductivity Particle,

Ratio of the conductive particle in the isotropic conductivity adhesive layer are as follows: led in the isotropism In 100 volume % of electrical adhesive layer, account for 50 volume % or more and 80 volume % hereinafter,

The average grain diameter of the conductive particle be 0.1 μm or more and 10 μm hereinafter,

The isotropic conductivity adhesive layer with a thickness of 5 μm or more and 20 μm hereinafter,

Storage modulus of the isotropic conductivity adhesive layer at 180 DEG C is 1 × 10³Pa or more and 5 × 10⁷Pa Hereinafter,

The sheet resistance of the isotropic conductivity adhesive layer is 0.05 Ω or more and 2.0 Ω or less.

The 9th mode as the utility model, which is characterized in that in the electromagnetic shielding film of above-mentioned first method,

Ratio of the conductive particle in the isotropic conductivity adhesive layer are as follows: led in the isotropism In electrical 100 volume % of adhesive layer, account for 60 volume % or more and 70 volume % hereinafter,

The average grain diameter of the conductive particle be 0.2 μm or more and 1 μm hereinafter,

The isotropic conductivity adhesive layer with a thickness of 7 μm or more and 17 μm hereinafter,

Storage modulus of the isotropic conductivity adhesive layer at 180 DEG C is 5 × 10³Pa or more and 1 × 10⁷Pa Hereinafter,

The sheet resistance of the isotropic conductivity adhesive layer is 0.1 Ω or more and 1.0 Ω or less.

The tenth mode as the utility model, which is characterized in that in the electromagnetic shielding film of above-mentioned first method,

The conductive layer has set on the metal film layer of the insulating resin layer side and set on the metal film layer The conductive adhesive layer of the side opposite with the insulating resin layer.

The 11st mode as the utility model, which is characterized in that in the electromagnetic shielding film of above-mentioned tenth mode,

The metal film layer is cvd metal layer.

The 12nd mode as the utility model, which is characterized in that in the electromagnetic shielding film of above-mentioned 11st mode In,

The cvd metal layer is silver-colored vapor deposition layer or copper vapor deposition layer.

The 13rd mode as the utility model, which is characterized in that in the electromagnetic shielding film of above-mentioned tenth mode,

The sheet resistance of the metal film layer be 0.001 Ω or more and 1 Ω hereinafter,

The metal film layer with a thickness of 0.01 μm or more and 5 μm or less.

The 14th mode as the utility model, which is characterized in that in the electromagnetic shielding film of above-mentioned tenth mode,

The sheet resistance of the metal film layer be 0.001 Ω or more and 0.5 Ω hereinafter,

The metal film layer with a thickness of 0.05 μm or more and 3 μm or less.

The 15th mode as the utility model, which is characterized in that in the electromagnetic shielding film of above-mentioned tenth mode,

The conductive layer further has melanism on the surface of the insulating resin layer side of the metal film layer Layer.

The 16th mode as the utility model, which is characterized in that in the electromagnetic shielding film of above-mentioned 15th mode,

The blackening layer with a thickness of 5nm or more and 20 μm hereinafter,

Brightness L* specified in the JIS Z8781-5 of the blackening layer is 5 or less.

The 17th mode as the utility model, which is characterized in that in the electromagnetic shielding film of above-mentioned 15th mode In,

The blackening layer with a thickness of 10nm or more and 1 μm hereinafter,

The tenth all directions formula as the utility model, which is characterized in that in the electromagnetic shielding film of above-mentioned first method,

Further there is carrier film on the face with the conductive layer opposite side of the insulating resin layer.

As the 19th mode of the utility model, in the electromagnetic shielding film of above-mentioned tenth all directions formula,

The carrier film has carrier film main body and the surface set on the insulating resin layer side of the carrier film main body Adhesive phase,

Storage modulus of the carrier film main body at 180 DEG C is 8 × 10⁷Pa or more and 5 × 10⁹Pa hereinafter,

The carrier film main body with a thickness of 3 μm or more and 75 μm hereinafter,

The carrier film with a thickness of 25 μm or more and 125 μm or less.

The 20th mode as the utility model, which is characterized in that in the electromagnetic shielding film of above-mentioned tenth all directions formula In,

Storage modulus of the carrier film main body at 180 DEG C is 1 × 10⁸Pa or more and 8 × 10⁸Pa hereinafter,

The carrier film main body with a thickness of 12 μm or more and 50 μm hereinafter,

The carrier film with a thickness of 38 μm or more and 105 μm or less.

21st mode of the utility model is the printed circuit board with electromagnetic shielding film, is included

Printed circuit board is equipped with printed circuit in at least single side of substrate；

Insulating film, it is adjacent with the face of the side equipped with the printed circuit of the printed circuit board；

Electromagnetic shielding film described in any one of above-mentioned first to the 20th mode, so that the electric conductivity is bonded The oxidant layer mode adjacent with the insulating film is arranged.

The effect of utility model

The electromagnetic shielding film of the utility model can sufficiently improve the viscous of the metalliferous conductive layer of packet and insulating resin layer Relay, and dielectric constant is low.

In the printed circuit board with electromagnetic shielding film of the utility model, metalliferous conductive layer and insulation tree are wrapped The bonding force of rouge layer is sufficiently high, and signal velocity is fast.

Detailed description of the invention

Fig. 1 is the cross-sectional view for indicating the first embodiment of electromagnetic shielding film of the utility model.

Fig. 2 is the cross-sectional view for indicating the second embodiment of electromagnetic shielding film of the utility model.

Fig. 3 is the cross-sectional view for indicating the third embodiment of electromagnetic shielding film of the utility model.

Fig. 4 is the section view for indicating an embodiment of the printed circuit board with electromagnetic shielding film of the utility model Figure.

Fig. 5 is the cross-sectional view for indicating the manufacturing process of the printed circuit board with electromagnetic shielding film of Fig. 4.

Specific embodiment

The definition of following term is suitable for the full scope of present specification and claims.

" isotropic conductivity adhesive layer " refers to that conductive electric conductivity on thickness direction and face direction is viscous Connect oxidant layer.

" anisotropic conductive adhesive layer " refer to it is conductive in a thickness direction, in the surface direction do not have lead Electrical conductive adhesive layer.

" conductive adhesive layer for not having electric conductivity in the surface direction " refers to that sheet resistance is 1 × 10⁴Ω's or more Conductive adhesive layer.

30 particles are randomly choosed from the MIcrosope image of particle, minimum diameter and the maximum for measuring each particle are straight Diameter, and using the intermediate value of minimum diameter and maximum gauge as the partial size of a particle, the partial size of 30 particles measured is carried out Arithmetic average, obtained value are the average grain diameter of particle.The average grain diameter of conductive particle is also identical.

Using the section of microscope Observe and measure object, measures the thickness at five and be averaged, obtained value is film The thickness of (release film, insulating film etc.), film (conductive adhesive layer etc.), metal film layer etc..

Storage modulus is calculated by the stress for being supplied to measure object and the deformation detected, used as temperature or time The measurement of dynamic viscoelasticity device of function output, measures as a viscoelastic property.

10% compression strength of conductive particle is by following formula (α) by using the measurement result of micro-compression tester to ask ?.

C (x)=2.48P/ π d²(α)

Wherein, C (x) is 10% compression strength (MPa), and P is the test force (N) when partial size 10% is displaced, and d is partial size (mm)。

Sheet resistance refers to the two thin-film metal electrodes (length formed using the vapor deposition of gold on quartz glass 10mm, width 5mm, interelectrode distance 10mm), determinand is placed on this electrode, above determinand, with 0.049N Loading pressing determinand 10mm × 20mm region, and electricity obtained from being measured with 1mA measurement electric current below Resistance between pole.

For convenience of explanation, the size ratio in FIG. 1 to FIG. 5 is from actual size than different.

The first method of the utility model be electromagnetic shielding film, the electromagnetic shielding film have insulating resin layer and with institute The adjacent conductive layer of insulating resin layer is stated, the insulating resin layer is the foaming layer containing aromatic polyether ketone, the conductive layer At least have and wraps metalliferous conductive adhesive layer.

Fig. 1 is the cross-sectional view for indicating the electromagnetic shielding film 1 of first embodiment, and Fig. 2 is to indicate second embodiment The cross-sectional view of electromagnetic shielding film 1, Fig. 3 are the cross-sectional view for indicating the electromagnetic shielding film 1 of third embodiment.

The electromagnetic shielding film 1 of first embodiment, second embodiment and third embodiment all has insulating resin The side adjoining opposite with conductive layer 20 of layer 10, the conductive layer 20 adjacent with insulating resin layer 10 and insulating resin layer 10 The adjacent release film 40 in the side opposite with insulating resin layer 10 of carrier film 30 and conductive layer 20.

In the electromagnetic shielding film 1 of first embodiment, conductive layer 20 has the metal adjacent with insulating resin layer 10 Film layer 22 and the anisotropic conductive adhesive layer 24 adjacent with release film 40.

In the electromagnetic shielding film 1 of second embodiment, conductive layer 20 has the metal adjacent with insulating resin layer 10 Film layer 22 and the isotropic conductivity adhesive layer 26 adjacent with release film 40.

In the electromagnetic shielding film 1 of third embodiment, conductive layer 20 includes isotropic conductivity adhesive layer 26.

(insulating resin layer)

Electromagnetic shielding film 1 is fitted in the surface of the insulating film set on flexible printed circuit board surface, and removes carrier After film 30, insulating resin layer 10 forms the protective layer of conductive layer 20.

Insulating resin layer 10 is the foaming layer containing aromatic polyether ketone.

Aromatic polyether ketone is with structure made of being mutually bonded phenyl ring via ehter bond and to make phenyl ring phase via ketone group The mutually polymer of structure made of bonding.

As aromatic polyether ketone, for example, can enumerate: the polyether-ether-ketone with chemical structure represented by chemical formula (1) (PEEK), the polyether-ketone (PEK) with chemical structure represented by chemical formula (2), have chemical formula (3) represented by chemistry tie The polyether ketone ketone (PEKK) of structure, has chemistry at the polyether ether ketone ketone (PEEKK) with chemical structure represented by chemical formula (4) The polyetherketoneetherketoneketone (PEKEKK) of chemical structure represented by formula (5).Aromatic polyether ketone contained by insulating resin layer 10 can Think independent one kind, or two or more.

In addition, aromatic polyether ketone can be being total to chemical structure represented by more than two chemical formulas (1)~(5) Polymers.

It should be noted that two ends of aromatic polyether ketone become hydrogen atom.

In the aromatic polyether ketone, from the angle for the insulating resin layer 10 for being easily formed foaming, preferred, polyethers ether ketone And at least one party in polyether ketone ketone.

Polyether-ether-ketone is higher one kind of heat resistance in resin, but requires the feelings of more high-fire resistance in electromagnetic shielding film 1 Under condition, in aromatic polyether ketone, preferred, polyethers ketone, polyether ketone ketone, polyetherketoneetherketoneketone.The glass transition temperature of polyether-ketone (hereinafter, referred to as " Tg ".) it is 152 DEG C, the Tg of polyether ketone ketone is 154 DEG C, and the Tg of polyetherketoneetherketoneketone is 162 DEG C, is above poly- 143 DEG C of ether ether ketone or more and 151 DEG C of Tg ranges below.Therefore, suitable for requiring the purposes of heat resistance.The Tg of resin passes through difference Show that scanning calorimetry (DSC) or Measurement of Dynamic Viscoelasticity acquire.

In the aromatic polyether ketone of the excellent heat resistance, not only excellent heat resistance, formability are also very excellent for polyether ketone ketone It is different, therefore more preferably.

[chemical formula 1]

From the viewpoint of mechanical performance, each n preferably 10 or more, more preferable 20 of chemical formula (1)~(5) with On.On the other hand, in terms of it aromatic polyether ketone can be easily manufactured, n be preferably 5000 hereinafter, more preferably 1000 with Under.That is, n is preferably 10 or more and 5000 hereinafter, more preferably 20 or more and 1000 or less.

In the range of not damaging the effect of the utility model, aromatic polyether ketone can be other copolymerizable with ether sulfone etc. Block copolymer, random copolymer or the modified body of monomer.

It is any in chemical formula (1)~(5) relative to 100 moles of % of aromatic polyether ketone as aromatic polyether ketone The ratio of polyether-ketone unit represented by one is preferably 50 moles of % or more and 100 mole of % hereinafter, more preferably 70 rub % or more and 100 mole of % of that is hereinafter, further preferably 80 moles of % or more and 100 mole of % are hereinafter, most preferably 100 rub You are %.If the ratio of aromatic polyether ketone unit described in aromatic polyether ketone is the lower limit value or more, can be into one Walk the bonding force of reinforced insulation resin layer 10 and conductive layer 20.

