CN102131345B - Metalized polyimide film and flexible circuit board with the same - Google Patents
Metalized polyimide film and flexible circuit board with the same Download PDFInfo
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- CN102131345B CN102131345B CN201010141682.XA CN201010141682A CN102131345B CN 102131345 B CN102131345 B CN 102131345B CN 201010141682 A CN201010141682 A CN 201010141682A CN 102131345 B CN102131345 B CN 102131345B
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B15/00—Layered products comprising a layer of metal
- B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
- B32B15/08—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B15/00—Layered products comprising a layer of metal
- B32B15/20—Layered products comprising a layer of metal comprising aluminium or copper
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/28—Layered products comprising a layer of synthetic resin comprising synthetic resins not wholly covered by any one of the sub-groups B32B27/30 - B32B27/42
- B32B27/281—Layered products comprising a layer of synthetic resin comprising synthetic resins not wholly covered by any one of the sub-groups B32B27/30 - B32B27/42 comprising polyimides
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- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K1/00—Printed circuits
- H05K1/02—Details
- H05K1/03—Use of materials for the substrate
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2311/00—Metals, their alloys or their compounds
- B32B2311/12—Copper
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2311/00—Metals, their alloys or their compounds
- B32B2311/22—Nickel or cobalt
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2379/00—Other polymers having nitrogen, with or without oxygen or carbon only, in the main chain
- B32B2379/08—Polyimides
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2457/00—Electrical equipment
- B32B2457/08—PCBs, i.e. printed circuit boards
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- Engineering & Computer Science (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Laminated Bodies (AREA)
Abstract
The present invention provides a metalized polyimide film which can be used for obtaining a flexible circuit board with an extensibility that is reduced for 50% compared with that of the prior-art flexible circuit board in an OLB (outer lead bonding) step, and a flexible circuit board with the film. The invention is provided according to the metalized polyimide film, etc. The invention is characterized in that: the metalized polyimide film is formed through directly setting a metal film on the polyimide film through a plating method. When the thickness of the polyimide film is 35-40 mu m, the water absorption is 1wt%-3wt%. Furthermore a thermal expansion coefficient in a TD direction (width direction) is 3-8ppm/DEG C, and the thermal expansion coefficient in a MD direction (length direction) is 9-15ppm/DEG C.
Description
Technical field
The present invention relates to metallized polyimide film and use its flexible PCB, in more detail, the present invention relates to following metallized polyimide film and use its flexible PCB, elongation when this metallized polyimide film can obtain OLB (lead wire bonding) operation reduces by 50% flexible PCB than existing product.
Background technology
The substrate that forms electronic circuit and these electronic units are installed comprise " the lead wire circuit plate " of hardboard shape and film-form and have flexibility, can free bend " flexible PCB " (following, sometimes also referred to as FPC).Wherein, FPC is owing to applying flexibly its flexibility, can require like that at the hinge portion of circuit board, hard disk drive (HDD), Digital video disc (DVD) module, mobile phone for lcd driver (driver) to use in the part of bendability, so its demand is increasing gradually.
, this flexible PCB is used and on the surface of polyimide film, is provided with the base material of metal level, by relief method or semi-additive process, this metal level is processed, thereby is obtained circuit.To obtain the situation of flexible PCB by relief method, describe in passing, first, on the layer on surface of metal of base material, resist layer is set, on this resist layer, places the mask with specified circuit pattern, by irradiation ultraviolet radiation on it, expose, develop, obtain the etching mask for etch metal layers, then, the metal part exposing is removed in etching, then remove residual resist layer, washing if needed, is carried out specific plating in the conductor terminal part of circuit etc.
In the situation that obtaining by semi-additive process, 1 dose of layer against corrosion is set in the metal surface of base material, on this resist layer, place the mask with specified circuit pattern, by irradiation ultraviolet radiation on it, exposed, develop, obtain for the plating mask in layer on surface of metal electro-coppering, the metal level that opening portion is exposed is electroplated as negative electrode, form circuit part, then remove resist layer, carry out soft etching, remove the metal level of circuit part above-mentioned substrate surface in addition, thereby completing circuit part, washing, if needed, in the conductor terminal part of circuit etc., carry out specific plating.
Now, that liquid crystal display (following, sometimes also referred to as LCD), mobile phone, digital camera and various electrical equipment all require is frivolous, small-sized, lightweight quantizes, cost degradation, and the electronic unit of installing therein is also carrying out the trend of miniaturization certainly.As a result, requiring the circuit spacing of the flexible PCB of use is below 25 μ m.
In order to meet this requirement, need to obtain the flexible PCB that circuit spacing is 25 μ m, in the situation that obtaining circuit by relief method, the impact producing is carved in lateral erosion owing to not having circuit to manufacture, therefore in order to obtain the circuit that cross section rectangular shape is good, the thickness of the above-mentioned metal level arranging on base material is necessary for below 20 μ m.In addition,, when obtaining circuit by semi-additive process, the thickness of above-mentioned metal level is necessary for several μ m.
Method as obtaining this base material, is recommended on insulative resin film surface, by dry plating, obtains metallic film, obtains copper film thereon by dry plating, by wet method plating, copper film is set thereon, thereby obtains the method for metal level.This is because this base material obtains whole formation films by plating method, therefore can control arbitrarily the thickness of metal level.
In addition,, in circuit fine pitch, also require to improve the tack of metal level and insulating properties film.This is owing to semiconductor element being installed in flexible PCB, and the electrode of semiconductor component surfaces and circuit inside conductor partly carry out Bonding, but in order to shorten production time per piece now, need at high temperature exert pressure and carry out Bonding.
Therefore in LCD, due to the fine pitch of circuit, during OLB (lead wire bonding) operation in being connected of the glass substrate of LCD and COF (covering brilliant film), need to use ACF (anisotropic conducting film) bonding.ACF is the film of pick-up metal particulate in thermosetting resin, in carrying out the position of OLB, glass substrate by LCD and COF seize on both sides by the arms and heat and pressurize, thus, the overlapping contact of metal particle in ACF, only on compression aspect, can guarantee conductivity, on the other hand, between the circuit between the circuit on glass substrate and on COF, can guarantee the insulating properties of AFC.
When this OLB (lead wire bonding) operation, AFC heats in the scope of 150 ℃～200 ℃, under the pressure more than 1MPa, pressurizes.Therefore,, under this condition, if the size of COF changes, cannot guarantee conductivity, the insulating properties of regulation, so the dimensional stability of COF is extremely important.
In addition, the adhesive strength of improving the metal level arranging on polyimide film and this surface is to develop the research topic not stopped since this base material, has carried out a large amount of tests.
Therefore, the applicant has proposed to use and has comprised pyromellitic acid dianhydride (PMDA) and 4,4 '-diaminodiphenyl ether (ODA) is as principal component, or contain by pyromellitic acid dianhydride (PMDA) and 4, the composition that 4 '-diaminodiphenyl ether (ODA) forms and by bibenzene tetracarboxylic dianhydride (BPDA) and 4, the composition that 4 '-diaminodiphenyl ether (ODA) forms is as the polyimide film of principal component, by being carried out to plasma treatment, corona discharge or wet treatment, this polyimide film surface carries out upgrading, thereby on this surface, import hydrophilic functional group, make the thickness of this upgrading layer be
below, pass through sputtering method thereon, adopt the preparation of metals kind layer that is at least selected from nickel, chromium and alloy thereof, the copper layer of thickness 8 μ m is set by plating method thereon, thus the method (referring to the 1st, 2 pages of patent documentations 1) of 2 layers of plating coating copper polyimide substrate of preparation.
Pass through the method, the initial stage adhesive strength of the polyimide surface of gained base material and metal level is at 150 ℃, in atmosphere, place after 168 hours, and the adhesive strength of carrying out under 121 ℃, humidity 95%, 2 atmospheric pressure after the PCT test of 100 hours is more than 400N/m excellent like this value (referring to the 5th page of patent documentation 1).
