CN1733473B - Flexible laminose plate and method for manufacturing the same - Google Patents
Flexible laminose plate and method for manufacturing the same Download PDFInfo
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- CN1733473B CN1733473B CN2005100831684A CN200510083168A CN1733473B CN 1733473 B CN1733473 B CN 1733473B CN 2005100831684 A CN2005100831684 A CN 2005100831684A CN 200510083168 A CN200510083168 A CN 200510083168A CN 1733473 B CN1733473 B CN 1733473B
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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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/28—Layered products comprising a layer of synthetic resin comprising synthetic resins not wholly covered by any one of the sub-groups B32B27/30 - B32B27/42
- B32B27/281—Layered products comprising a layer of synthetic resin comprising synthetic resins not wholly covered by any one of the sub-groups B32B27/30 - B32B27/42 comprising polyimides
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B37/00—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
- B32B37/14—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the properties of the layers
- B32B37/24—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the properties of the layers with at least one layer not being coherent before laminating, e.g. made up from granular material sprinkled onto a substrate
-
- 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
- B32B37/00—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
- B32B37/14—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the properties of the layers
- B32B37/24—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the properties of the layers with at least one layer not being coherent before laminating, e.g. made up from granular material sprinkled onto a substrate
- B32B2037/243—Coating
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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
- B32B2307/00—Properties of the layers or laminate
- B32B2307/20—Properties of the layers or laminate having particular electrical or magnetic properties, e.g. piezoelectric
- B32B2307/206—Insulating
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2307/00—Properties of the layers or laminate
- B32B2307/50—Properties of the layers or laminate having particular mechanical properties
- B32B2307/51—Elastic
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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
- B32B2307/00—Properties of the layers or laminate
- B32B2307/50—Properties of the layers or laminate having particular mechanical properties
- B32B2307/538—Roughness
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Abstract
To provide a flexible laminated board coping with mounting conditions under high temperature and high pressure while retaining characteristics possessed by the flexible laminated board. In the flexible laminated board having a metal foil on one surface or both surfaces of an insulating resin layer, the insulating resin layer comprises a plurality of layers of a polyimide resin provided with at least one high elastic modulus resin layer in contact with the metal foil of a polyimide resin with >=1*10<8>Pa storage elastic modulus at 350[deg.]C, and at least one low thermal expansion resin layer of <=20*10<-6>/K linear expansion coefficient, where the rate of thickness of the high elastic modulus layer in the insulating resin layer is in the range of 3-45%.
Description
Technical field
The present invention relates to flexible laminose plate and manufacture method thereof, in field of electronic materials, the special flexible laminose plate that is constituted by metal forming and polyimide insulative resin bed that is being adopted in order to form circuit.
Background technology
Kapton is all superior at aspects such as thermal characteristics, insulating properties, solvent resistances, uses the material as electrical/electronic machine parts such as mobile phones widely.In recent years, with the slimming of mobile phone etc., the evolution of multifunction, the substrate that its machine parts material is carried changes flexible printed circuit into from rigid substrates.So flexible printed circuit is to be extensive use of flexible laminose plate, wherein Yi Bufen flexible laminose plate is to use adherence resins such as epoxy resin at the insulating resin layer with the metal forming adjacency, and the insulating resin layer of basal part then uses polyimide resin.But, in response to Pb-free solder in recent years, time shortening, high efficiency with the semiconductor subassembly installation, temperature, pressure when prediction is installed will rise, this situation, when using the flexible laminose plate of epoxy resin,, thereby have and point out to produce difficult problem of installing in response to high temperature because the thermal characteristics such as hear resistance of epoxy resin are on the low side.