As the manufacturing method of aromatic polyether ketone, particularly the manufacturing method of polyether-ether-ketone, for example, Japanese Unexamined Patent Application 50-27897 bulletin, Japanese Unexamined Patent Application 51-119797 bulletin, Japanese Unexamined Patent Application 52-38000 bulletin, Japanese Unexamined Patent Application 54-90296 bulletin, Japanese Patent Publication 55-23574 bulletin are made public in Japanese Patent Publication 56-2091 bulletin.

As the manufacturing method of polyether ketone ketone, for example, U.S. Patent No. 3,516,966, U.S. Patent No. 3,637,592 Number, U.S. Patent No. 3,441,538, Japanese Patent Publication 4-63900 bulletin, Japanese Patent Publication 6-10258 bulletin etc. do It is open.

It can also include other resins in addition to aromatic polyether ketone in insulating resin layer 10.As other resins, for example, It can enumerate: polyimides, polyamidoimide, polyamide, polysulfones, polyether sulfone, polyphenylsulfone, polyphenylene sulfide, polyphenylene sulfide Sulfone, polyphenylene sulfide ketone etc..

Relative to all resins contained in insulating resin layer 10, the content of aromatic polyether ketone be preferably 50 mass % with Upper and 100 mass % hereinafter, more preferably 70 mass % or more and 100 mass % hereinafter, further preferably 80 mass % with Upper and 100 mass % or less.Resin contained in insulating resin layer 10 can be only made of aromatic polyether ketone.If relative to exhausted The content of all resins contained in edge resin layer 10, aromatic polyether ketone is the lower limit value or more, then can further increase Bonding force of the strong insulating resin layer 10 to conductive layer 20.

Foaming in insulating resin layer 10 can be independent foaming, or continuous foamed.

The expansion ratio of insulating resin layer 10 be preferably greater than 1 times and 10 times hereinafter, more preferably 1.1 times or more and 5 times with Under.If the expansion ratio of insulating resin layer 10 is the lower limit value or more, Jie of insulating resin layer 10 can be further decreased Electric constant, as a result, the whole dielectric constant of electromagnetic shielding film 1 can also be further decreased.If the hair of insulating resin layer 10 Steeping multiplying power is the upper limit value hereinafter, can then be readily formed the insulating resin layer 10 of foaming.

The expansion ratio [again] of insulating resin layer 10 is acquired by following formula.

Specific gravity (the ρ of insulating resin layer 10 before expansion ratio=foaming₀Specific gravity (the ρ of)/insulating resin layer 10_f)

The specific gravity ρ₀、ρ_fIt is the value that is measured at 23 DEG C of temperature according to the A method in JIS K7112:1999.

The expansion ratio can pass through the type and average molecular weight of aromatic polyether ketone, the type of foaming agent, foaming The foamed strips such as size of used mold when temperature and pressure, the foaming when additive amount of agent, the adding method of foaming agent, foaming Part is adjusted.

The mean air bubble diameter of bubble contained in insulating resin layer 10 is preferably 0.1 μm or more and 30 μm hereinafter, more excellent 0.5 μm or more and 10 μm is selected as hereinafter, further preferably 1 μm or more and 5 μm or less.If the average air in insulating resin layer 10 Bulb diameter is the lower limit value or more, then can further decrease the dielectric constant of insulating resin layer 10, as a result, can also be into One step reduces the whole dielectric constant of electromagnetic shielding film 1.If the mean air bubble diameter in insulating resin layer 10 is the upper limit Value is hereinafter, can then prevent the deformation of insulating resin layer 10.

Mean air bubble diameter [μm] in insulating resin layer 10 is measured by following methods.

Using the section of scanning electron microscope shooting insulating resin layer 10, image procossing is carried out to obtained image, is surveyed The diameter of fixed 100 bubbles.Herein, the diameter of bubble uses the maximum long axis of bubble.It is calculated by the diameter of 100 bubbles flat Equal diameter, using obtained value as mean air bubble diameter.

Identical as expansion ratio, the mean air bubble diameter can also be set by foaming condition described in appropriate adjustment It is set to the range.

The bubble density of insulating resin layer 10 is preferably 1.0 × 10⁷A/cm³Above and 1.0 × 10¹³A/cm³Hereinafter, more Preferably 1.0 × 10⁸A/cm³Above and 1.0 × 10¹²A/cm³Hereinafter, further preferably 1.0 × 10¹⁰A/cm³Above and 1.0×10¹¹A/cm³Below.If the bubble density of insulating resin layer 10 is the lower limit value or more, can further decrease The dielectric constant of insulating resin layer 10, as a result, the whole dielectric constant of electromagnetic shielding film 1 can also be further decreased.If The bubble density of insulating resin layer 10 is the upper limit value hereinafter, can then prevent the deformation of insulating resin layer 10.

Bubble density [a/cm of insulating resin layer³] use the specific gravity ρ₀、ρ_f, mean air bubble diameter D, pass through following formula It acquires.

Bubble density=6 { (ρ₀/ρ_f)-1}/(πD³)

Identical as expansion ratio, the bubble density can also be set it to by foaming condition described in appropriate adjustment The range.

The relative crystallinity of insulating resin layer 10 be preferably 80% or more and 100% hereinafter, more preferably 90% or more and 100% or less.If the relative crystallinity of insulating resin layer 10 is the lower limit value or more, insulating resin layer 10 can be improved Heat resistance and mechanical strength, as a result, can also be improved electromagnetic shielding film 1 whole heat resistance and mechanical strength.

The relative crystallinity of insulating resin layer 10 can be acquired by following methods.

It is measured using differential scanning calorimeter for the sample being cut into from insulating resin layer 10 with 10 DEG C/min of liter The heat Δ H at recrystallization peak when warm speed heats up_cThe heat Δ H of [J/g] and crystalline melting peak_m[J/g]。

Pass through obtained Δ H_c、ΔH_mAnd following formula, acquire relative crystallinity [%].

Relative crystallinity={ 1- (Δ H_c/ΔH_m)}×100

The heating of foamed process and heat treatment later when relative crystallinity can be by formation insulating resin layer 10 Temperature and heating time are adjusted.Heating temperature is higher, heating time is longer, and relative crystallinity is higher.

The relative dielectric constant of insulating resin layer 10 be preferably 1.5 or more and 3.3 hereinafter, preferably 1.8 or more and 3.0 with Under.Herein, relative dielectric constant refers to permittivity ε/vacuum permittivity ε of insulating resin layer 10₀, it is without single The characteristic of position.ε₀For constant (8.854187 ... × 10^-12[F/m])。

If the relative dielectric constant of insulating resin layer 10 is the lower limit value or more, easy to accomplish, if the upper limit Value is hereinafter, the then available sufficiently fast signal velocity of electromagnetic shielding film 1.

The dielectric constant of insulating resin layer 10 is to be measured using the device that can measure dielectric constant with frequency 1GHz Value.

Although aromatic polyether ketone is the lower material of dielectric constant, if only constituting insulating resin by aromatic polyether ketone Layer 10, then dielectric constant is still not low enough.By improving the expansion ratio of insulating resin layer 10, it can easily make opposite dielectric normal Number is in the range.

In order to hide the printed circuit of printed circuit board or assign the PCB design with electromagnetic shielding film, Insulating resin layer 10 may include colorant (pigment, dyestuff etc.) and either side or two sides in filler.

As in colorant and filler either side or two sides, it is excellent from the aspect of weatherability, heat resistance, hiding Select pigment or filler, from the aspect of the hiding of printed circuit, design, more preferable black pigment or black pigment and its The combination of its pigment or filler.

In the range of not damaging the characteristic of the utility model, insulating resin layer 10 may include antioxidant, light is stablized Agent, plasticizer, lubricant, fire retardant, antistatic agent, heat resistance improver, inorganic filler, organic is filled out ultra-violet stabilizer Fill the additives such as agent.

From the aspect of electrical insulating property, the sheet resistance of insulating resin layer 10 is preferably 1 × 10⁶Ω or more.From practical side Face considers that the sheet resistance of insulating resin layer 10 is preferably 1 × 10¹⁹Ω or less.

The thickness of insulating resin layer 10 be preferably 3 μm or more and 100 μm hereinafter, more preferably 5 μm or more and 50 μm hereinafter, Further preferably 5 μm or more and 20 μm or less.If more than the lower limit value with a thickness of the range of insulating resin layer 10, absolutely Edge resin layer 10 can give full play to the function as protective layer.If the upper limit value with a thickness of the range of insulating resin layer 10 Hereinafter, electromagnetic shielding film 1 can then be thinned.

(conductive layer)

Conductive layer at least has the metalliferous conductive adhesive layer of packet.Metal can be film-form, or particle Shape can also be other shapes.

Specifically, as described above, the conductive layer 20 in first embodiment has the gold adjacent with insulating resin layer 10 Belong to film layer 22 and the anisotropic conductive adhesive layer 24 adjacent with release film 40.

Conductive layer 20 in second embodiment have the metal film layer 22 adjacent with insulating resin layer 10 and with it is release The adjacent isotropic conductivity adhesive layer 26 of film 40.

Conductive layer 20 in third embodiment includes isotropic conductivity adhesive layer 26.

As conductive layer 20, from the aspect of sufficiently improving from electromagnetic wave shielding performance, preferably there is metal film layer 22 and each Anisotropy conductive adhesive layer 24 or isotropic conductivity adhesive layer 26.That is, conductive layer 20 preferably has metallic film This two layers of layer and conductive adhesive layer.

[metal film layer]

Metal film layer 22 be include metal film layer.The shape in a manner of being unfolded along the plane direction of metal film layer 22 At, therefore it is conductive in the surface direction, it works as electromagnetic wave shielding etc..

As metal film layer 22, can enumerate: by physical vapour deposition (PVD), (vacuum vapor deposition, sputtering, ion beam gas phase are heavy Product, electron-beam vapor deposition etc.) or the chemical vapor deposition vapor-deposited film formed, the plated film, the metal foil that are formed by plating etc.. In terms of excellent electric conductivity in face direction, conductive layer 20 is preferably vapor-deposited film, plated film.Conductive layer 20 can be thinned, and, Even if thickness is smaller, the electric conductivity in face direction is also very excellent, can use dry process simplicity and forms aspect, conductive layer 20 is more excellent It is selected as vapor-deposited film, further preferably the vapor-deposited film to be formed by physical vapour deposition (PVD).

As the metal for constituting metal film layer 22, can enumerate: aluminium, silver, copper, gold, conductive ceramic etc., from conductivity side Face consideration, preferably silver or copper.

It is preferably golden from electromagnetic wave shielding performance height, and from the aspect of metal film layer easy to form in metal film layer 22 Belong to vapor deposition layer, more preferably silver vapor deposition layer or copper vapor deposition layer.

The sheet resistance of metal film layer 22 is preferably 0.001 Ω or more and 1 Ω hereinafter, more preferably 0.001 Ω or more And 0.5 Ω or less.If the sheet resistance of metal film layer 22 is the lower limit value of the range or more, metal can sufficiently be thinned Film layer 22.If metal film layer 22 sheet resistance be the range upper limit value hereinafter, if be used as electromagnetic wave shielding energy Enough play one's part to the full.

The thickness of metal film layer 22 be preferably 0.01 μm or more and 5 μm hereinafter, more preferably 0.05 μm or more and 3 μm with Under.If metal film layer 22 with a thickness of 0.01 μm or more, the electric conductivity in face direction is better.If metal film layer 22 With a thickness of 0.05 μm or more, then the screening effect of electromagnetic noise is better.If metal film layer 22 with a thickness of the range Upper limit value hereinafter, electromagnetic shielding film 1 can then be thinned.In addition, the productivity of electromagnetic shielding film 1, flexibility become good.

[blackening layer]

The light reflective of the metal film layers such as silver-colored vapor deposition layer and copper vapor deposition layer 22 is high, has metallic luster.For Inhibit their metallic luster, conductive layer 20 can have on the face of 10 side of insulating resin layer of metal film layer 22 black Change layer.For example, in the case where electromagnetic shielding film 1 is used for display flexible printed circuit board, metal foil in order to prevent The gloss of film layer 22 influences that melanism preferably is arranged between metal film layer 22 and insulating resin layer 10 to the visibility of display Layer.

Blackening layer is the black layer for constituting and having preventing light reflection by light absorbent.Specifically, as blackening layer, Brightness L specified in JIS Z8781-5^*Preferably 5 or less.With following tendency, that is, brightness L^*Value it is smaller, degree of blackness is got over Greatly, can more light be inhibited to reflect.

Blackening layer is made of light absorbent arbitrary in for example following (i)~(iii).