In addition, excellent in dimensional stability has been proposed, be suitable for fine pitch circuit substrate, especially in thin-film width direction with the polyimide film of the COF (covering brilliant film) of thin space distribution with cover copper laminated body (patent documentation 2) used as base material.Wherein, recorded to be desirably in two amine components and used more than specified quantitative 4,4 '-diaminobenzene formailide, from the viewpoint of dimensional stability, the thermal coefficient of expansion of regulation polyimide film, makes thermal coefficient of expansion consistent with the thermal coefficient of expansion of metal.In using the circuit substrate of metallized polyimide film, not only require dimensional stability, also require adhesive strength.Yet, in patent documentation 2, for adhesive strength, not record, metallized polyimide is not the material that can have both dimensional stability and tack.
[prior art document]
[patent documentation]
[patent documentation 1] TOHKEMY 2007-318177 communique (referring to the 1st, 2,5 pages)
[patent documentation 2] TOHKEMY 2009-67859 communique
Summary of the invention
Problem points in view of above-mentioned prior art, the object of this invention is to provide a kind of can acquisition when carrying out OLB operation (lead wire bonding), elongation reduces the metallized polyimide film of 50% flexible PCB and uses its flexible PCB than existing product.
The inventor is in order to solve above-mentioned problem, carried out various research, found that if used when thickness is 35 μ m～40 μ m, thermal coefficient of expansion is 3ppm/ ℃～8ppm/ ℃ in TD direction (Width), it in MD direction (compared with length direction), is the specific metallization polyimide film of 9ppm/ ℃～15ppm/ ℃, can obtain more than initial stage adhesion strength has 600N/m, when OLB operation, elongation is reduced to 50% circuit substrate of existing product, thereby completes the present invention.
; according to the 1st invention of the present invention; a kind of metallized polyimide film is provided; this metallized polyimide film is by plating method, on the surface of polyimide film, metal film to be directly set to form; it is characterized in that: this polyimide film is when thickness is 35 μ m～40 μ m; water absorption rate is 1 quality %～3 quality %; and; thermal coefficient of expansion is 3ppm/ ℃～8ppm/ ℃ in TD direction (Width), in MD direction (compared with length direction), is 9ppm/ ℃～15ppm/ ℃.
In addition, according to the 2nd invention of the present invention, a kind of metallized polyimide film is provided, it is characterized in that, in above-mentioned the 1st invention, the humidity expansion coefficient of above-mentioned polyimide film is 7ppm/%HR～13ppm/%HR in TD direction (Width), in MD direction (compared with length direction), is 12ppm/%HR～15ppm/%HR.
In addition, according to the 3rd invention of the present invention, a kind of metallized polyimide film is provided, it is characterized in that, in the above-mentioned the 1st or the 2nd invention, above-mentioned polyimide film contains the imide bond being formed by bibenzene tetracarboxylic and diamine compound in polyimide molecule, while measuring (Cu K α incidence angle=0.1 °) its surperficial TD direction (Width) by film X-ray diffraction method, within the scope of each of 2 θ=12 °～18 °, 2 θ=26 °～32 °, 2 θ=42 °～48 °, having halfwidth is 1.5 ° of following peaks.
In addition, according to the 4th invention of the present invention, a kind of metallized polyimide film is provided, it is characterized in that, in above-mentioned the 3rd invention, above-mentioned metal film consists of at least a kind that is selected from nickel, chromium or the nickel alloy underlying metal film forming and the copper layer that is arranged on this underlying metal film.
In addition, according to the 5th invention of the present invention, provide a kind of metallized polyimide film, it is characterized in that, in above-mentioned the 4th invention, above-mentioned copper layer is copper film.
In addition, according to the 6th invention of the present invention, provide a kind of metallized polyimide film, it is characterized in that, in above-mentioned the 4th invention, in above-mentioned copper layer, on the surface of copper film, be also laminated with copper film.
In addition, according to the 7th invention of the present invention, provide a kind of metallized polyimide film, it is characterized in that, in the above-mentioned the 5th or the 6th invention, above-mentioned metallic film and copper film form by dry plating.
In addition, according to the 8th invention of the present invention, provide a kind of metallized polyimide film, it is characterized in that, in the above-mentioned the 6th or the 7th invention, above-mentioned copper film forms by wet method plating.
In addition, according to the 9th invention of the present invention, provide a kind of metallized polyimide film, it is characterized in that, in any one of above-mentioned the 1st～8th invention, the thickness of above-mentioned metal film is below 20 μ m.
In addition, according to the 10th invention of the present invention, a kind of flexible PCB is provided, in this circuit board, on the surface of polyimide film, be provided with the circuit pattern of metal film, it is characterized in that: aforementioned polyimide film contains the imide bond being formed by bibenzene tetracarboxylic and diamine compound in polyimide molecule, while measuring (Cu K α incidence angle=0.1 °) its surperficial TD direction by film X-ray diffraction method, in 2 θ=12 °～18 °, 2 θ=26 °～32 °, within the scope of each of 2 θ=42 °～48 °, having halfwidth is 1.5 ° of following peaks.
In addition, according to the 11st invention of the present invention, a kind of flexible PCB is provided, it is characterized in that, in above-mentioned the 10th invention, above-mentioned metal film consists of at least a kind that is selected from nickel, chromium or the nickel alloy underlying metal film forming and the copper layer that is arranged on this underlying metal film.
In addition, according to the 12nd invention of the present invention, provide a kind of flexible PCB, it is characterized in that, in the above-mentioned the 10th or the 11st invention, the thickness of above-mentioned metal film is below 20 μ m.
In addition, according to the 13rd invention of the present invention, a kind of flexible PCB is provided, it is characterized in that, in above-mentioned the 10th～12nd any one invention, in etching, remove aforementioned metal rete, while exposing the film surface after circuit fabrication, by film X-ray diffraction method, measure the TD direction on (Cu K α incidence angle=0.1 °) polyimide film surface, within the scope of each of 2 θ=12 °～18 °, 2 θ=26 °～32 °, 2 θ=42 °～48 °, having halfwidth is 1.5 ° of following peaks.
In addition, according to the 14th invention of the present invention, provide a kind of flexible PCB, it is characterized in that, the metallized polyimide film that uses the 1st～9th any one invention to record, processes by relief method or semi-additive process.
Metallized polyimide film of the present invention is owing to being 35 μ m～40 μ m at thickness, thermal coefficient of expansion is 3ppm/ ℃～8ppm/ ℃ in TD direction (Width), in MD direction (compared with length direction), be 9ppm/ ℃～15ppm/ ℃, less, therefore can be reduced to below 50% of existing product by the elongation when carrying out OLB (lead wire bonding) operation, having initial stage bonding density is the above such characteristic of 600N/m, can obtain the flexible PCB of the circuit part with fine pitch.Therefore,, by using this metallized polyimide film, even the line bonding operation under the high temperature requiring in current fitting operation also can fully meet the requirements, industrial value of the present invention is very high.
Accompanying drawing explanation
Fig. 1 is the spectrogram of the film X-ray diffraction of the TD direction of the polyimide film of use in the embodiment of the present invention 1.
Fig. 2 is in the present invention (embodiment 1) COF, to there is no covering metal layer, exposes the spectrogram that film X-ray diffraction that polyimides face carries out TD direction obtains.
Fig. 3 means the skeleton diagram of metallized polyimide film structure of the present invention.
Fig. 4 means the skeleton diagram of other structures of metallized polyimide film of the present invention.
Embodiment
Below, use accompanying drawing, metallized polyimide film of the present invention, flexible PCB and their manufacture method are elaborated.
1. metallized polyimide film
Metallized polyimide film of the present invention is that the metallized polyimide film of metal film is directly set on the surface of polyimide film by plating method, above-mentioned polyimide film is characterised in that, when thickness is 35 μ m～40 μ m, water absorption rate is 1 quality %～3 quality %, and, thermal coefficient of expansion is 3ppm/ ℃～8ppm/ ℃ in TD direction (Width), in MD direction (compared with length direction), is 9ppm/ ℃～15ppm/ ℃.
In addition, metallized polyimide film of the present invention is direct on the surface of the following specific polyimide film describing in detail, by adhesive, does not form metal film.Metal film forms by underlying metal film with at the surperficial copper layer arranging of underlying metal film.Copper layer forms by copper film or by copper film and copper film.; metallized polyimide film of the present invention is not use adhesive that the duplexer of metal film is just set on the surface of polyimide film 1, and metal film is underlying metal film 2 and forms the copper film 3 of copper layer and the stepped construction (referring to Fig. 4) of the copper film 3 of the stepped construction (referring to Fig. 3) of copper film 4 or underlying metal film 2 and formation copper layer.
2. polyimide film
The polyimide film using in the present invention is when thickness is 35 μ m～40 μ m, and water absorption rate is 1 quality %～3 quality %.
Surface at polyimide film forms underlying metal film and copper film by dry plating, and then, by wet method plating, especially galvanoplastic form in the situation of specific thickness copper film, form the tensile stress of electrostatic stress form in copper film.This tensile stress is the reason that metal film and polyimide layer are peeled off.
When copper film being set by wet method plating, polyimide film is dipping in plating is bathed.The water absorption of polyimide film is good, if flooded in plating is bathed, can absorb water and expand.In addition, due to after finishing at plating, carry out heat drying, therefore can shrink the state being returned to before plating is processed.Therefore, as long as the speed of expansion causing due to polyimide film water suction is suitable, can complete copper film on the surface of the polyimide film suitably expanding, then pass through heat drying, polyimide film shrinks, can extend copper film, thereby reduce in copper film with the residual tensile stress of internal stress form.
In addition, in the present invention, except the speed of expansion causing due to polyimide film water suction, also must consider water absorption rate.In the present invention, using water absorption rate is the polyimide film of 1～3 quality %, if water absorption rate less than 1 quality %, the swell increment of the polyimide film being caused by water suction is less, cannot realize object of the present invention.If water absorption rate surpasses 3 quality %, the swell increment causing due to the water suction of polyimide film is excessive, the in the situation that of heat drying, in copper layer, as internal stress, compression stress be can produce, enough initial stage adhesive strengths and PCT adhesive strength sometimes cannot be obtained.
In addition, as polyimide film, have as above-mentioned absorptive reason, can consider as follows.
Conventionally, due to its thermal endurance and forming method, easily there is crystallization in known polyimide film.In the polyimide film of crystallization, polyimide molecule proper alignment, easily passes in and out moisture between this molecule and molecule.That is, in the polyimides of suitable crystallization, using thickness is the polyimide film of 35 μ m～40 μ m, and can make water absorption rate is 1～3 quality %.
In order to confirm whether crystallization of polyimide film, can carry out film X-ray diffraction method mensuration to polyimide film surface.The in the situation that of crystallization, its crystallization degree is also inconsistent, and conventionally, a plurality of peaks can be confirmed on spectrogram.In the present invention, if measure TD direction (Width), as shown in fig. 1, preferably, within the scope of each of 2 θ=12 °～18 °, 2 θ=26 °～32 °, 2 θ=42 °～48 °, having halfwidth is 1.5 ° of following peaks.The number at peak as long as there is 1 in scope separately.This is due to so long as the crystallization polyimide film of this degree, it is exactly the polyimide film that the present invention has suitable water absorption rate and the coefficient of expansion, as a result, by processing, thereby can guarantee the adhesive strength of expectation and the dimensional stability of COF on metallized polyimide film.
In addition, in the polyimide film using in the present invention, if carry out film X-ray diffraction method mensuration (Cu K α incidence angle=0.1 °) in TD direction (Width), preferably there is no halfwidth be the peak below 1.5 ° to the position below 2 θ=11 °.In current polyimide film, if carry out same mensuration, to have halfwidth be the peak below 1.5 ° to the position below 2 θ=11 °, the film using in metallized polyimide film of the present invention demonstrates by the elongation technology in improved thin film film formation process, thereby can realize the speciality of low-thermal-expansion.Specifically, use and at present same raw material, by the mixed proportion of feed change, and in film formation process, embody anisotropy, thereby can improve elongation technology, in addition, by making glass transition temperature also rise to Tg:350 ° of left and right from Tg:320 ° of left and right of existing product, by being controlled at, the thermal coefficient of expansion of TD direction (Width) approaches 3ppm/ ℃～8ppm/ ℃ of silicon and glass, if thereby carry out film X-ray diffraction method mensuration (Cu K α incidence angle=0.1 °) in TD direction (Width), obtaining position below 2 θ=11 °, there is no halfwidth be the polyimide film at the peak below 1.5 °.
By adopting this polyimide film, the circuit and the LSI that cause due to the heating that can suppress due to bonding process, or the departing from or be offset of mutual alignment between circuit and glass, therefore can be high-precision bonding, promotes the possibility that productivity ratio improves to improve.If this is owing to existing product being carried out in TD direction (Width) to film X-ray diffraction method mensuration (Cu K α incidence angle=0.1 °), because the position below 2 θ=11 ° has halfwidth, be the peak below 1.5 °, therefore have deviation such problem greatly of carrying out elongation in OLB bond sequence by orientation.
Polyimide film can directly arrange on surface metal level, now, the coefficient of thermal expansion differences of metal level and polyimide film is larger, on the circuit part that high-temperature heating during online bonding causes narrow width and polyimide film bonding face, produces load, just more easily peels off.Therefore,, in order to avoid this problem, the thermal coefficient of expansion of polyimide film used is necessary for 3ppm/ ℃～8ppm/ ℃ in TD direction, in MD direction, is necessary for 9ppm/ ℃～15ppm/ ℃.By within the scope of this, thereby the in the situation that of directly metal level being set on polyimide film surface, even produce load on the circuit part that high-temperature heating during online bonding causes narrow width and polyimide film bonding face, being also difficult to generation and peeling off.
In addition, humidity expansion coefficient is 7ppm/%HR～13ppm/%HR in TD direction, in MD direction, is 12ppm/%HR～15ppm/%HR.This is due to so long as the polyimide film of humidity expansion coefficient within the scope of this, just can be by being processed into metallized polyimide film, thus guarantee the adhesive strength of expectation and the dimensional stability of COF.
As the polyimide film using in the present invention, as long as have above-mentioned characteristic, in addition, just there is no particular limitation.As described later, preferably use and take the polyimide film that bibenzene tetracarboxylic is principal component.The polyimide film that the bibenzene tetracarboxylic of take is principal component, due to thermal endurance, excellent in dimensional stability, is therefore preferred.
The thickness of the polyimide film using in the present invention has no particular limits, but qualification rate while considering to guarantee bendability and metal film forming is 25～50 μ m, is preferably 25～45 μ m.
In addition,, in order to improve the various characteristics of the films such as sliding, heat conductivity, can also use the product that adds filler.In this case, as the material of filler, be preferably silicon dioxide, titanium oxide, aluminium oxide, silicon nitride, boron nitride, calcium monohydrogen phosphate, calcium phosphate, mica etc.
The particle diameter of filler as required the film characteristics of upgrading and the filling kind of interpolation different, there is no particular limitation, conventionally average grain diameter is 0.05～100 μ m, is preferably 0.1～75 μ m, more preferably 0.1～50 μ m, is particularly preferably 0.1～25 μ m.If particle diameter, lower than this scope, is difficult to embody the effect of upgrading, if exceed this scope, probably can damage significantly surface characteristic, greatly reduce mechanical property.