(i) oxide of silver-colored oxide or copper

(ii) selected from least one of the group being made of copper nitride, copper oxide, nickel oxide and nickel oxide (iii) zinc, copper With any one in the alloy for closing gold, silver and zinc of zinc

In the case where blackening layer is made of (i), can enumerate: being formed by vapor deposition or plating includes silver The method of the layer of the oxide of oxide or copper.As vapour deposition process, for example, can be used: vaccum gas phase sedimentation method, sputtering method Deng well known vapour deposition process.

In the case where blackening layer is made of (ii), can enumerate: by vapor deposition or plating is formed comprising be selected from by The method of the layer of at least one of the group that copper nitride, copper oxide, nickel oxide and nickel oxide are constituted.

In the case where blackening layer is made of (iii), can enumerate: by vapor deposition or plating formed comprising zinc, The method of the layer of any one in the alloy for closing gold, silver and zinc of copper and zinc.

As the thickness of blackening layer, be not particularly limited, preferably 5nm or more and 20 μm hereinafter, more preferably 10nm with It is upper and 1 μm or less.If blackening layer with a thickness of the lower limit value more than, sufficiently light can be inhibited to reflect, if the upper limit Value is hereinafter, can then be readily formed blackening layer.

[anisotropic conductive adhesive layer]

Anisotropic conductive adhesive layer 24 in first embodiment is conductive in a thickness direction, in face side Do not have electric conductivity upwards, and, there is cementability.

Anisotropic conductive adhesive layer 24 is easy thinned conductive adhesive layer, it is possible to reduce aftermentioned conductive particle Amount improve the flexible advantage of electromagnetic shielding film 1 as a result, electromagnetic shielding film 1 can be thinned by having.

As anisotropic conductive adhesive layer 24, from the aspect of heat resistance can be played after solidification, preferably thermosetting The conductive adhesive layer for the property changed.The anisotropic conductive adhesive layer 24 of Thermocurable can be uncured state, can also Think B-staged state.

The anisotropic conductive adhesive layer 24 of Thermocurable is including, for example, Thermocurable bonding agent 24a and electric conductivity Grain 24b.As needed, the anisotropic conductive adhesive layer 24 of Thermocurable may include fire retardant.

It as Thermocurable bonding agent 24a, can enumerate: epoxy resin, phenolic resin, amino resins, alkyd resin, poly- ammonia Ester resin, synthetic rubber, UV light-curable acrylate resin etc..From the aspect of excellent heat resistance, preferred epoxy.Ring Oxygen resin may include for assigning flexible rubber constituent (carboxy-modified nitrile rubber, acrylic rubber etc.), tackifier etc..

In order to improve the intensity of anisotropic conductive adhesive layer 24, improve punching press characteristic, Thermocurable bonding agent 24a It may include celluosic resin, microfibre (glass fibre etc.).The Thermocurable bonding agent, which can according to need, not to be damaged It include other ingredients in the range of the effect of the utility model.

It as conductive particle 24b, can enumerate: particle, the graphite of metal (silver, platinum, gold, copper, nickel, palladium, aluminium, solder etc.) Powder, calcining carbon particle, calcining carbon particle of plating etc..As conductive particle 24b, from anisotropic conductive adhesive layer 24 It is examined in terms of the pressure loss of anisotropic conductive adhesive layer 24 when with more particularly suitable hardness and further decreasing hot pressing Consider, preferably metallic particles, more preferable copper particle.

10% compression strength of conductive particle 24b is preferably 30MPa or more and 200MPa hereinafter, more preferably 50MPa Above and 150MPa is hereinafter, further preferably 70MPa or more and 100MPa or less.If 10% compression strength of conductive particle More than the lower limit value of the range, then anisotropic conductive adhesive layer 24 via insulating film through-hole and printed circuit board Printed circuit be more reliably electrically connected, without the damage for causing the pressure for being applied to metal film layer 22 excessive in hot pressing It loses.If conductive particle 24b 10% compression strength be the range upper limit value hereinafter, if with the contact of metal film layer 22 Become good, electrical connection becomes reliable.

The average grain diameter of conductive particle 24b in anisotropic conductive adhesive layer 24 be 2 μm or more and 26 μm with Under, more preferably 4 μm or more and 16 μm or less.If the average grain diameter of conductive particle 24b is the lower limit value of the range or more, It then may insure the thickness of anisotropic conductive adhesive layer 24, sufficient adhesive strength can be obtained.If conductive particle The average grain diameter of 24b is the upper limit value of the range hereinafter, then may insure the flowing of anisotropic conductive adhesive layer 24 Property, when anisotropic conductive adhesive layer 24 being pressed into the through-hole of insulating film as described as follows, it is viscous to can use electric conductivity Agent is connect to be sufficient filling with inside the through-hole of insulating film.

As ratio of the conductive particle 24b in anisotropic conductive adhesive layer 24, in anisotropic conductive In 100 volume % of adhesive layer 24, preferably 1 volume % or more and 30 volume % hereinafter, more preferably 2 volume % or more and 15 volume % or less.If the ratio of conductive particle 24b is the lower limit value of the range or more, anisotropic conductive bonding The electric conductivity of oxidant layer 24 becomes good.If conductive particle 24b ratio be the range upper limit value hereinafter, if anisotropy The cementability of conductive adhesive layer 24, mobility (to the tracing ability of the shape of the through-hole of insulating film) become good.In addition, electric The flexibility of magnetic wave screened film 1 becomes good.

Storage modulus of the anisotropic conductive adhesive layer 24 at 180 DEG C is preferably 1 × 10³Pa or more and 5 × 10⁷Pa is hereinafter, more preferably 5 × 10³Pa or more 1 × 10⁷Pa or less.If anisotropic conductive adhesive layer 24 is at 180 DEG C Storage modulus be the range lower limit value more than, then anisotropic conductive adhesive layer 24 have more suitable hardness, Pressure loss when can reduce hot pressing in conductive adhesive layer.As a result, conductive adhesive layer and printed circuit board Printed circuit is sufficiently bonded, and anisotropic conductive adhesive layer 24 is via the through-hole of insulating film and the printing electricity of printed circuit board Road is more reliably electrically connected.If conductive adhesive layer the storage modulus at 180 DEG C be the range upper limit value hereinafter, if The flexibility of electromagnetic shielding film 1 becomes good.As a result, electromagnetic shielding film 1 is easy to sink in the through-hole of insulating film, respectively to different Property conductive adhesive layer 24 is more reliably electrically connected via the through-hole of insulating film with the printed circuit of printed circuit board.

The sheet resistance of anisotropic conductive adhesive layer 24 is preferably 1 × 10⁴Ω or more 1 × 10¹⁶Ω is hereinafter, more excellent It is selected as 1 × 10⁶Ω or more and 1 × 10¹⁴Ω or less.If the sheet resistance of anisotropic conductive adhesive layer 24 is the range Lower limit value more than, then the content of conductive particle 24b can be inhibited lower.If anisotropic conductive adhesive layer 24 Sheet resistance be the range upper limit value hereinafter, then there is no problem in practical aspect, anisotropy.

The thickness of anisotropic conductive adhesive layer 24 is preferably 3 μm or more and 25 μm hereinafter, more preferably 5 μm or more And 15 μm or less.If more than the lower limit value with a thickness of the range of anisotropic conductive adhesive layer 24 may insure The mobility (to the tracing ability of the shape of the through-hole of insulating film) of anisotropic conductive adhesive layer 24, can use electric conductivity Bonding agent is sufficient filling with inside the through-hole of insulating film.If anisotropic conductive adhesive layer 24 with a thickness of the upper of the range Limit value is hereinafter, can then be thinned electromagnetic shielding film 1.In addition, the flexibility of electromagnetic shielding film 1 becomes good.

[isotropic conductivity adhesive layer]

Isotropic conductivity adhesive layer 26 in second embodiment or third embodiment is in thickness direction and face It is conductive on direction, and, there is cementability.

Isotropic conductivity adhesive layer 26 has the electromagnetic wave shielding performance that can be further improved electromagnetic shielding film 1 The advantages of.

As isotropic conductivity adhesive layer 26, from the aspect of heat resistance can be played after solidification, preferably thermosetting The conductive adhesive layer for the property changed.The isotropic conductivity adhesive layer 26 of Thermocurable can be uncured state, can also Think B-staged state.

The isotropic conductivity adhesive layer 26 of Thermocurable is for example comprising Thermocurable bonding agent 26a and electric conductivity Grain 26b.The isotropic conductivity adhesive layer 26 of Thermocurable can according to need comprising fire retardant.

The ingredient and conductive particle 26b of Thermocurable bonding agent 26a contained by isotropic conductivity adhesive layer 26 Material and anisotropic conductive adhesive layer 24 contained by Thermocurable bonding agent 24a ingredient and conductive particle 24b Material it is identical.

The average grain diameter of conductive particle 26b in isotropic conductivity adhesive layer 26 be preferably 0.1 μm or more and 10 μm hereinafter, more preferably 0.2 μm or more and 1 μm or less.If the average grain diameter of conductive particle 26b is the lower limit of the range More than value, then the contact of conductive particle 26b, which is counted, increases, and can steadily improve the conduction of three-dimensional.If electric conductivity The average grain diameter of particle 26b is the upper limit value of the range hereinafter, then may insure isotropic conductivity adhesive layer 26 Mobility (to the tracing ability of the shape of the through-hole of insulating film), can use the through-hole that conductive adhesive is sufficient filling with insulating film It is internal.

As ratio of the conductive particle 26b in isotropic conductivity adhesive layer 26, in isotropic conductivity In 100 volume % of adhesive layer 26, preferably 50 volume % or more and 80 volume % are hereinafter, more preferably 60 volume % or more And 70 below volume %.If the ratio of conductive particle 26b is the lower limit value of the range or more, isotropic conductivity is viscous The electric conductivity for connecing oxidant layer 26 becomes good.If conductive particle 26b ratio be the range upper limit value hereinafter, if respectively to same The cementability of property conductive adhesive layer 26, mobility (to the tracing ability of the shape of the through-hole of insulating film) become good.In addition, The flexibility of electromagnetic shielding film 1 becomes good.

Storage modulus of the isotropic conductivity adhesive layer 26 at 180 DEG C preferably 1 × 10³Pa or more and 5 × 10⁷Pa Hereinafter, more preferable 5 × 10³Pa or more and 1 × 10⁷Pa or less.The preferred reason of the range and anisotropic conductive adhesive Layer 24 is identical.

The sheet resistance of isotropic conductivity adhesive layer 26 is preferably 0.05 Ω or more and 2.0 Ω hereinafter, more preferably For 0.1 Ω or more and 1.0 Ω or less.If the sheet resistance of isotropic conductivity adhesive layer 26 is the lower limit value of the range More than, then the content of conductive particle 26b can be inhibited lower, the viscosity of conductive adhesive will not become excessively high, apply Cloth becomes be more good.Furthermore it is possible to further ensure that the mobility of isotropic conductivity adhesive layer 26 (to insulating film Through-hole shape tracing ability).If the sheet resistance of isotropic conductivity adhesive layer 26 is the upper limit value of the range Hereinafter, then the whole face of isotropic conductivity adhesive layer 26 has uniform electric conductivity.

The thickness of isotropic conductivity adhesive layer 26 is preferably 5 μm or more and 20 μm hereinafter, more preferably 7 μm or more And 17 μm or less.If it is more than the lower limit value with a thickness of the range of isotropic conductivity adhesive layer 26, isotropism The electric conductivity of conductive adhesive layer 26 becomes well, to can be used as electromagnetic wave shielding and play one's part to the full.Furthermore it is possible to really The mobility (to the tracing ability of the shape of the through-hole of insulating film) for protecting isotropic conductivity adhesive layer 26, can use conduction Property bonding agent is sufficient filling with inside the through-hole of insulating film, and folding resistance is also ensured, even if bending repeatedly, isotropic conductivity Adhesive layer 26 will not be broken.If the upper limit value with a thickness of the range of isotropic conductivity adhesive layer 26 hereinafter, Electromagnetic shielding film 1 can then be thinned.In addition, the flexibility of electromagnetic shielding film 1 becomes good.

(carrier film)

Carrier film 30 is to strengthen and protect the supporter of insulating resin layer 10 and conductive layer 20, makes electromagnetic shielding film 1 It is operational good.In particular, using relatively thin film, specifically using with a thickness of 20 μm of films below as insulating resin layer In the case where 10, by that insulating resin layer 10 can be prevented to be broken with carrier film 30.

Carrier film 30 is removed after electromagnetic shielding film 1 to be attached to printed circuit board etc. above from insulating resin layer 10.

Carrier film 30 used in present embodiment has carrier film main body 32 and the insulation of carrier film main body 32 is arranged in Adhesive phase 34 on the surface of 10 side of resin layer.

As the resin material of carrier film main body 32, can enumerate: polyethylene terephthalate is (in the following, otherwise referred to as "PET".), polyethylene naphthalate, polyethylene glycol isophthalate, polybutylene terephthalate (PBT), polyolefin, Poly- acetic acid esters, polyphenylene sulfide, polyamide, vinyl-vinyl acetate copolymer, polyvinyl chloride, gathers inclined two chloroethene at polycarbonate Alkene, synthetic rubber, liquid crystal polymer etc..As resin material, from heat resistance (dimensionally stable when manufacturing electromagnetic shielding film 1 Property) and consider in price, preferably PET.

Carrier film main body 32 may include colorant (pigment, dyestuff etc.) and either side or two sides in filler.

As in colorant and filler either side or two sides, distinguished from that can define with insulating resin layer 10, And it is easy after hot pressing from the aspect of the removing residual of discovery carrier film 30, preferably the object different from 10 color of insulating resin layer Matter, the combination of more preferable white pigment, filler or white pigment and other pigment or filler.

Storage modulus of the carrier film main body 32 at 180 DEG C is preferably 8 × 10⁷Pa or more and 5 × 10⁹Pa is hereinafter, more preferably 1×10⁸Pa or more and 8 × 10⁸Pa or less.If storage modulus of the carrier film main body 32 at 180 DEG C is the lower limit value of the range More than, then carrier film 30 has suitable stiffness, and pressure loss when can reduce hot pressing in carrier film 30.If carrier film master Storage modulus of the body 32 at 180 DEG C is the upper limit value of the range hereinafter, then the flexibility of carrier film 30 becomes good.

The thickness of carrier film main body 32 is preferably 3 μm or more and 75 μm hereinafter, more preferably 12 μm or more and 50 μm or less. If more than the lower limit value with a thickness of the range of carrier film main body 32 operability of electromagnetic shielding film 1 becomes good.If The upper limit value with a thickness of the range of carrier film main body 32 is hereinafter, the then hot pressing electromagnetic shielding film 1 on the surface of insulating film Conductive adhesive layer (anisotropic conductive adhesive layer 24 or isotropic conductivity adhesive layer 26) when, be easy to Conductive adhesive layer conducts heat.

Adhesive phase 34 be for example on the surface of carrier film main body 32 coating comprising adhesive adhesive composition and It is formed.There is adhesive phase 34 by carrier film 30, when removing release film 40 from conductive adhesive layer or pass through hot pressing In the upper stickup electromagnetic shielding film 1 such as printed circuit board, carrier film 30 can be inhibited to remove from insulating resin layer 10.Therefore, Carrier film 30 can give full play to the effect as protective film.

As adhesive, the substance of the appropriate adhesiveness of adhesive phase 34 is preferably assigned, wherein appropriate adhesiveness refers to hot pressing Preceding carrier film 30 is not easy to remove from insulating resin layer 10, can remove carrier film 30 from insulating resin layer 10 after hot pressing.

It as adhesive, can enumerate: acrylic adhesives, polyurethane binding, rubber adhesive etc..

The Tg of adhesive is preferably -100 DEG C or more and 60 DEG C hereinafter, more preferably -60 DEG C or more and 40 DEG C or less.

The thickness of carrier film 30 is preferably 25 μm or more and 125 μm hereinafter, more preferably 38 μm or more and 100 μm or less. If more than the lower limit value with a thickness of the range of carrier film 30 operability of electromagnetic shielding film 1 becomes good.If carrier The upper limit value with a thickness of the range of film 30 is hereinafter, the electric conductivity of hot pressing electromagnetic shielding film 1 is viscous on the surface of insulating film When connecing oxidant layer, it is easy to transmit heat to conductive adhesive layer.

(release film)

Release film 40 protects conductive adhesive layer, keeps the operability of electromagnetic shielding film 1 good.By electromagnetic shielding film 1 be pasted onto printed circuit board etc. it is upper before, release film 40 is by from conductive adhesive layer (anisotropic conductive adhesive layer 24 Or isotropic conductivity adhesive layer 26) on remove.

Release film 40 is for example with release film main body 42 and the conductive adhesive layer side that release film main body 42 is arranged in Parting agent layer 44 on surface.

As the resin material of release film main body 42, material identical with the resin material of carrier film main body 32 can be enumerated.

Release film main body 42 may include colorant, filler etc..

The thickness of release film main body 42 be preferably 5 μm or more and 500 μm hereinafter, more preferably 10 μm or more and 150 μm with Under, further preferred 25 μm or more and 100 μm or less.

Parting agent layer 44 is formed using the surface of mould release processing release film main body 42.Have by release film 40 release Oxidant layer 44 is easily peeled off release film 40, conductive adhesive layer is not easily broken when removing release film 40 from conductive adhesive layer It splits.

As mould release, well known mould release is used.

The thickness of parting agent layer 44 be preferably 0.05 μm or more and 30 μm hereinafter, more preferably 0.1 μm or more and 20 μm with Under.If the thickness of parting agent layer 44 is in the range, more easily peelable release film 40.

(thickness of electromagnetic shielding film)

The thickness (in addition to carrier film 30 and release film 40) of electromagnetic shielding film 1 be preferably 3 μm or more and 50 μm hereinafter, More preferably 5 μm or more and 30 μm or less.If do not include the electromagnetic shielding film 1 of carrier film 30 and release film 40 with a thickness of institute The lower limit value of range or more is stated, then not easy to break when removing carrier film 30, upper limit value if the range is hereinafter, then can be with The printed circuit board with electromagnetic shielding film is thinned.

The second method of the utility model is the manufacturing method of electromagnetic shielding film, with following processes: forming insulation Resin layer, the insulating resin layer be configured to it is membranaceous and including foaming after aromatic polyether ketone；The one of the insulating resin layer Face forms conductive layer.

Specifically, the manufacturing method of the electromagnetic shielding film as first embodiment, can enumerate: following methods (A1), method (A2).The manufacturing method of electromagnetic shielding film as second embodiment can enumerate following methods (B1), side Method (B2).The manufacturing method of electromagnetic shielding film as a third embodiment can enumerate following methods (C1), method (C2).

Method (A1) is with following processes (A1-1)~(A1-5) method.

Process (A1-1): formed insulating resin layer 10, the insulating resin layer 10 be configured to it is membranaceous, and, including foaming after Aromatic polyether ketone；

Process (A1-2): insulating resin layer 10 is layered in carrier film 30.

Process (A1-3): metal film layer 22 is formed on the face with 30 opposite side of carrier film of insulating resin layer 10.

Process (A1-4): anisotropy is formed on the face with 10 opposite side of insulating resin layer of metal film layer 22 and is led Electrical adhesive layer 24.

Process (A1-5): on the face upper layer with 22 opposite side of metal film layer of anisotropic conductive adhesive layer 24 Folded release film 40.

In the following, each process of method (A1) is described in detail.

In process (A1-1), aromatic polyether ketone can be configured to it is membranaceous after make its foaming, can also be will be fragrant Fragrant race's polyether-ketone makes its foaming while being configured to membranaceous.Can manufacture at low cost can prevent wrinkle or deformation and 10 aspect of the low insulating resin layer of relative dielectric constant, preferably by aromatic polyether ketone be configured to it is membranaceous after make its foaming.

As an example that aromatic polyether ketone is configured to the membranaceous method for making it foam later, can enumerate with following works The method of sequence: extrusion shaper melting mixing aromatic polyether ketone is used, fusant is configured to foaming aromatic polyether ketone Film (in the following, referred to as " foaming film ")；Make in the foaming film comprising foaming agent；Heat the foaming film containing foaming agent Make its foaming.

As extrusion shaper, for example, can enumerate: (twin-screw extruder, three screw rods squeeze multiscrew extrusion shaper Forming machine, four Screw Extrusion forming machines, eight Screw Extrusion forming machines etc. out), single screw rod extrusion shaper, mixing mill, pressurization pinch Conjunction machine, mixer etc..

As long as the temperature of melting mixing be can with melting mixing aromatic polyether ketone and aromatic polyether ketone it is not resolvent Temperature is not particularly limited.Specifically, melting mixing temperature preferably uses the fusing point of aromatic polyether ketone or more and low In thermal decomposition temperature, more preferably use 320 DEG C or more and 450 DEG C hereinafter, it is further preferred use 360 DEG C or more and 420 DEG C with Under, particularly preferably use 380 DEG C or more and 400 DEG C or less.If melting mixing temperature is the lower limit value or more, it is easy to virtue Fragrant race's polyether-ketone carries out melting extrusion forming, if the upper limit value hereinafter, can then prevent aromatic polyether ketonic decomposition.

The moisture content for being supplied to the aromatic polyether ketone of extrusion shaper is preferably 0ppm or more and 2000ppm hereinafter, more Preferably 0ppm or more and 1000ppm are hereinafter, further preferably 100ppm or more and 1000ppm or less.If aromatic polyether The moisture content of ketone is the upper limit value hereinafter, can then prevent the unnecessary foaming before making it foam by foaming agent.

The oxidative degradation of aromatic polyether ketone and oxygen crosslinking when melting mixing in order to prevent, preferably makes the confession of melting mixing machine Material mouth is inert gas atmosphere.As inert gas, for example, can be used: helium, neon, argon gas, Krypton, nitrogen, carbon dioxide Gas etc..

In addition, vacuum pump etc., which can be used, makes decompression in melting mixing machine when melting mixing, aromatic series is removed to volatilize Moisture and low molecular compound contained in polyether-ketone etc..

When fusant is configured to membranaceous, aromatic polyether ketone is melted in extrusion shaper, obtains fusant, from being set to The continuous extrusion melt of T die head of the front end of extrusion shaper is formed band-like.Foaming film is obtained as a result,.

The temperature of T die head preferably uses the fusing point of aromatic polyether ketone more than or lower than thermal decomposition temperature, more preferably uses 320 DEG C or more and 450 DEG C hereinafter, further preferably using 360 DEG C or more and 420 DEG C hereinafter, particularly preferably using 380 DEG C or more And 400 DEG C or less.If the temperature of T die head be the lower limit value more than, be easy to aromatic polyether ketone carry out melting extrusion at Shape, if the upper limit value hereinafter, can then prevent aromatic polyether ketonic decomposition.

It is preferred that being equipped with gear pump and filter between melting extrusion forming machine and T die head.It, can by using gear pump Easily T die head will be supplied to certain flow using the mixture after the melting of melting extrusion forming machine, to stablize landform Film-like.By using filter, film is can be improved in the foreign matters such as gel compound contained in the mixture after can removing melting Quality.

It is allowed to cool it is preferred that the film of the molten condition squeezed out from T die head is made to be close to chill roll.

Preferably at least 1 or more press bonding roller is contacted with the chill roll.It can use chill roll and clamp molten condition Film, and pressed using press bonding roller to the direction of chill roll, so that film is close to chill roll reliably to be cooled to as a result,.

As press bonding roller, it is preferable to use the circumferential surface of the roller main body of metal manufacture is covered with roller made of rubber layer.As structure At the rubber of rubber layer, for example, can enumerate: silicon rubber, fluorubber, natural rubber, isoprene rubber, butadiene rubber, drop Norbornene rubber, nitrile rubber, polyurethane rubber etc..In these rubber, from the aspect of heat resistance height, preferably silicon rubber, Fluorubber.

The temperature of chill roll be preferably (Tg+20) DEG C of aromatic polyether ketone hereinafter, more preferably (Tg-10) DEG C hereinafter, Further preferably 50 DEG C or more and (Tg-20) DEG C or less.

The temperature of press bonding roller is preferably (Tg+20) DEG C of aromatic polyether ketone hereinafter, more preferably Tg DEG C hereinafter, further Preferably 50 DEG C or more and (Tg-10) DEG C or less.

If chill roll temperature and press bonding roller temperature be the upper limit value hereinafter, if can easily realize aftermentioned hair The bubble relative crystallinity and storage modulus of film.Therefore, it is easier to containing foaming agent, foaminess can be improved.

The abutting time for making the film abutting chill roll of molten condition is preferably 0.1 second or more and 120 seconds hereinafter, more preferably 0.5 second or more and 60 seconds hereinafter, further preferably 1 second or more and 30 seconds or less.If being close to the time in the range, hold Easily realize aftermentioned storage modulus and the relative crystallinity.

From the aspect of easy foaming, foaming preferably obtained as described above has specific elasticity modulus with film.It is specific and Speech is using measurement of dynamic viscoelasticity device, on one side at least -60 DEG C or more and 360 DEG C or less as preferred foaming film Range temperature when measuring dynamic viscoelastic on one side, in the range of (Tg-10) DEG C or more and (Tg+50) DEG C or less, storage Energy modulus is reduced to 2 × 10⁸Pa or less and have minimum.