In addition,, because the addition of filler is also by the decisions such as particle diameter that need film characteristics and the filler of upgrading, therefore there is no particular limitation.Conventionally, with respect to 100 weight portion polyimides, the addition of filler is 0.01～100 weight portion, is preferably 0.01～90 weight portion, more preferably 0.02～80 weight portion.If filler addition lower than this scope, is difficult to embody the upgrading effect obtaining due to filler, if surpass this scope, probably can greatly damage the mechanical property of film.
As the example of this polyimide film, can enumerate the KAPTON 150EN-A (registered trade mark) for example being sold by East レデユポ Application Co., Ltd..
2. the manufacture method of polyimide film
The polyimide film using in the present invention does not limit its manufacture method, can the following method of illustration: first manufacture the polyamic acid as precursor, be then converted to polyimides, then carry out filming.
(1) as the manufacture of the polyamic acid of precursor
In order to obtain polyamic acid, the method that can use known method and their are combined.As representational polymerization, can be listed below (a)～method (e).That is,
(a) in organic polar solvent, dissolve aromatic diamine, add wherein equimolar aromatic tetracarboxylic acid's dianhydride and carry out polymerization.
(b) in organic polar solvent, make the aromatic diamine compound reaction less with relative its mole of aromatic tetracarboxylic acid's dianhydride, obtain the prepolymer at two ends with anhydride group.Then, add aromatic diamine compound and carry out polymerization, finally make substantially first-class mole of aromatic tetracarboxylic acid's dianhydride and aromatic diamine compound.
(c) in organic polar solvent, make the aromatic diamine compound reaction more with relative its mole of aromatic tetracarboxylic acid's dianhydride, obtain and there is amino prepolymer at two ends.Then, add aromatic tetracarboxylic acid's dianhydride compound and carry out polymerization, finally make substantially first-class mole of aromatic tetracarboxylic acid's dianhydride and aromatic diamine compound.
(d) in organic polar solvent, dissolve and/or disperse, after aromatic tetracarboxylic acid's dianhydride, to add equimolar aromatic diamine compound substantially, carrying out polymerization.
(e) in organic polar solvent, equimolar aromatic tetracarboxylic acid's dianhydride is substantially reacted with the mixture of aromatic diamine, carry out polymerization.
In order to obtain polyamic acid, can use this (a)～any method (e), also can partly be used in combination.The polyamic acid obtaining by either method all can be as the raw material of polyimide film used in the present invention.
In addition,, as above-mentioned acid dianhydride, comprise pyromellitic acid dianhydride, 2,3,6,7-naphthalenetetracarbacidic acidic dianhydride, 3,3 ', 4,4 '-bibenzene tetracarboxylic dianhydride, 1,2,5,6-naphthalenetetracarbacidic acidic dianhydride, 2,2 ', 3,3 '-bibenzene tetracarboxylic dianhydride, 3,3 ', 4,4 '-benzophenone tetracarboxylic dianhydride (BTDA), 4,4 '-oxo O-phthalic acid dianhydride, two (3,4-dicarboxyl phenyl) the propane dianhydrides of 2,2-, 3,4,9,10-perylene tetracarboxylic acid dianhydride, two (3,4-dicarboxyl phenyl) propane dianhydride, two (2,3-dicarboxyl phenyl) the ethane dianhydrides of 1,1-, two (3,4-dicarboxyl phenyl) the ethane dianhydrides of 1,1-, two (2,3-dicarboxyl phenyl) methane dianhydride, two (3,4-dicarboxyl phenyl) ethane dianhydride, oxydiphthalic acid dianhydride, two (3,4-dicarboxyl phenyl) sulfone dianhydride, TOPOT 2,2′ p phenylenebis (trimellitic acid monoesters acid anhydrides), ethylenebis (trimellitic acid monoesters acid anhydrides), bisphenol-A two (trimellitic acid monoesters acid anhydrides) and their analogs, these materials are preferably used or use separately the mixture of arbitrary proportion.
In these acid dianhydrides, particularly preferably use pyromellitic acid dianhydride and/or 3,3 ', 4,4 '-bibenzene tetracarboxylic dianhydride and/or 4,4 '-oxo O-phthalic acid dianhydride, and/or 3,3 ', 4,4 '-bibenzene tetracarboxylic dianhydride, more preferably use and contain 3,3 ', 4, the mixture of the acid dianhydride of 4 '-bibenzene tetracarboxylic dianhydride.
As above-mentioned aromatic diamine compound, can enumerate 4,4 '-diamino-diphenyl propane, 4,4 '-diaminodiphenyl-methane, benzidine, 3,3 '-dichloro-benzidine, 3,3 '-dimethylbenzidine, 2,2 '-dimethylbenzidine, 3,3 '-dimethoxy benzidine, 2,2 '-dimethoxy benzidine, 4,4 '-diamino-diphenyl thioether, 3,3 '-diamino diphenyl sulfone, 4,4 '-diamino diphenyl sulfone, 4,4 '-oxo diphenylamines, 3,3 '-oxo diphenylamines, 3,4 '-oxo diphenylamines, 1,5-diaminonaphthalene, 4,4 '-diamino-diphenyl diethylsilane, 4,4 '-diamino-diphenyl silane, 4,4 '-diamino-diphenyl ethyl sulfinyl oxide, 4,4 '-diamino-diphenyl N-methylamine, 4,4 '-diamino-diphenyl N-aniline, Isosorbide-5-Nitrae-diaminobenzene (P-pHENYLENE dI AMINE), 1,3-diaminobenzene, 1,2-diaminobenzene, two { 4 (4-amino-benzene oxygen) phenyl } sulfone, two { 4 (3-amino-benzene oxygen) phenyl } sulfone, 4,4 '-bis-(4-amino-benzene oxygen) biphenyl, 4,4 '-bis-(3-amino-benzene oxygen) biphenyl, two (3-amino-benzene oxygen) benzene of 1,3-, two (4-amino-benzene oxygen) benzene of 1,3-, two (4-amino-benzene oxygen) benzene of 1,3-, two (3-amino-benzene oxygen) benzene of 1,3-, 3,3 '-diaminourea benzophenone, 4,4-diaminourea benzophenone and their analog etc.
The polyamic acid that the polyimide film using in the present invention is used can be by selecting kind, the mixing ratio of aromatic acid tetracarboxylic dianhydride and aromatic diamine in the above range, and then polymerization obtains.
For the synthesis of the preferred solvent of polyamic acid, so long as can dissolve the solvent of polyamic acid, just can use material arbitrarily.Preferred amide kind solvent, i.e. DMF, DMA, METHYLPYRROLIDONE etc., particularly preferably DMF, DMA.
(2) by polyamic acid, be converted into polyimides and filming
Then, the organic solution that comprises thus obtained polyamic acid is cast on the supports such as glass plate, aluminium foil, metal tape loop processed, metal cylinder processed as resin molding.Now, by heating on support, thus can be partly solidified and/or dry, now, so long as give hot blast or far-infrared radiation heat.In addition, can also be directly to support conducting self-heating.In addition, can combine the method that gives hot blast or far-infrared radiation heat and the method that directly heats support self.
The resin molding of casting by heating is the semi-solid preparation film with self-supporting, and so-called gel film, can be peeled off by support.This gel film is by polyamic acid, to be solidified into the interstage of polyimides, by part imidizate, has self-supporting, has the residual volatile ingredients such as solvent.
Then, heat above-mentioned gel film, dry to remove residual solvent, complete curing (imidizate) simultaneously, the contraction of gel film when dry and curing in order to avoid, can be fixed on the end of gel film on stenter framework with safety pin or stenter clamp etc., is delivered in heating furnace, heating at 200～400 ℃, obtains polyimide film.
3. metallized polyimide film and manufacture method thereof
Metallized polyimide film of the present invention can on the specific polyimide film surface as above-mentioned acquisition directly, just form metal film without adhesive.
As shown in Figure 3,4, metal film consists of with copper layer 4 underlying metal film 2 and the copper film 3 arranging on the surface of underlying metal film 2 or copper film 3.; metallized polyimide film of the present invention is, on the surface of polyimide film 1, the duplexer of metal film is not set by adhesive, and metal film is underlying metal film 2 and the stepped construction or the underlying metal film 2 and the copper film 3 of formation copper layer and the stepped construction of copper layer 4 that form the copper film 3 of copper layer.Underlying metal film 2 forms by plating method with 3 expectations of copper film.In the latter, can, after underlying metal film 2 and copper film 3 are set, the copper film 4 of specific thickness be set by wet method plating.
(a) underlying metal film
Underlying metal film is for guaranteeing the film of the reliabilities such as polyimide film and metal film tack and thermal endurance.Therefore, the material of underlying metal film, in order to improve the adhesive force of polyimide film and copper layer, is selected from any in nickel, chromium and their alloy, and while being prepared by bond strength and circuit, easy etching is set out, preferably nichrome.In addition,, for the concentration gradient of nichrome is set, can also form metallic film with the different a plurality of nichrome layers of chromium concn.As long as form with these metals, just can improve corrosion resistance, the resistance to migration of metallized polyimide film.
In addition,, in order further to improve the corrosion resistance of underlying metal film, can also in above-mentioned metal, add palladium, titanium, molybdenum, cobalt etc.
In addition, before carrying out dry plating, in order to improve the tack of polyimide film and underlying metal film, preferably passing through corona discharge or ion exposure etc., polyimide film surface is carried out after surface treatment, under oxygen atmosphere, carry out ultraviolet treatment with irradiation.To these treatment conditions, there is no particular limitation, can be the condition adopting in the manufacture method of common metallized polyimide film.
The thickness of above-mentioned underlying metal film is preferably 3～50nm.Not enough 3nm, if the metal level of above-mentioned metallized polyimide film is carried out etching and prepares circuit, the above-mentioned metallic film of etching solution meeting etch, invades between polyimide film and above-mentioned metallic film, circuit can float sometimes, is not preferred.On the other hand, if surpass 50nm,, in the situation that circuit is prepared in etching, cannot remove metallic film completely, its form with residue remains between circuit, probably can produce the defective insulation between circuit.
Above-mentioned underlying metal film is preferably by dry plating film forming.In dry plating, comprise sputtering method, magnetron sputtering system, ion plating method, ion beam method, vacuum vapour deposition, CVD method etc., can use arbitrarily, in industry, use magnetron sputtering system.This is because production efficiency is higher.
(b) copper film
In the present invention, on underlying metal film, stacked copper film preferably forms by dry plating.The dry plating adopting can be used any of above-mentioned sputtering method, magnetron sputtering system, ion plating method, ion beam method, vacuum vapour deposition, CVD method etc.Can also by magnetron sputtering system by after above-mentioned metallic film film forming, by vapour deposition method, above-mentioned copper film is set.That is, can adopt the identical above-mentioned metallic film of method dry plating and copper film, also can adopt different dry platings to form.
If the reason of above-mentioned copper film is set, be owing to directly by galvanoplastic, above-mentioned copper layer being set on above-mentioned metallic film, the resistance of switching on improves, and the current density of plating is unstable.By above-mentioned copper film is set, thereby can reduce energising resistance, the current density stabilisation while making to electroplate.The thickness of this copper film is 10nm～1 μ m, is preferably 20nm～0.8 μ m.If this is due to thinner than this value, cannot fully reduce the energising resistance while electroplating, if blocked up, when film forming, can spend a large amount of time, productivity is worsened, economy incurs loss.
(c) copper film
In metallized polyimide film of the present invention, can as required, on copper film, copper film be set.The necessity of copper film suitably determines according to the manufacturing process of flexible PCB.
The thickness of copper film is preferably 1.0～20.0 μ m.If this is due to less than 1.0 μ m,, when forming circuit, sometimes cannot obtain enough conductivity, if surpass 20 μ m, the internal stress of copper film is excessive.
Copper film preferably arranges by wet method plating.In dry plating, the thickness for plating becomes to stipulate, requires a great deal of time, and productivity is worsened, and economy incurs loss.In wet method plating, comprise galvanoplastic and electroless plating method, can use any, also can be used in combination, galvanoplastic are simple, and gained copper film is careful, are therefore preferred.In addition, plating condition can be carried out under known condition.
In the situation that copper film being set by galvanoplastic, if use sulfuric acid bath, can obtain the electroplating copper film with suitable tensile stress, flexible by the expansion of polyimide film, can more easily obtain the balance of internal stress, so be preferred.
In the situation that obtaining copper film by galvanoplastic, under the state of the internal stress of this copper film before polyimide film dry is dry, be preferably the tensile stress of 5～30MPa.If this is due to not enough 5MPa,, when dry polyimide film, the flexible effect of polyimide film is large not, if surpass the tensile stress of 30MPa, the flexible effect of the polyimide film while being dried polyimide film is too small.
The copper being undertaken by sulfuric acid bath is electroplated as long as under common condition.As plating bath, can use the commercially available copper sulphate plating bath of using in common copper is electroplated.In addition, the average cathode-current density of the preferred coating bath of cathode-current density is 1～3A/dm
2.This is the not enough 1A/dm of average cathode-current density due to cathode-current density
2, the hardness of gained copper film is higher, is difficult to guarantee bendability, even if use gained metallized polyimide film to obtain flexible PCB, gained flexible PCB also can't become well in flexibility.On the other hand, if be because average cathode-current density surpasses 3A/dm
2, in the residual stress producing in gained copper film, can produce inhomogeneous.
Use the electro-coppering device of sulfuric acid bath identical with dry plating operation, from being arranged on the machine that rolls out of electro-coppering device portal side, roll out the polyimide film of roller shape, carry and also pass through successively plating coating groove, the electroplanting device of the roll-to-roll mode of carrying out when batching with coiling machine, because production efficiency improves, manufacturing cost reduces, and is therefore preferred.In this case, the transporting velocity of film is preferably adjusted into 50～150m/h.If transporting velocity deficiency 50m/h, productivity is too low, if surpass 150m/h, needs to improve electrical current amount, must use large-scale supply unit, has the higher such problem of equipment price.
In thus obtained metallized polyimide film of the present invention, based on JPCABM01-11.5.3 (B method) (peel strength), evaluate, be that initial stage adhesive strength is more than 600N/m, elongation when ACF during OLB operation is bonding is that 0.023mm has so below and reduces the circuit substrate of existing product 50% elongation function and use its flexible PCB obtaining.
4. flexible PCB and manufacture method thereof
Flexible PCB of the present invention is used metallized polyimide film of the present invention, by relief method or semi-additive process processing, obtains.
Above-mentioned metal film is by least a kind that is selected from nickel, chromium or the nickel alloy metallic film forming, the copper film arranging on this metallic film and the 3 layers of formation of copper layer that arrange thereon again, and above-mentioned thickness of metal film is below 20 μ m.
In addition, in etching, remove above-mentioned metallic diaphragm, while exposing the film surface after circuit fabrication, if the TD direction on polyimide film surface is carried out to film X-ray diffraction method mensuration (Cu K α incidence angle=0.1 °), as shown in Figure 2, within the scope of each of 2 θ=12 °～18 °, 2 θ=26 °～32 °, 2 θ=42 °～48 °, having halfwidth is 1.5 ° of following peaks.The quantity at peak exists 1 above in scope separately.Wherein, the peak of 2 θ=12 °～18 °, 2 θ=26 °～32 °, 2 θ=42 °～48 ° conforms to the peak compared with the polyimide film of length direction as metallized polyimide film raw material.
In addition,, if the TD direction on polyimide film surface is carried out to film X-ray diffraction method mensuration (Cu K α incidence angle=0.1 °), preferably there is no halfwidth be the peak below 1.5 ° to the position below 2 θ=11 °.If this is to be the peak below 1.5 ° because the position below 2 θ=11 ° exists halfwidth, exist the elongation in OLB bond sequence to disperse to become large such problem.