When foaming can be easily prevented from bubble merge or rupture in terms of, preferably the storage modulus of foaming film is 300 DEG C or less range in be 1 × 10⁵Pa or more.

The relative crystallinity of foaming film is preferably 80% hereinafter, more preferably 50% hereinafter, further preferably 30% Below.If the relative crystallinity of foaming film is the upper limit value hereinafter, in particular range as described above, storage modulus has There is minimum, foaming and molding improves.

In addition, the relative crystallinity of foaming film is preferably 5% or more from the aspect of practical.

The relative crystallinity of foaming film is based on when using differential scanning calorimeter with the heating of 10 DEG C/minute of heating rate Heat analysis by following formula as a result, acquired.

Relative crystallinity={ 1- (Δ H_c/ΔH_m)}×100

Here, Δ H_mFor the heat (J/g) of crystalline melting peak, Δ H_cThe heat (J/g) for peak crystallization of attaching most importance to.

The thickness of foaming film is preferably 2 μm or more and 100 μm hereinafter, more preferably 5 μm or more and 90 μm or less.If hair Bubble film with a thickness of the lower limit value more than, then foam and be easy in film comprising foaming agent, therefore hair can be readily formed Vacuolar membrane.In addition, until the inside of foaming film can sufficiently contain foaming agent being easy that it is made equably to foam.

As foaming agent used in the process containing foaming agent in the foaming film is made, can be used: heat decomposition type Liquid obtained from foaming agent, organic solvent, inert gas, compressed inert and supercritical fluid etc..Heat decomposition type foaming Agent can be classified as organic foaming agent, inorganic foaming agent.

As organic foaming agent, for example, can enumerate: azo-compound, nitroso compound, hydrazine compound, hydrazides Close object etc..These compounds can generate nitrogen when heated.

As azo-compound, for example, can enumerate: azodicarbonamide, Barium azodicarboxylate, azodiisobutyronitrile etc.. As nitroso compound, for example, can enumerate: N, N '-dinitrosopentamethylene tetramine etc..As hydrazine compound, for example, can It enumerates: biruea etc..As hydrazide compound, for example, can enumerate: unifor, 4,4 '-oxobenzenesulfonyl hydrazide etc.

As inorganic compound, for example, can enumerate: sodium bicarbonate, ammonium carbonate, ammonium hydrogen carbonate etc..These compounds are equal Carbonic acid gas can be generated when heated.

It as organic solvent, can enumerate: hydrocarbon, halogenated hydrocarbons, alcohol, ketone etc..

As hydrocarbon, for example, can enumerate: the lower aliphatics such as propane, normal butane, iso-butane, pentane, isopentane, hexane Hydrocarbon compound；The ester ring type hydrocarbons compound such as cyclobutane, pentamethylene；Aromatic hydrocarbon compounds such as benzene,toluene,xylene etc..

As halogenated hydrocarbon compound, for example, can enumerate: chloromethyl, chloroethyl, 1- chlorine-1,1-difluoroethane etc..

As alcoholic compound, for example, can enumerate: methanol, ethyl alcohol, propyl alcohol etc..

As ketone compound, for example, can enumerate: acetone, methyl ethyl ketone etc..

It as inert gas, can enumerate: carbon dioxide gas (carbonic acid gas), nitrogen, argon gas, helium, fluorochlorohydrocarbon gas Deng.

In these foaming agents, the preferred inert gas of inert gas, liquefied inert gas or supercriticality, to hair From the aspect of bubble permeability of the membrane is high, operability is excellent, more preferable supercritical carbon dioxide (liquefied carbon dioxide).

In the following, to use the inert gas of inert gas, liquefied gas or supercriticality (hereinafter, referred to as " inertia Gas class foaming agent ".) method as foaming agent to form the insulating resin layer 10 of foaming is illustrated.

In the case where foaming agent is inert gas class foaming agent, having makes to be impregnated with the foaming of inert gas class in foaming film The process (impregnation process) of agent.

When being impregnated with inert gas class foaming agent in making foaming film, preferably ventilative substrate is overlayed on foaming film simultaneously Winding forms roll, and inert gas class foaming agent is provided around the roll.If providing indifferent gas to the roll Body class foaming agent can then make foaming with being sufficiently impregnated with inert gas class foaming agent in film.

As ventilative substrate, for example, can enumerate: the formation such as paper, non-woven fabrics, synthetic fibers mixed copy paper, metal mesh, resin web Enable air to the material in the gap penetrated from one towards another side.

The impregnation pressure (gauge pressure) of inert gas class foaming agent is preferably normal pressure or more, more preferably 5MPa or more and 30MPa or less.If being impregnated with pressure is the lower limit value or more, inert gas class foaming agent can be made sufficiently to contain and be immersed in foaming use In film, if the upper limit value hereinafter, then can simplify the equipment in impregnation process.

The impregnation temperature of inert gas class foaming agent is preferably 15 DEG C of Tg DEG C more than or lower than foam films, and more preferably 25 DEG C or more and (Tg-50) DEG C hereinafter, further preferably 40 DEG C or more and (Tg-70) DEG C or less.Under if impregnation temperature is described More than limit value, then it can easily make inert gas class foaming agent containing being immersed in foaming film, if the upper limit value hereinafter, then Foaming membrane crystallization can be prevented, the obstruction being impregnated with to foaming agent can be inhibited.

The impregnation time of inert gas can suitably be adjusted according to impregnation pressure and impregnation temperature, for example, at 30 minutes or more To in the range of 96 hours.

In the case where using carbon dioxide as inert gas, preferably makes to be impregnated with pressure 7.4MPa or more and make to be impregnated with Temperature is 31 DEG C or more, makes carbon dioxide supercriticality.It is right when using supercritical carbon dioxide as foaming agent The impregnation of foaming film is fast, can easily control expansion ratio or foamed state by adjusting the impregnation time.

It is preferred that being impregnated with after inert gas class foaming agent in foaming film, stop providing inert gas class to foaming film Foaming agent, and release stress (pressure release process).At this point, it is preferred that pressure discharges suddenly, specifically, it is preferable that with 1MPa/ seconds Above speed releases stress.The faster the better for the rate of release of pressure.If releasing stress according to the speed, heat can be passed through Mechanics it is instable induction and easily foaming film inside formed foaming core.Therefore, the hair of sufficient quantity can be formed Complex, the bubble diameter after can making foaming is uniformly and in the appropriate range.

There are the tendencies that Tg is reduced for foaming film after being impregnated with inert gas class foaming agent.

It is formed in foam films after foaming core, foamable film makes the gas expansion to foam in core to (the hair that foams Steep process).The insulating resin layer 10 including foaming layer is formed as a result,.

The heating temperature of foaming film is preferably (Tg-60) DEG C of foaming film or more and (Tg+70) DEG C hereinafter, more preferably (Tg-60) DEG C for foaming film or more and (Tg+60) DEG C hereinafter, further preferably foaming film (Tg-50) DEG C or more And (Tg+50) DEG C or less.It if heating temperature is the lower limit value or more, can sufficiently soften foaming film, it is made to be easy hair Bubble, for example described upper limit value is hereinafter, can then prevent bubble from merging and rupturing, furthermore it is possible to which the foam films prevented are stuck up It rises, bending, wrinkle, expansion etc. deform.

As the heating means of foaming film, for example, can be used: the side of foamable film in mold after the heating Method, Hot-blast Heating method, hot bath heating, oil bath heating method, hot plate contact heating, steam heating, superheated steam heating Method etc..

In the case where improving expansion ratio, being repeated several times includes the impregnation process, the pressure release process and institute State a series of process of foamed process.Wherein, the heating temperature in second of later foamed process is preferably (Tg- 60) DEG C more than or lower than Tg DEG C.

In the lower situation of relative crystallinity of the membranaceous insulating resin layer 10 of the foaming as above obtained, further implement Heat treatment.By heat treatment, relative crystallinity is improved, and the heat resistance and mechanical strength of insulating resin layer 10 are further It improves.

The heating temperature when heat treatment is preferably Tg DEG C more than or lower than fusing point, more preferably (Tg+20) DEG C or more And (fusing point -50) DEG C or less.If heating temperature is Tg DEG C or more, it is easy to improve crystallinity, if being lower than fusing point, can prevents Bubble merges or rupture, and sufficiently maintains membranaceous shape.

Insulating resin layer 10 can also be formed by the method other than the above method, which is configured to film Shape, and, including the aromatic polyether ketone after foaming.

For example, as the other methods for forming insulating resin layer 10, the following methods can be used: using extrusion shaper, it is right Melting mixing is carried out comprising the mixture of aromatic polyether ketone and foaming agent, then, fusant is discharged from T die head, formation is membranaceous, Make its foaming simultaneously.When the fusant is discharged from T die head, carry out the gas expansion of self foaming agent, therefore aromatic series can be made poly- The foaming of ether ketone.

In addition, following method can be enumerated as the other methods for forming insulating resin layer 10: melting virtue using extruder Fragrant race's polyether-ketone, while the inert gas after pressurization is imported into extruder, aromatic polyether ketone and lazy is kneaded in extruder Property gas after, fusant is discharged from T die head, is formed membranaceous, while making its foaming.

In process (A1-2), the membranaceous insulating resin layer 10 of the foaming as above obtained is layered in being equipped with for carrier film 30 On the face of adhesive phase 34.The insulating resin layer 10 for being just formed as foaming membranaceous can be directly layered in carrier film 30, It is membranaceous that foaming can also be sent out from the volume after the insulating resin layer 10 for being formed into foaming membranaceous winds and forms web-like Insulating resin layer 10 and be layered in carrier film 30.

It as the forming method of the metal film layer 22 in process (A1-3), can enumerate: by physical vapour deposition (PVD), CVD (chemical vapor deposition) forms the method for vapor-deposited film, forms the method for plated film, the method for pasting metal foil etc. by plating. From the aspect of can be with the metal film layer 22 of the excellent electric conductivity in forming face direction, gas be preferably formed by physical deposition, CVD The method of phase deposition film or the method that plated film is formed by plating.From the thickness that metal film layer 22 can be thinned, and, even if Thickness is smaller, can also can pass through dry process simplicity landform with the metal film layer 22 of the excellent electric conductivity in forming face direction From the aspect of metal film layer 22, the method that vapor-deposited film is more preferably formed by physical vapour deposition (PVD), CVD, into one The method that step preferably forms vapor-deposited film by physical vapour deposition (PVD).

In process (A1-4), the applying conductive on the face with 10 opposite side of insulating resin layer of metal film layer 22 Bonding agent coating.Conductive adhesive coating contains Thermocurable bonding agent 24a, conductive particle 24b and solvent.By from institute Solvent flashing in the conductive adhesive coating of coating forms anisotropic conductive adhesive layer 24.

As solvent contained by conductive adhesive coating, for example, can enumerate: ester (butyl acetate, ethyl acetate, acetic acid Methyl esters, isopropyl acetate, ethylene glycol acetate etc.), ketone (methyl ethyl ketone, methyl iso-butyl ketone (MIBK), acetone, methyl-isobutyl Ketone, cyclohexanone etc.), alcohol (methanol, ethyl alcohol, isopropanol, butanol, propylene glycol monomethyl ether, propylene glycol etc.) etc..

As the coating method of conductive adhesive, for example, using the method for using following coating machines: molding coating Machine, gravure coater, roll coater, curtain flow coater, spin coater, metering bar coater, reverse roll coater, engagement Coating machine, fountain coater, rod coater, Kohler coater, blade coating machine, knife type coater, cast coat The various coating machines such as machine, silk screen coating machine.

It, will be from such a way that parting agent layer 44 is contacted with anisotropic conductive adhesive layer 24 in process (A1-5) Type film 40 is layered on the face with 22 opposite side of metal film layer of anisotropic conductive adhesive layer 24.

After release film 40 is layered on anisotropic conductive adhesive layer 24, set including carrier film 30, insulation The laminated body implementation pressurized treatments of rouge layer 10, metal film layer 22, anisotropic conductive adhesive layer 24 and release film 40, with Improve the close property between each layer.

Pressure when as pressurized treatments, preferably 0.1kPa or more and 100kPa hereinafter, more preferably 0.1kPa or more and 20kPa is hereinafter, further preferred 1kPa or more and 10kPa or less.

It can be heated while pressurized treatments.As heating temperature at this time, preferably 50 DEG C or more and 100 DEG C with Under.

Method (A2) is with following processes (A2-1)~(A2-5) method.

Process (A2-1): formed insulating resin layer 10, the insulating resin layer 10 be configured to it is membranaceous, and, including foaming after Aromatic polyether ketone.