In the manufacture method of flexible PCB of the present invention, circuit pattern can obtain by relief method or semi-additive process processing.
For example, when obtaining flexible PCB by null method, can resist layer be set in the metallic film surface of above-mentioned metallized polyimide film of the present invention, the exposed mask with predetermined pattern is set thereon, irradiation ultraviolet radiation exposes, develops from it, obtains for obtaining the etching mask of circuit part.Then, the metal film exposing is removed in etching, then removes residual etching mask, washing, the plating of expecting at necessary position, thus obtain flexible PCB of the present invention.
On the other hand, when obtaining flexible PCB by semi-additive process, can resist layer be set in the metallic film surface of above-mentioned metallized polyimide film of the present invention, the mask with specified circuit pattern is set thereon, and irradiation ultraviolet radiation exposes, develops, and the plating mask that circuit is opening portion is take in acquisition, pass through electrocoppering, on the surface of metal film of exposing opening portion, separate out copper, forming circuit, then removes plating mask.Then, the metal film beyond circuit is removed in soft etching, guarantees the insulating properties of circuit, washing, and the plating of expecting at necessary position, thus obtain flexible PCB of the present invention.
The circuit structure of flexible PCB of the present invention, by any preparation of null method or semi-additive process, all can form the structure that is stacked gradually the metal film consisting of underlying metal film, copper film, copper layer by polyimide film surface.
In addition, as mentioned above, when manufacturing flexible PCB by semi-additive process, the copper layer of metallized polyimide film can suitably be selected only copper film, to consist of, or consists of copper film and copper film.
Embodiment
Below, by embodiment, the present invention will be described in more detail, but the present invention is not subject to any restriction of these embodiment.In addition, the condition determination of film X-ray diffraction using in embodiment is, the conditions such as assay method of adhesive strength are as described below.
(1) film X-ray diffraction method condition determination: as diffraction instrument, use (strain) リ ガ Network manufacture level type X-ray diffraction device SmartLab, in TD direction, the following condition of take is measured: incidence angle (ω) is 0.1 °, specimen width is 0.1 °, measuring angle 2 θ is 2 °～60 °, and sweep speed is 4 °/minute.
(2) adhesive strength: form line width 1mm by null method, the circuit pattern of length 50mm, is used its stretch release method of passing through regulation in JPCA BM01-11.5.3 (B method) (stretch release intensity) to obtain.
(3) water absorption rate: by stipulating in ASTM D570 20 ℃, 24hr infusion process (Immergion) are obtained.
(4) thermal coefficient of expansion: use TMA (Thermal Mechanical Analysis (thermo-mechanical analysis)) device, in the TD direction in the scope of 50 °～200 °, obtain by pulling method.
(5) humidity expansion coefficient: will control the dew point of atmosphere gas, the device of energy controlled humidity is connected with TMA (Thermal Mechanical Analysis (thermo-mechanical analysis)) device, under relative humidity 20,80% atmosphere, measure and extend, calculate humidity expansion coefficient.
(embodiment 1)
First, preparing water absorption rate is 1.8 quality %, thermal coefficient of expansion is 5ppm/ ℃ in TD direction, in MD direction, be 11ppm/ ℃, and film X-ray diffraction result can be clear and definite as shown in Figure 1, when 2 θ are 14 °, 29 °, 44 °, having respectively halfwidth is the peak below 1.0 °, and thickness is the rectangular polyimide film (East レ デ ユ Port Application, KAPTON 150EN-A) that bibenzene tetracarboxylic is principal component of take of 38 μ m.Its humidity expansion coefficient is 11ppm/%HR in TD direction, in MD direction, is 12ppm/%HR.
In the one side of this polyimide film, use the sputtering equipment forming by rolling out machine, sputter equipment, coiling machine, by DC sputtering, form average thickness
cr is that the chromium-nickel alloy layer of 7 quality % is as metallic film.In addition, on underlying metal film, form equally average thickness
copper film.
Then, on copper film, the copper film of thickness 8 μ m is set by copper galvanoplastic, obtains metallized polyimide film.The copper sulphate plating bath that the electroplating bath using is copper concentration 23g/l, bath temperature during plating is 27 ℃.In addition, coating bath, for connecting many structure grooves of a plurality of coating baths, by rolling out machine and coiling machine, is carried the polyimide film continuous impregnating in each groove that is provided with metal film in one side, electroplates simultaneously.Transporting velocity is 75m/h, and the average cathode density of coating bath is adjusted into 1.0～2.5A/dm
2, carry out copper facing.
Obtain the initial stage adhesive strength of gained metallized polyimide film, it is 728N/m, and elongation when ACF during OLB operation engages is the circuit substrate that 0.021mm has the function that reduces existing product 50% elongation below like this, and use the flexible PCB of its acquisition.
Then, use this metallized polyimide film, prepare circuit be spaced apart 35 μ m by relief method, whole circuit width is the COF (covering brilliant film) of 15000 μ m.In relief method operation, by iron chloride, carry out etch processes.IC chip is installed thereon, is used line bonding apparatus, at 400 ℃, under the bonding treatment conditions of 0.5 second, the lead portion of the electrode of IC chip surface and circuit is carried out to line bonding.Now, the not good ratio of the lead-in wire producing in inner lead portion and the bonding of polyimide film is 0.0001%.
(embodiment 2)
First, preparing water absorption rate is 1.7 quality %, thermal coefficient of expansion is 5ppm/ ℃ in TD direction, in MD direction, be 13ppm/ ℃, and film X-ray diffraction result is the peak below 1.0 ° for have respectively halfwidth when 2 θ are 14 °, 29 °, 44 °, thickness is 38 μ m, the rectangular polyimide film (East レ デ ユ Port Application that the bibenzene tetracarboxylic of take is principal component, KAPTON 150EN-A).Its humidity expansion coefficient is 9ppm/%HR in TD direction, in MD direction, is 14ppm/%HR.
In the one side of this polyimide film, use the sputtering equipment forming by rolling out machine, sputter equipment, coiling machine, by DC sputtering, form average thickness
cr is that the chromium-nickel alloy layer of 20 quality % is as metallic film.In addition, on metallic film, form equally average thickness
copper film.
Then, on copper film, by copper galvanoplastic, the copper film of thickness 8 μ m is set, obtains metallized polyimide film.The copper sulphate plating bath that the electroplating bath using is copper concentration 23g/l, bath temperature during plating is 27 ℃.In addition, coating bath, for connecting many structure grooves of a plurality of coating baths, by rolling out machine and coiling machine, is carried polyimide film continuous impregnating in each groove that metal film is set in one side, electroplates simultaneously.Transporting velocity is 75m/h, and the average cathode-current density of coating bath is adjusted into 1.0～2.5A/dm
2, carry out copper facing.
Obtain the initial stage adhesive strength of gained metallized polyimide film, it is 728N/m, and elongation when ACF during OLB operation engages is the circuit substrate that 0.020mm has the function that reduces existing product 50% elongation below like this, and use the flexible PCB of its acquisition.
Then, use this metallized polyimide film, prepare circuit be spaced apart 35 μ m by relief method, whole circuit width is the COF (covering brilliant film) of 15000 μ m.In relief method operation, by iron chloride, carry out etch processes.IC chip is installed thereon, is used line bonding apparatus, at 400 ℃, under the bonding treatment conditions of 0.5 second, the lead portion of the electrode of IC chip surface and circuit is carried out to line bonding.Now, the not good ratio of the lead-in wire producing in inner lead portion and the bonding of polyimide film is 0.0002%.
The polyimide film that use is used in this embodiment 2, forms metallic film, copper film, copper film successively on its surface, then by using the etching method etching of iron chloride to remove the metal level of formation.This state is called as the polyimide film that exposes the film surface after circuit fabrication.This film is carried out to X-ray diffraction, obtain the chart of Fig. 2.
As shown in Figure 2, the value of discovery 2 θ is 14 °, 29 ° and 44 ° and has peak value result.Wherein, the peak of 14 ° is the peak causing due to the rectangular polyimide film as metallized polyimide raw material.
(embodiment 3)
First, preparing water absorption rate is 1.6 quality %, thermal coefficient of expansion is 5ppm/ ℃ in TD direction, in MD direction, be 15ppm/ ℃, and film X-ray diffraction result is the rectangular polyimide film (East レ デ ユ Port Application, KAPTON 150EN-A) that peak, thickness below 1.0 ° is 38 μ m, the bibenzene tetracarboxylic of take is principal component for have respectively halfwidth when 2 θ are 14 °, 29 °, 44 °.Its humidity expansion coefficient is 13ppm/%HR in TD direction, in MD direction, is 15ppm/%HR.
Then, in the one side of this polyimide film, use the sputtering equipment forming by rolling out machine, sputter equipment, coiling machine, by DC sputtering, form average thickness
cr is that the chromium-nickel alloy layer of 20 quality % is as metallic film.In addition, on underlying metal film, form equally average thickness
copper film.
Then, on copper film, by copper galvanoplastic, the copper film of thickness 1 μ m is set, obtains metallized polyimide film.The copper sulphate plating bath that the electroplating bath using is copper concentration 23g/l, bath temperature during plating is 27 ℃.In addition, coating bath, for connecting many structure grooves of a plurality of coating baths, by rolling out machine and coiling machine, is carried polyimide film continuous impregnating in each groove that metal film is set in one side, electroplates simultaneously.Transporting velocity is 75m/h, and the average cathode-current density of coating bath is adjusted into 1.0～2.5A/dm
2, carry out copper plating.
Obtain the initial stage adhesion strength of gained metallized polyimide film, it is 728N/m, and elongation when ACF during OLB operation engages is the circuit substrate that 0.021mm has the function that reduces existing product 50% elongation below like this, and use the flexible PCB of its acquisition.
Then, use this metallized polyimide film, by relief method, prepare that circuit is spaced apart 35 μ m, whole circuit width is the COF (covering brilliant film) of 15000 μ m.In relief method operation, by iron chloride, carry out etch processes.IC chip is installed thereon, is used line bonding apparatus, at 400 times, under the bonding treatment conditions of 0.5 second, the lead portion of the electrode of IC chip surface and circuit is carried out to line bonding.Now, the not good ratio of the lead-in wire producing in inner lead portion and the bonding of polyimide film is 0.0001%.
(embodiment 4)
Use the metallized polyimide film obtaining in embodiment 1, except circuit is spaced apart 25 μ m, prepare similarly to Example 1 flexible PCB, obtain similarly to Example 1 the not good ratio of bonding.The not good ratio of the bonding of lead and polyimide film is 0.005%, even in fine pitch, also has enough size reliabilities.
(comparative example 1)
Except as polyimide film, using water absorption rate is 1.7 quality %, thermal coefficient of expansion is 16ppm/ ℃ in TD direction, in MD direction, be 17ppm/ ℃, humidity expansion coefficient is 13ppm/%HR in TD direction, in MD direction, is 17ppm/%HR, take bibenzene tetracarboxylic as principal component, thickness is that the polyimide film (East レ デ ユ Port Application of 38 μ m is produced, KAPTON 150EN) in addition, obtain similarly to Example 1 metallized polyimide film.In addition, KAPTON 150EN is carried out to film X-ray diffraction, confirm to exist large peak when 2 θ are 10 ° and 14 °.In addition, confirm in 2 θ=26 °～32 °, within the scope of each of 2 θ=42 °～48 °, there is no halfwidth is 1.5 ° of following peaks.
Gained metallized polyimide film is evaluated similarly to Example 1, and it is 720N/m that the initial stage is adhered to density, and elongation during ACF bonding during OLB operation is 0.043mm.
Then, except using above-mentioned metallized polyimide film, similarly to Example 1, prepare the flexible PCB of circuit width 35 μ m, obtain similarly to Example 1 the not good ratio of bonding.The not good ratio of the bonding producing in the inner lead portion of circuit is 0.001%, and comparing with embodiment is poor value, even if circuit width is 35 μ m, also cannot obtain the circuit board with enough reliabilities.
(comparative example 2)
Except circuit is spaced apart 25 μ m, prepare equally flexible PCB with comparative example 1, obtain similarly to Example 1 the not good ratio of bonding.The not good ratio of bonding producing in the inner lead portion of circuit is 0.1%, the in the situation that of fine pitch, cannot obtain the circuit board with enough reliabilities.
(comparative example 3)
Except as polyimide film, using water absorption rate is 1.4 quality %, thermal coefficient of expansion is 14ppm/ ℃ in TD direction, in MD direction, be 16ppm/ ℃, humidity expansion coefficient is 15ppm/%HR in TD direction, in MD direction, is 16ppm/%HR, take bibenzene tetracarboxylic as principal component, thickness is that the polyimide film (ProductName, emerging the producing of space portion made UPILEX 35SGA) of 35 μ m in addition, obtains metallized polyimide film similarly to Example 1.In addition, UPILEX 35SGA being carried out to film X-ray diffraction, there is large peak in the position that to confirm at θ be 11 ° and 14 °.In addition, confirm in 2 θ=26 °～32 °, within the scope of each of 2 θ=42 °～48 °, there is no halfwidth is 1.5 ° of following peaks.
Gained metallized polyimide film is evaluated similarly to Example 1, and for the initial stage, to adhere to density be 756N/m for it, and the elongation of the ACF while having OLB operation while engaging is the circuit substrate of the such function of 0.044mm and the flexible PCB that uses its acquisition.
Then, except using above-mentioned metallized polyimide film, similarly to Example 1, prepare the flexible PCB of circuit width 35 μ m, obtain similarly to Example 1 the not good ratio of bonding.The not good ratio of the bonding producing in the inner lead portion of circuit is 0.001%, and comparing with embodiment is poor value.
(comparative example 4)
Except circuit is spaced apart 25 μ m, prepare equally flexible PCB with comparative example 3, obtain similarly to Example 1 the not good ratio of bonding.The not good ratio of bonding producing at the electrode part of circuit is 0.1%, finds, the in the situation that of fine pitch, cannot obtain the circuit board with enough reliabilities.
" evaluation "
Clear and definite by above embodiment 1～4, PCT adhesive force after metallized polyimide film initial stage adhesive strength of the present invention and PCT test is very high, therefore use it can prepare the flexible PCB of fine pitch, while IC being installed in this circuit board, even line bonding is carried out in pressurization at more than 400 ℃ temperature, lead-in wire can not peeled off from polyimide film yet, as flexible PCB, obtains extreme high reliability.
On the contrary, clear and definite by comparative example 1～4, if use the metallized polyimide film that does not meet condition of the present invention, in the flexible PCB of fine pitch, or in the existing like this circuit spacing of circuit width 35 μ m, all cannot obtain the flexible PCB that reliability is high.
Industrial utilizability
Elongation when ACF when metallized polyimide film of the present invention can be used as initial stage adhesive strength and OLB operation engages is the following material of excellent circuit substrate like this of 0.023mm.If use metallized polyimide film of the present invention, prepare the flexible PCB of fine pitch, while IC being installed in this circuit board, even line bonding is carried out in pressurization at more than 400 ℃ temperature, lead-in wire can not peeled off from polyimide film yet, as flexible PCB, can obtain extreme high reliability.Therefore, metallized polyimide film of the present invention is very useful as the base material of the flexible PCB manufacture use of nearest requirement.
Claims (12)
1. a metallized polyimide film, this metallized polyimide film is by plating method, on the surface of polyimide film, metal film to be directly set to form, it is characterized in that: this polyimide film contains the imide bond being formed by aromatic tetracarboxylic acid's dianhydride and aromatic diamine in polyimide molecule, when thickness is 35 μ m～40 μ m, water absorption rate is 1 quality %～3 quality %, and, thermal coefficient of expansion is 3ppm/ ℃～8ppm/ ℃ in TD direction, in MD direction, be 9ppm/ ℃～15ppm/ ℃, in addition, humidity expansion coefficient is 7ppm/%HR～13ppm/%HR in TD direction, in MD direction, be 12ppm/%HR～15ppm/%HR.