Process (A2-2): obtained insulating resin layer 10 is layered in process in carrier film 30.

Process (A2-3): forming metal film layer 22 on the face with 30 opposite side of carrier film of insulating resin layer 10, To form laminated body (I).

Process (A2-4): anisotropic conductive adhesive layer 24 is formed on release film 40, to form laminated body (II)。

Process (A2-5): with the anisotropic conductive of the metal film layer 22 of laminated body (I) and laminated body (II) bonding The mode that oxidant layer 24 contacts is bonded laminated body (I) and laminated body (II).

Process (A2-1), process (A2-2) and process (A2-3) and process (A1-1), process in the method (A1) (A1-2) and process (A1-3) is identical.

In process (A2-4), the applying conductive bonding agent coating on the face equipped with parting agent layer 44 of release film 40. By forming anisotropic conductive adhesive layer 24 from the conductive adhesive coating solvent flashing being coated with.Electric conductivity is viscous It is identical as process (A1-4) in the method (A) to connect agent coating and coating method.

In process (A2-5), when being bonded laminated body (I) and laminated body (II), it is possible to implement pressurized treatments, to improve stacking The close property of body (I) and laminated body (II).Pressurized conditions are identical as the pressurized treatments in process (A1-5).In addition, in process (A2-5) it in, can also be heated in the same manner with process (A1-5).

In method (B1), conductive adhesive coating is changed to containing Thermocurable bonding agent 26a, conductive particle Isotropic conductivity adhesive layer 26 is consequently formed in the coating of 26b and solvent, and in addition to this, method (B1) is and method (A1) identical method.

In method (B2), conductive adhesive coating is changed to containing Thermocurable bonding agent 26a, conductive particle Isotropic conductivity adhesive layer 26 is consequently formed in the coating of 26b and solvent, and in addition to this, method (B2) is and method (A2) identical method.

Method (C1) is with following processes (C1-1)~(C1-4) method.

Process (C1-1): formed insulating resin layer 10, the insulating resin layer 10 be configured to it is membranaceous, and, including foaming after Aromatic polyether ketone.

Process (C1-2): insulating resin layer 10 is layered in carrier film 30.

Process (C1-3): isotropic conductivity is formed on the face with 30 opposite side of carrier film of insulating resin layer 10 Adhesive layer 26.

Process (C1-4): on the face upper layer with 10 opposite side of insulating resin layer of isotropic conductivity adhesive layer 26 Folded release film 40.

In method (C1), the formation of metal film layer is omitted, uses isotropic conductivity bonding agent as electric conductivity Bonding agent, directly on insulating resin layer 10 formed isotropic conductivity adhesive layer 26, in addition to this, method (C1) be with The identical method of method (A1).

Method (C2) is with following processes (C2-1)~(C2-4) method.

Process (C2-1): formed insulating resin layer 10, the insulating resin layer 10 be configured to it is membranaceous, and, including foaming after Aromatic polyether ketone.

Process (C2-2): insulating resin layer 10 is layered in carrier film 30, to form laminated body (I).

Process (C2-3): isotropic conductivity adhesive layer 26 is formed on release film 40, to form laminated body (II)。

Process (C2-4): with the isotropic conductivity of the insulating resin layer 10 of laminated body (I) and laminated body (II) bonding The mode that oxidant layer 26 contacts is bonded laminated body (I) and laminated body (II).

In method (C2), the formation of metal film layer is omitted, uses isotropic conductivity bonding agent as electric conductivity Bonding agent is bonded isotropic conductivity adhesive layer 26 on insulating resin layer 10, and in addition to this, method (C2) is and method (A2) identical method.

(function and effect)

The electromagnetic shielding film 1 of the method according to insulating resin layer 10 containing aromatic polyether ketone, can be improved insulation Resin layer 10 is relative to the bonding force for wrapping metalliferous conductive layer 20.Accordingly it is possible to prevent during processing electromagnetic shielding film 1 Insulating resin layer 10 and conductive layer 20 generate splitting.Especially in the case where conductive layer 20 has metal film layer 22, The effect is played, and the insulating resin layer 10 containing aromatic polyether ketone is Nian Jie with metal film layer 22 with high bonding force.

In addition, dielectric constant is low since insulating resin layer 10 includes aromatic polyether ketone foaming layer.Therefore, our The dielectric constant that the electromagnetic shielding film 1 of formula is whole also reduces.Therefore, the printing electricity of the electromagnetic shielding film 1 equipped with the method The signal velocity of circuit can be improved in road plate.

In addition, thermal conductivity reduces since insulating resin layer 10 is the foaming layer containing aromatic polyether ketone.Therefore, The thermal conductivity of the electromagnetic shielding film 1 of the method also reduces.

In addition, having since aromatic polyether ketone is the high resin of Tg high, heat resistance and containing aromatic polyether ketone The heat resistance of the electromagnetic shielding film 1 of insulating resin layer 10 is high.

(other embodiment)

The electromagnetic shielding film of the method is not limited to above embodiment.

For example, in the surface adhesion of anisotropic conductive adhesive layer 24 or isotropic conductivity adhesive layer 26 In lesser situation, it is convenient to omit release film 40.

In the case where insulating resin layer 10 has sufficient flexibility and intensity, it is convenient to omit carrier film 30.

In the case where carrier film 30 is the film that carrier film main body 32 has self adhesion, it is convenient to omit adhesive phase 34.

In the case where release film 40 only has sufficient release by release film main body 42, it is convenient to omit parting agent layer 44。

The Third Way of the utility model is the printed circuit board with electromagnetic shielding film, includes printed circuit board, Printed circuit is equipped in at least single side of substrate；Insulating film, one equipped with the printed circuit with the printed circuit board The surface contiguous of side；And the electromagnetic shielding film of the mode, so that the adhesive layer and insulating film adjoining Mode is arranged.

Fig. 4 is the cross-sectional view for indicating an embodiment of the printed circuit board with electromagnetic shielding film for the method.

Printed circuit board 2 with electromagnetic shielding film has flexible printed circuit board 50, insulating film 60 and the first implementation The electromagnetic shielding film 1 of mode.

Flexible printed circuit board 50 is equipped with printed circuit 54 in at least single side of basement membrane 52.

Insulating film 60 is arranged on the surface equipped with 54 side of printed circuit of flexible printed circuit board 50.

The anisotropic conductive adhesive layer 24 of electromagnetic shielding film 1 is adhered to the surface of insulating film 60, and solidifies.Separately Outside, anisotropic conductive adhesive layer 24 is electrically connected via being formed by through-hole (not shown) on insulating film 60 with printed circuit 54 It connects.

In the printed circuit board 2 with electromagnetic shielding film, release film is by from anisotropic conductive adhesive layer 24 Removing.

When being not necessarily to carrier film 30 in the printed circuit board 2 with electromagnetic shielding film, carrier film 30 is by from insulating resin Layer 10 is removed.

Near the printed circuit 54 (signal circuit, earthed circuit, ground plane etc.) in addition to the part with through-hole, electricity The metal film layer 22 of magnetic wave screened film 1 separates via insulating film 60 and anisotropic conductive adhesive layer 24 and matches relatively It sets.

The spacing distance of printed circuit 54 and metal film layer 22 in addition to the part with through-hole and insulating film 60 The summation of the thickness of thickness and anisotropic conductive adhesive layer 24 is roughly equal.Spacing distance be preferably 30 μm or more and 200 μm hereinafter, more preferably 60 μm or more and 200 μm or less.If spacing distance, less than 30 μm, the impedance of signal circuit is dropped It is low, therefore, in order to have the characteristic impedances such as 100 Ω, it is necessary to reduce the line width of signal circuit, the unevenness of line width becomes characteristic impedance Unevenness, reflection resonance noise caused by impedance mismatch is easy to be mixed into electric signal.If spacing distance is greater than 200 μm, have The printed circuit board 2 of electromagnetic shielding film thickens, flexible insufficient.

(flexible printed circuit board)

In flexible printed circuit board 50, the copper foil of copper-clad laminated board is processed as required pattern using well known etching method And form printed circuit 54.

It as copper-clad laminated board, can enumerate: be pasted with via adhesive layer (not shown) in the single or double of basement membrane 52 The plate of copper foil；On the surface of copper foil, curtain coating is used to form plate made of resin solution of basement membrane 52 etc. etc..

As the material of adhesive layer, can enumerate: epoxy resin, polyester, polyimides, polyamidoimide, polyamide, Phenolic resin, polyurethane resin, acrylic resin, melamine resin etc..

The thickness of adhesive layer is preferably 0.5 μm or more and 30 μm or less.

[basement membrane]

As basement membrane 52, preferably with the film of heat resistance, more preferable polyimide film, liquid crystalline polymer film are further excellent Select polyimide film.

From the aspect of electrical insulating property, the sheet resistance of basement membrane 52 is preferably 1 × 10⁶Ω or more.From the aspect of practical, The sheet resistance of basement membrane 52 is preferably 1 × 10¹⁹Ω or less.

The thickness of basement membrane 52 is preferably 5 μm or more and 200 μm hereinafter, from the aspect of bendability, preferably 6 μm or more and 50 μm hereinafter, more preferably 10 μm or more and 25 μm or less.

[printed circuit]

As the copper foil for constituting printed circuit 54, can enumerate: rolled copper foil, electrolytic copper foil etc., from the aspect of bendability, It is preferred that rolled copper foil.Printed circuit 54 may be used as such as signal circuit, earthed circuit, ground plane.

The thickness of copper foil is preferably 1 μm or more and 50 μm hereinafter, more preferably 18 μm or more and 35 μm or less.

The end (terminal) of the length direction of printed circuit 54 is not covered by insulating film 60 or electromagnetic shielding film 1 but is revealed Out, to realize solder connection, connector connection, component mounting etc..

(insulating film)

Insulating film 60 (cover film) is by coating adhesive, stickup bonding agent sheet material etc. insulating film main body (not shown) Single side formed adhesive layer (not shown) obtained from.

From the aspect of electrical insulating property, the sheet resistance of insulating film main body preferably 1 × 10⁶Ω or more.It is examined in terms of practical Consider, the sheet resistance of insulating film main body preferably 1 × 10¹⁹Ω or less.

As insulating film main body, preferably with the film of heat resistance, more preferable polyimide film, liquid crystalline polymer film, into one Walk preferred polyimide film.

Preferably 1 μm or more of the thickness of insulating film main body and 100 μm hereinafter, from the aspect of flexibility, more preferable 3 μm or more and 25 μm or less.

As the material of adhesive layer, can enumerate: epoxy resin, polyester, polyimides, polyamidoimide, polyamide, Phenolic resin, polyurethane resin, acrylic resin, melamine resin, polystyrene, polyolefin etc..Epoxy resin can also be with Comprising for assigning flexible rubber constituent (carboxy-modified nitrile rubber etc.).

The thickness of adhesive layer is preferably 1 μm or more and 100 μm hereinafter, more preferably 1.5 μm or more and 60 μm or less.

The shape for being formed in the opening portion of the through-hole of insulating film 60 is not particularly limited.The shape of opening portion as through-hole Shape, for example, can enumerate: circle, ellipse, quadrangle etc..

The manufacturing method of the printed circuit board with electromagnetic shielding film of the fourth way of the utility model is with electricity The manufacturing method of the printed circuit board of magnetic wave screened film, with following processes: being pressed together on at least single of substrate via insulating film Face is equipped with the printed circuit board of printed circuit and the electromagnetic shielding film of the mode, when pressing, is tightly attached to the insulating film On the face of the side equipped with the printed circuit of the printed circuit board, meanwhile, it is tightly attached to the institute of the electromagnetic shielding film It states in conductive adhesive layer.

The printed circuit board 2 with electromagnetic shielding film of the embodiment for example can be by with following processes (a)~(d) method manufactures (referring to Fig. 5).

Process (a): on the surface of the side equipped with printed circuit 54 of flexible printed circuit board 50 setting with printing It is formed with the insulating film 60 of through-hole 62 at the corresponding position of circuit 54, obtains the printed circuit board 3 with insulating film.

Process (b): it after process (a), is in contact with anisotropic conductive adhesive layer 24 with the surface of insulating film 60 Mode, make with insulating film printed circuit board 3 and removing release film 40 after electromagnetic shielding film 1 be overlapped and press.

Process (c): after process (b), when not needing carrier film 30, carrier film 30 is removed.

Process (d): as needed, between process (a) and process (b) or after process (c), make anisotropic conductive 24 formal solidification of adhesive layer.

In the following, each process is described in detail with reference to Fig. 5.

(process (a))

Process (a) is that insulating film 60 is laminated on flexible printed circuit board 50 to obtain the printed circuit for having insulating film The process of plate 3.

Specifically, firstly, overlapping shape at position corresponding with printed circuit 54 on flexible printed circuit board 50 At the insulating film 60 for having through-hole 62.Then, the adhesive layer (nothing of insulating film 60 is bonded on the surface of flexible printed circuit board 50 Diagram) and solidify adhesive layer, thus to obtain the printed circuit board 3 for having insulating film.It can also be in flexible printed circuit board The adhesive layer of temporary bond insulating film 60 on 50 surface carries out formal solidification to adhesive layer in process (d).

The bonding of adhesive layer and solidification are carried out using such as press machine (not shown) etc. by hot pressing.

(process (b))

Process (b) is the process that electromagnetic shielding film 1 is pressed on the printed circuit board 3 with insulating film.

Specifically, the electromagnetic shielding film on the printed circuit board 3 with insulating film after overlapping removing release film 40 1, and pass through the pressing such as hot pressing.Anisotropic conductive adhesive layer 24 is bonded on the surface of insulating film 60 as a result, simultaneously will Anisotropic conductive adhesive layer 24 is pressed into through-hole 62, is filled inside through-hole 62, is electrically connected with printed circuit 54.As a result, Obtain the printed circuit board 2 for having electromagnetic shielding film.

The bonding of anisotropic conductive adhesive layer 24 and solidification, which are used, passes through hot pressing such as press machine (not shown) Come carry out.

Hot pressing time is preferably 20 seconds or more and 60 points hereinafter, more preferably 30 seconds or more and 30 points or less.If when hot pressing Between be the range lower limit value more than, then can easily on the surface of insulating film 60 be bonded anisotropic conductive bonding Oxidant layer 24.If hot pressing time be the range upper limit value hereinafter, if can shorten the printed circuit with electromagnetic shielding film The manufacturing time of plate 2.

Hot pressing temperature (temperature of the hot plate of press machine) is preferably 140 DEG C or more and 190 DEG C hereinafter, more preferably 150 DEG C Above and 175 DEG C or less.If the temperature of hot pressing is the lower limit value of the range or more, can be easily in the table of insulating film 60 Anisotropic conductive adhesive layer 24 is bonded on face.Furthermore it is possible to shorten hot pressing time.If hot pressing temperature is the range Upper limit value is hereinafter, can then easily suppress the deterioration etc. of electromagnetic shielding film 1, flexible printed circuit board 50 etc..

Hot pressing pressure is preferably 0.5MPa or more and 20MPa hereinafter, more preferably 1MPa or more and 16MPa or less.If hot Pressure pressure is the lower limit value of the range or more, then can be bonded anisotropic conductive adhesive on the surface of insulating film 60 Layer 24.Furthermore it is possible to shorten hot pressing time.If hot pressing pressure be the range upper limit value hereinafter, if can inhibit electromagnetic wave The breakage etc. of screened film 1, flexible printed circuit board 50 etc..

(process (c))

Process (c) is the process for removing carrier film 30.

Specifically, removing carrier film 30 from insulating resin layer 10 when not needing carrier film.

(process (d))

Process (d) is to make the process of 24 formal solidification of anisotropic conductive adhesive layer.

In the case that hot pressing time in process (b) is 20 seconds or more and 10 points of short periods below, preferably in work The formal solidification of anisotropic conductive adhesive layer 24 is carried out between sequence (b) and process (c) or after process (c).

The formal solidification of anisotropic conductive adhesive layer 24 is carried out using heating devices such as such as ovens.

Heating time is preferably 15 points or more and 120 points hereinafter, more preferably 30 points or more and 60 points or less.If when heating Between be the range lower limit value more than, then can make anisotropic conductive adhesive layer 24 sufficiently solidify.If heating time For the range upper limit value hereinafter, can then shorten the manufacturing time of the printed circuit board 2 with electromagnetic shielding film.

Heating temperature (atmosphere temperature in oven) be preferably 120 DEG C or more and 180 DEG C hereinafter, more preferably 120 DEG C with It is upper and 150 DEG C or less.If heating temperature is the lower limit value of the range or more, heating time can be shortened.If heating temperature For the range upper limit value hereinafter, can then inhibit the deterioration etc. of electromagnetic shielding film 1, flexible printed circuit board 50 etc..

(function and effect)

The printed circuit board 2 with electromagnetic shielding film of the method uses above-mentioned electromagnetic shielding film 1, therefore, insulation Resin layer 10 and the bonding force for wrapping metalliferous conductive layer 20 are very high.Accordingly it is possible to prevent insulating resin layer 10 and conductive layer Splitting between 20.

In addition, the electromagnetic wave that the printed circuit board 2 with electromagnetic shielding film of the method is low using above-mentioned dielectric constant Screened film 1, therefore the signal velocity in the circuit formed on flexible printed circuit board 50 is fast.

(other embodiment)

The printed circuit board with electromagnetic shielding film of the method is not limited to above embodiment.

For example, flexible printed circuit board 50 overleaf can have ground plane in side.In addition, flexible printed circuit board 50 can be with There is printed circuit 54 two-sided, and post insulating film 60 and electromagnetic shielding film 1 in double-sided adhesive.

Also the rigid printed base plate of no flexibility can be used to replace flexible printed circuit board 50.

Also the electromagnetic shielding film 1 of second embodiment or the electromagnetic shielding film 1 of third embodiment can be used Instead of the electromagnetic shielding film 1 of first embodiment.

[embodiment]

(Production Example 1)

Use dehumidifying air drier (manufacture of Matsui manufacturing company, ProductName: Multijet for being heated to 160 DEG C MJ3), by polyether-ether-ketone (manufacture of Solvay Specialty Polymers company, ProductName: KetaSpire PEEK Grade:KT-851NL SP) it is 12 hours dry.Make the moisture content 300ppm or less of polyether-ether-ketone as a result,.The moisture content is Using micro-water analyzer (Mitsubishi Chemical Ind's manufacture, CA-100 type), the value measured by Carl Fischer titration method.

Then, the pellet after drying is packed into single screw rod extrusion shaper (the screw rod class for having the T die head of width 400mm Type: full flight screw, screw diameter: compression ratio: 40mm, L/D:32 make its melting in 2.5).At this point, with 18L/ points of flow Nitrogen is provided to the pellet loading port of single screw rod extrusion shaper, nitrogen atmosphere is made.In addition, as single screw rod extrusion shaper Barrel temperature while making 380 DEG C of feeding port side, makes 400 DEG C of die end, die head temperature is 400 DEG C.In addition, will be used for The temperature of the connecting tube of connection single screw rod extrusion shaper and T die head is adjusted to 400 DEG C.

From T die head continuously squeeze out in the extrusion shaper melt after fusant, and extrusion molding be it is band-like, obtain The film of molten.The temperature for measuring the fusant being just discharged from T die head exit is 397 DEG C.

The film for having concave-convex 130 DEG C of metallic rolls clamping molten using the press bonding roller and circumferential surface of silicon rubber keeps its cold But, obtain polyether-ether-ketone film (hereinafter, referred to as " PEEK film ").At this point, measuring the circumferential surface of press bonding roller using contactless thermometer Temperature is 131 DEG C.

Then, the both ends of the width direction of the PEEK film obtained using cutting blade severing, are made width 300mm, made It is wound with 3 inches of diameter (7.62mm) of rolling tubes.

Pass through thickness, specific gravity, relative crystallinity and the Tg of the PEEK film that aftermentioned method measures.As a result shown in table 1.

In addition, measuring the storage modulus of the PEEK film of Production Example 1 by aftermentioned method, as a result, at (Tg-10) DEG C or more and Or less (Tg+50) DEG C within the temperature range of (by the measurement result of Tg it is found that being 145 DEG C or more and 176 DEG C or less), storage modulus With down to 2 × 10⁸Minimum below.

[table 1]

Then, it is cut with the size of 20cm in 20cm on the extrusion direction in extrusion molding, width direction PEEK film.After the PEEK film that this is cut is enclosed in metal pressure vessel, liquefaction dioxy is imported into the pressure vessel Change carbon, stands 24 hours under the conditions of 40 DEG C and 8.4MPa (gauge pressure) of supercriticality, make to be impregnated with carbon dioxide in PEEK film. When flowing into liquefied carbon dioxide in pressure vessel, importing and the operation of discharge carbon dioxide are repeated three times, then, importing is used for Containing the carbon dioxide being immersed in PEEK film, stand under the described conditions.

Make to be impregnated with after carbon dioxide in PEEK film as described above, with the pressure of 2MPa/ seconds speed release pressure vessels Power is returned to atmospheric pressure, the PEEK film (hereinafter referred to as " CO after taking out impregnation carbon dioxide in pressure vessel₂It is impregnated with PEEK Film ").Then, rapidly by CO₂Impregnation PEEK film is put into the mold for being heated to 190 DEG C.As mold, using being formed with length 30cm, wide 30cm, thick 50 μm of space mold.In the mold, the space of thickness direction uses 50 μm of thickness of brass pad Piece is formed.

By CO₂Impregnation PEEK sheet material heats 1 minute in mold, thus obtains foaming PEEK film.

Specific gravity, expansion ratio, mean air bubble diameter, the gas of obtained foaming PEEK film are measured or evaluated by aftermentioned method Steep density, relative crystallinity, relative dielectric constant, thermal coefficient and solder heat resistance.As a result shown in table 1.

[thickness]

It uses micrometer (manufacture of Mitutoyo company, ProductName: Coolant Proof Micrometer, MDC-25PJ) It is measured.When measurement, measure at any 5 in PEEK film width direction, its average value is (single as the thickness of PEEK film Position: μm).

[specific gravity and expansion ratio]

According to the A method of JIS K7112 defined, specific gravity (no unit) is measured under conditions of 23 DEG C of temperature.

When the ratio of PEEK film before foaming is reset to ρ₀, foaming PEEK film ratio be reset to ρ_fWhen, expansion ratio (unit: Times) by formula ρ₀/ρ_fIt acquires.

[relative crystallinity]

The measuring method of following relative crystallinities be suitable for foam before PEEK film, foam both PEEK films.

Use differential scanning calorimeter (manufacture of SII nanosecond science and technology company, ProductName: EXSTAR7000 series of X- DSC7000), the test film obtained from film is heated with 10 DEG C/minute of heating rate.The heat of crystalline melting peak is measured as a result, ΔH_m(unit: J/g) and the heat Δ H for recrystallizing peak_c(unit: J/g).

The Δ H that will be measured_c、ΔH_mFollowing formula is substituted into, relative crystallinity (unit: %) is acquired.

Relative crystallinity={ 1- (Δ H_c/ΔH_m)}×100

[Tg]

When measuring dynamic viscoelastic while changing temperature, the temperature when value of loss modulus is reached very big as Tg (unit: DEG C).

Specifically, to squeeze out 60mm on direction, the 6mm on the direction vertical with direction is squeezed out in extrusion molding Size cuts the film for measuring Tg, prepares test film.Using viscoelastic spectrometer (TA Instruments Japan company manufacture, ProductName: RSA-G2), by stretch mode, in frequency 1Hz, strain 0.1%, 3 DEG C/min of heating rate, measuring temperature model Enclose under conditions of distance 21mm, measured between -60 DEG C or more and 360 DEG C or less, fixture the test film loss modulus (unit: Pa)。

[storage modulus]

The Measurement of Dynamic Viscoelasticity carried out when by seeking the Tg, measured simultaneously with loss modulus storage modulus (unit: Pa)。

[mean air bubble diameter]

Using scanning electron microscope (Japan Electronics Corporation's manufacture, ProductName: 5300LV), shooting foaming PEEK film is cutd open Face uses the general image processing packet (manufacture of three paddy Itochus, ProductName: WinROOF) for Windows (registered trademark) Carry out image procossing.Using treated image, the diameter of 100 bubbles is measured, their average value is acquired, by the average value As mean air bubble diameter D (unit: μm).It should be noted that the diameter of bubble is the maximum long axis of bubble.

[bubble density]

Bubble density (unit: a/cm³) pass through the specific gravity ρ₀、ρ_fIt is asked with the mean air bubble diameter D and following formula ?.

Bubble density=6 { (ρ₀/ρ_f)-1}/(πD³)

[relative dielectric constant]

Using RF impedance material analyzer (manufacture of Hewlett-Packard company, ProductName: HP4291A), in frequency The relative dielectric constant (no unit) of measurement foaming PEEK film under conditions of 1GHz.

[thermal coefficient]

Use rapid thermal coefficient meter (manufacture of capital of a country Electronics Industry Company, ProductName: QTM-500), measurement foaming PEEK The heat transfer of film acquires thermal coefficient (unit: W/mK) by being compared with standard substance.As standard substance, hair is used Steep polyethylene (thermal coefficient: 0.0357W/mK), silicon rubber (thermal coefficient: 0.238W/mK) and quartz glass (thermal coefficient: 1.409W/mK) these three.Thermal coefficient is smaller, and thermal conductivity is lower.