2. the metallized polyimide film of recording according to claim 1, it is characterized in that: aforementioned polyimide film contains the imide bond being formed by bibenzene tetracarboxylic dianhydride and aromatic diamine compound in polyimide molecule, take Cu K α incidence angle when 0.1 ° is measured its surperficial TD direction by film X-ray diffraction method, within the scope of each of 2 θ=12 °～18 °, 2 θ=26 °～32 °, 2 θ=42 °～48 °, having halfwidth is 1.5 ° of following peaks.
3. the metallized polyimide film of recording according to claim 1, is characterized in that: aforementioned metal film consists of at least a kind that is selected from nickel, chromium or the nickel alloy underlying metal film forming and the copper layer that is arranged on this underlying metal film.
4. the metallized polyimide film of recording according to claim 3, is characterized in that: aforementioned copper layer is copper film.
5. the metallized polyimide film of recording according to claim 3, is characterized in that: in aforementioned copper layer, be also laminated with copper film on the surface of copper film.
6. the metallized polyimide film of recording according to claim 4 or 5, is characterized in that: aforementioned metal film and copper film form by dry plating.
7. the metallized polyimide film of recording according to claim 5, is characterized in that: aforementioned copper film forms by wet method plating.
8. the metallized polyimide film of recording according to claim 1, is characterized in that: the thickness of aforementioned metal film is below 20 μ m.
9. a flexible PCB in this circuit board, is provided with the circuit pattern of metal film on the surface of polyimide film, it is characterized in that:
Aforementioned polyimide film contains the imide bond being formed by bibenzene tetracarboxylic dianhydride and aromatic diamine compound in polyimide molecule, take Cu K α incidence angle when 0.1 ° is measured its surperficial TD direction by film X-ray diffraction method, within the scope of each of 2 θ=12 °～18 °, 2 θ=26 °～32 °, 2 θ=42 °～48 °, having halfwidth is 1.5 ° of following peaks, in addition, humidity expansion coefficient is 7ppm/%HR～13ppm/%HR in TD direction, in MD direction, is 12ppm/%HR～15ppm/%HR.
10. the flexible PCB of recording according to claim 9, is characterized in that: aforementioned metal film consists of at least a kind that is selected from nickel, chromium or the nickel alloy underlying metal film forming and the copper layer that is arranged on this metallic film.
11. flexible PCBs of recording according to claim 9 or 10, is characterized in that: the thickness of aforementioned metal film is below 20 μ m.
12. rights to use require the metallized polyimide film that in 1～8, any one is recorded, the flexible PCB processing by relief method or semi-additive process.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2010005546A JP5347980B2 (en) | 2010-01-14 | 2010-01-14 | Metallized polyimide film and flexible wiring board using the same |
| JP2010-005546 | 2010-01-14 |
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| Publication Number | Publication Date |
|---|---|
| CN102131345A CN102131345A (en) | 2011-07-20 |
| CN102131345B true CN102131345B (en) | 2014-11-19 |
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| CN201010141682.XA Active CN102131345B (en) | 2010-01-14 | 2010-03-29 | Metalized polyimide film and flexible circuit board with the same |
Country Status (4)
| Country | Link |
|---|---|
| JP (1) | JP5347980B2 (en) |
| KR (1) | KR101702128B1 (en) |
| CN (1) | CN102131345B (en) |
| TW (1) | TWI445618B (en) |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| JP5918943B2 (en) * | 2011-08-10 | 2016-05-18 | 味の素株式会社 | Manufacturing method of semiconductor package |
| KR101669745B1 (en) * | 2012-04-24 | 2016-10-27 | 스미토모 긴조쿠 고잔 가부시키가이샤 | Two-layered flexible wiring substrate, flexible wiring board, and methods for producing same |
| JP6090148B2 (en) * | 2013-12-19 | 2017-03-08 | 住友金属鉱山株式会社 | Method for determining adhesion strength of metal thin film / polyimide laminate, and metallized polyimide film substrate using the same |
| TWI692385B (en) * | 2014-07-17 | 2020-05-01 | 美商應用材料股份有限公司 | Method, system and polishing pad for chemical mechancal polishing |
| JP6361550B2 (en) * | 2015-03-30 | 2018-07-25 | 住友金属鉱山株式会社 | Method for judging quality of polyimide film, and method for producing copper-clad laminate and flexible wiring board using the polyimide film |
| CN110241389A (en) * | 2018-03-08 | 2019-09-17 | 日铁化学材料株式会社 | Deposition mask, deposition mask form the manufacturing method formed with polyamic acid, deposition mask with laminated body and deposition mask |
| KR20220093615A (en) | 2020-12-28 | 2022-07-05 | 주식회사 클랩 | Conductive metal layer, fine metal pattern, and manufacturing method thereof |
| KR20220093621A (en) | 2020-12-28 | 2022-07-05 | 주식회사 클랩 | Flexible copper foil film and manufactruing method thereof |
| CN112875639A (en) * | 2021-01-25 | 2021-06-01 | 上海交通大学 | Composite flexible substrate and manufacturing method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101151946A (en) * | 2005-03-31 | 2008-03-26 | 新日铁化学株式会社 | Multi-layer laminate and flexible copper-clad laminated substrate production method |
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| JP2002100655A (en) * | 2000-09-20 | 2002-04-05 | Hitachi Cable Ltd | Tape carrier and semiconductor device using the same |
| JP2004217785A (en) * | 2003-01-15 | 2004-08-05 | Teijin Ltd | Polyimide film |
| JP2005314669A (en) * | 2004-03-30 | 2005-11-10 | Du Pont Toray Co Ltd | Polyimide film and copper-clad laminate using the same as substrate |
| JP2008166555A (en) * | 2006-12-28 | 2008-07-17 | Du Pont Toray Co Ltd | Flexible printed wiring board |
| JP4947297B2 (en) * | 2007-05-23 | 2012-06-06 | 東レ・デュポン株式会社 | Copper plate |
| JP2008290304A (en) * | 2007-05-23 | 2008-12-04 | Du Pont Toray Co Ltd | Copper-clad plate |
| JP5151297B2 (en) * | 2007-07-27 | 2013-02-27 | 宇部興産株式会社 | Manufacturing method of resin film, manufacturing method of conductive layer laminated resin film |
| JP5262030B2 (en) * | 2007-09-12 | 2013-08-14 | 東レ・デュポン株式会社 | Polyimide film and copper-clad laminate based thereon |
| TWI398350B (en) * | 2008-02-05 | 2013-06-11 | Du Pont | Highly adhesive polyimide copper clad laminate and method of making the same |
| WO2009148060A1 (en) * | 2008-06-02 | 2009-12-10 | 宇部興産株式会社 | Method for producing aromatic polyimide film wherein linear expansion coefficient in transverse direction is lower than linear expansion coefficient in machine direction |
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- 2010-01-14 JP JP2010005546A patent/JP5347980B2/en active Active
- 2010-03-29 TW TW099109298A patent/TWI445618B/en active
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| CN101151946A (en) * | 2005-03-31 | 2008-03-26 | 新日铁化学株式会社 | Multi-layer laminate and flexible copper-clad laminated substrate production method |
Also Published As
| Publication number | Publication date |
|---|---|
| CN102131345A (en) | 2011-07-20 |
| TWI445618B (en) | 2014-07-21 |
| KR101702128B1 (en) | 2017-02-13 |
| JP2011143595A (en) | 2011-07-28 |
| TW201124266A (en) | 2011-07-16 |
| JP5347980B2 (en) | 2013-11-20 |
| KR20110083448A (en) | 2011-07-20 |
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