[solder heat resistance]

Foaming PEEK film is impregnated 10 seconds in 260 DEG C of solder bath, visual observations deformation extent is commented according to following standards Valence solder heat resistance.

A: without deformation

B: there is deformation

(Production Example 2)

After obtaining PEEK film identically as Production Example 1, with 20cm, width direction on the extrusion direction in extrusion molding The size of upper 20cm cuts the PEEK film.After the PEEK film that this is cut is enclosed in metal pressure vessel, to the pressure resistance Liquefied carbon dioxide is imported in container, is stood 24 hours under conditions of 40 DEG C and 8.1MPa (gauge pressure) of supercriticality, is made PEEK film is impregnated with carbon dioxide.When liquefied carbon dioxide is imported in pressure vessel, the behaviour for importing and being discharged carbon dioxide is repeated Make three times, to be then introduced into the carbon dioxide for being impregnated with PEEK film, stand under the described conditions.

It is impregnated with PEEK film after carbon dioxide, with the pressure of 2MPa/ seconds speed release pressure vessels Power is returned to atmospheric pressure, takes out from pressure vessel containing the CO for being soaked with carbon dioxide₂It is impregnated with PEEK film.Then, rapidly by CO₂Contain Leaching PEEK film is put into the oil bath for being heated to 70 DEG C, is heated 1 minute, and foaming PEEK film is thus obtained.

The expansion ratio of obtained foaming PEEK film is 1.04 times, relative dielectric constant 3.0.

(embodiment 1)

Prepare carrier film, which is to be equipped on the single side of PET film (carrier film main body) including acrylic adhesive Made of the adhesive phase of agent.It include foaming PEEK sheet material obtained in Production Example 1 in the adhesive layer surface fitting of carrier film Insulating resin layer.

Then, by electron-beam vapor deposition method, the object on the face with carrier film opposite side of the insulating resin layer Physical vapor deposition copper is formed metal film layer (copper vapor-deposited film, 0.07 μm of thickness, 0.3 Ω of sheet resistance).

Make include epoxy resin Thermocurable bonding agent (DIC company manufacture, EXA-4816) 100 mass parts, curing agent (Ajinomoto Fine-Techno Co., Inc. manufacture, PN-23) 20 mass parts mixing, obtains potential curable epoxy resin Composition.

Make the potential curable epoxy resin composition and the conductive particle (7.5 μm of average grain diameter) including copper particle 40 mass parts are dissolved or dispersed in 200 mass parts of solvent including methyl ethyl ketone, obtain conductive adhesive coating.

Then, using molding coating machine, the conductive adhesive coating is coated on the metal film layer with it is exhausted On the face of edge resin layer opposite side, and solvent flashing carries out B-staged, and it is (thick to form anisotropic conductive adhesive layer as a result, Spend 7 μm, 4.5 volume % of copper particle).

Prepare release film (manufacture of lintec company, T157), which set on the single side of PET film (50 μm of thickness) Have made of the parting agent layer (0.1 μm of thickness) including non-organic silicon class mould release.

In such a way that the parting agent layer is contacted with the anisotropic conductive adhesive layer, led in the anisotropy The release film is pasted on the face with metal film layer opposite side of electrical adhesive layer, obtains the electromagnetism wave screen of embodiment 1 Cover film.

(comparative example 1)

As the coating for being used to form insulating resin layer, by bisphenol A type epoxy resin (manufacture of DIC company, epichlone 840-S) 100 mass parts, curing agent (Mitsubishi Chemical Ind's manufacture, JERCure113) 20 mass parts, 2-ethyl-4-methylimidazole 2 mass parts and 2 mass parts of carbon black are dissolved in 200 mass parts of methyl ethyl ketone, prepare coating.

The coating for being used to form insulating resin layer is coated on carrier identical with carrier film used in embodiment 1 It in the adhesive layer surface of film, heats 2 minutes and makes it dry at 60 DEG C, and semi-solid preparation, form 5 μm of thickness of insulating resin layer. 1/m is observed on the insulating resin layer²Above and 3/m²Pin hole below.In addition, measuring the opposite of the insulating resin layer Dielectric constant is 3.5.

The region of not pin hole is selected, and passes through insulating resin layer of the electron-beam vapor deposition method in selected region Surface on physical vapour deposition (PVD) copper, formed metal film layer (copper vapor-deposited film, 0.07 μm of thickness, 0.3 Ω of sheet resistance).

Same as Example 1ly, anisotropy is formed on the face with insulating resin layer opposite side of metal film layer Conductive adhesive layer, and release film is pasted on anisotropic conductive adhesive layer, obtain the electromagnetic wave shielding of comparative example 1 Film.

[evaluation]

By following methods, the insulating resin layer of the electromagnetic shielding film of each example and the cementability of metal film layer are evaluated.

Electromagnetic shielding film on 25 μm of thickness of polyimide film after overlapping removing release film, uses hot-press arrangement (manufacture of Zhe Yuan manufacturing company, G-12), hot pressing 120 seconds at 180 DEG C of hot plate temperature, load 2MPa.Then, carrier is removed Film.It is temporarily bonded anisotropic conductive adhesive layer on the surface of insulating film as a result, is obtained poly- with electromagnetic shielding film Acid imide.

Using high temperature slot (Nanben Chemical Company manufacture, HT210), at 160 DEG C of temperature, heating is described to have electromagnetism wave screen It covers the polyimide film of film 1 hour, makes anisotropic conductive adhesive layer formal solidification.

Then, via bonding sheet (dexerials company manufacture, D3410), in the insulating resin layer of electromagnetic shielding film 25 μm of hot pressing thickness of polyimides stiffening plate, is made the test film for tension test on surface.

The fixture that cupping machine is installed on the polyimide film of the test film and polyimides stiffening plate, according to JIS Z0237 carries out disbonded test under conditions of 180 ° of peeling directions, tensile speed 50mm/ points.

[result]

In the test film using the electromagnetic shielding film of embodiment 1, when peel strength is 9.1N/cm, bonding sheet is produced Wood destruction is given birth to, the bonding of insulating resin layer and metal film layer is maintained.

In the test film using the electromagnetic shielding film of comparative example 1, when peel strength is 3.5N/cm, insulating resin Splitting is produced between layer and metal film layer.

As knowen from these results, compared with the insulating resin layer including thermosetting resin used in the past, as aromatic series The insulating resin layer of polyether-ketone foaming layer and the bonding force of metal film layer are stronger.

Insulating resin layer in embodiment 1 includes the foaming PEEK film of Production Example 1, relative dielectric constant 2.5.This is opposite Dielectric constant is smaller than the relative dielectric constant 3.5 of the insulating resin layer in the comparative example 1 of the solidfied material including epoxy resin, separately Outside, the relative dielectric constant 3.0 of the PEEK film of the Production Example 2 more unexpanded than almost is also smaller.It follows that including fragrant adoption The relative dielectric constant of insulating resin layer in the embodiment 1 of ether ketone foaming layer is lower.

The insulating resin layer that the electromagnetic shielding film of embodiment 1 has relative dielectric constant low, electromagnetic shielding film are whole Relative dielectric constant be also lower, therefore speculate, the signal of the printed circuit board of the electromagnetic shielding film equipped with embodiment 1 is propagated Fast speed.

As shown in table 1, compared with the foaming PEEK film of almost unexpanded Production Example 2, the foaming PEEK film of Production Example 1 Thermal coefficient is low.Thus speculate, in reality of the foaming PEEK film for using Production Example 1 as the insulating resin layer of electromagnetic shielding film In the printed circuit board for applying example 1, outside heat is not easy conduction to printed circuit intralamellar part, or, internal heat is not easy conduction to print Outside printed circuit board.

In addition show that solder heat resistance improves by constituting insulating resin layer with aromatic polyether ketone.Therefore it can push away It surveys, the heat resistance of the electromagnetic shielding film of the embodiment 1 with the insulating resin layer containing aromatic polyether ketone is higher.

Symbol description

1 electromagnetic shielding film

2 have the printed circuit board of electromagnetic shielding film

3 have the printed circuit board of insulating film

10 insulating resin layers

22 metal film layers

20 conductive layers

24 anisotropic conductive adhesive layers

24a Thermocurable bonding agent

24b conductive particle

26 isotropic conductivity adhesive layers

26a Thermocurable bonding agent

26b conductive particle

30 carrier films

32 carrier film main bodys

34 adhesive phases

40 release films

42 release film main bodys

44 parting agent layers

50 flexible printed circuit boards

52 basement membranes

54 printed circuits

60 insulating films

62 through-holes

Claims

1. a kind of electromagnetic shielding film, the conductive layer with insulating resin layer and with insulating resin layer adjoining,

2. electromagnetic shielding film according to claim 1, which is characterized in that

3. electromagnetic shielding film according to claim 1, which is characterized in that

The sheet resistance of the insulating resin layer is 1 × 10⁶Ω or more and 1 × 10¹⁹Ω or less.

4. electromagnetic shielding film according to claim 1, which is characterized in that the insulating resin layer is to contain fragrant adoption The foaming layer of ether ketone, the conductive layer at least have the metalliferous conductive adhesive layer of packet.

5. electromagnetic shielding film according to claim 4, wherein the aromatic polyether ketone is polyether-ether-ketone and polyether-ketone At least one party in ketone.

6. electromagnetic shielding film according to claim 1, which is characterized in that

The conductive adhesive layer is anisotropic conductive adhesive layer, includes Thermocurable bonding agent and electric conductivity Grain,

Ratio of the conductive particle in the anisotropic conductive adhesive layer are as follows: in the anisotropic conductive In 100 volume % of adhesive layer, account for 1 volume % or more and 30 volume % hereinafter,

7. electromagnetic shielding film according to claim 1, which is characterized in that

Ratio of the conductive particle in the anisotropic conductive adhesive layer are as follows: in the anisotropic conductive In 100 volume % of adhesive layer, account for 2 volume % or more and 15 volume % hereinafter,

8. electromagnetic shielding film according to claim 1, which is characterized in that

The conductive adhesive layer is isotropic conductivity adhesive layer, includes Thermocurable bonding agent and electric conductivity Grain,

Ratio of the conductive particle in the isotropic conductivity adhesive layer are as follows: in the isotropic conductivity In 100 volume % of adhesive layer, account for 50 volume % or more and 80 volume % hereinafter,

9. electromagnetic shielding film according to claim 1, which is characterized in that

Ratio of the conductive particle in the isotropic conductivity adhesive layer are as follows: in the isotropic conductivity In 100 volume % of adhesive layer, account for 60 volume % or more and 70 volume % hereinafter,

10. electromagnetic shielding film according to claim 1, which is characterized in that the conductive layer, which has, is set to the insulation Metal film layer on resin layer side and on the side opposite with the insulating resin layer of the metal film layer Conductive adhesive layer.

11. electromagnetic shielding film according to claim 10, wherein the metal film layer is cvd metal layer.

12. electromagnetic shielding film according to claim 11, wherein the cvd metal layer is silver-colored vapor deposition layer Or copper vapor deposition layer.

13. electromagnetic shielding film according to claim 10, which is characterized in that

The metal film layer with a thickness of 0.01 μm or more and 5 μm or less.

14. electromagnetic shielding film according to claim 10, which is characterized in that

The metal film layer with a thickness of 0.05 μm or more and 3 μm or less.

15. electromagnetic shielding film according to claim 10, which is characterized in that

The conductive layer further has blackening layer on the face of the insulating resin layer side of the metal film layer.

16. electromagnetic shielding film according to claim 15, which is characterized in that

The blackening layer with a thickness of 5nm or more and 20 μm hereinafter,

17. electromagnetic shielding film according to claim 15, which is characterized in that

The blackening layer with a thickness of 10nm or more and 1 μm hereinafter,

18. electromagnetic shielding film according to claim 1, which is characterized in that in being led with described for the insulating resin layer Further there is carrier film on the face of electric layer opposite side.

19. electromagnetic shielding film according to claim 18, which is characterized in that

The carrier film has carrier film main body and on the surface of the insulating resin layer side of the carrier film main body Adhesive phase,

The carrier film with a thickness of 25 μm or more and 125 μm or less.

20. electromagnetic shielding film according to claim 18, which is characterized in that

The carrier film with a thickness of 38 μm or more and 105 μm or less.

21. a kind of printed circuit board with electromagnetic shielding film, includes

Printed circuit board, wherein printed circuit is equipped on at least single side of substrate；

Electromagnetic shielding film described according to claim 1~any one of 20, so that the conductive adhesive layer and institute The adjacent mode of insulating film is stated to be arranged.