So, known as patent documentation 1 just develop with the insulating resin layer of metal forming adjacency, use the flexible laminose plate of the higher polyimide resin of hear resistance, but, even the double-deck flexible laminose plate that this kind is made of metal forming and polyimide resin layer, because up to now still need be on insulating resin layer laminated metal forming, thereby the polyimide resin layer of metal forming institute adjacency just generally uses the thermoplasticity polyimide resin.But, even use the flexible laminose plate of at present known thermoplasticity polyimide resin, in fact, and can't bear the superior thermal characteristics of installing, and not possess all characteristic of flexible laminose plate in response to high temp/high pressure semiconductor subassembly that condition is implemented.
[patent documentation 1] WO02/085616 communique
[patent documentation 2] Japan Patent spy opens the 2003-338525 communique
[patent documentation 3] Japan Patent spy opens the 2003-264374 communique
On the other hand, with the requirement of e-machine miniaturization, just there is exploitation that the technology of semiconductor subassembly is installed on the wiring substrate that forms circuit.For example just disclose about semiconductor device and manufacture method thereof at patent documentation 2, containing its record technology in the technology of interior similar approach, when in the middle of resin occupy, being installed on semiconductor subassembly on the wiring substrate, in order to make resinous principle sclerosis placed in the middle or softening, just semiconductor subassembly is heated to high temperature with the encapsulation anchor clamps.About this heating-up temperature, in patent documentation 2, put down in writing and be heated to more than 280 to 300 ℃, but this temperature will be with the characteristic of resin placed in the middle about, be heated to usually more than 250 ℃.In addition, also there is resin not placed in the middle, but makes adjacent metal form the method for eutectic mutually, in the case, will be heated to higher temperature.As patent documentation 2, semiconductor subassembly is to the installation of substrate, be under heating, with the projection of semiconductor subassembly towards the conductor layer pressurization of wiring substrate and install, in the case, the jut of the semiconductor subassembly projection of the conductor circuit institute adjacency of laminated plates etc., because under the condition of high temperature, be crimped on the substrate and push then, therefore if wiring substrate on the low side in abutting connection with the hear resistance of resin bed, or belong to the words of soft material, to produce the pressure concentration phenomenon with temperature in the office, convergence part, circuit on the resin bed of wiring substrate, or part semiconductor assembly, depression in the insulating resin layer of substrate, can't be carried out stable unfavorable condition of installing and produce.
Though the problems referred to above are filled inorganic material in wiring substrate, just the situation that might solve still in the case, can't keep the bendability of wiring substrate etc., cause only using in the field that is different from industrial use flexible laminose plate.The relevant heat-resistant resin constituent that is conceived to the elastic modelling quantity of heat-resistant resin under high temperature (300 ℃), and using the technology of its multi-layered wiring board, is to put down in writing to some extent in patent documentation 3.But; the resin combination that patent documentation 3 is put down in writing; can use the surface protection film as semiconductor chip, the interlayer dielectric of semiconductor packages, the aspects such as substrate interlayer dielectric that the confession semiconductor subassembly is installed usefulness; but in fact under the state that keeps the pliability characteristic; discussion when being applicable to semiconductor installation purposes still dislikes not enough; and same with known flexible laminose plate, do not consider that design is to installing being suitable for of purposes.
Summary of the invention
The present invention provide a kind of do not undermine and metal forming between adherence, and can promote metal forming in abutting connection with the glass transition temperature (Tg) of polyimide resin, with high-temperature area (350 ℃) in storage elastic modulus, can obtain bearing the superior flexible laminose plate of heat-resistant quality of high temperature mounting condition by this.
In order to solve above-mentioned problem through deeply inquiring into the result, the inventor finds to be designed to particular configuration by the insulating resin layer structure with flexible laminose plate, just can become through promoting the flexible laminose plate of heat-resistant quality, finishes the present invention.
In other words, flexible laminose plate of the present invention is on the single or double of insulating resin layer, has the flexible laminose plate of metal forming; Wherein, insulating resin layer is made of the multilayer polyimide resin, and with metal forming in abutting connection with the polyimide resin of one deck at least, be 1 * 10 at 350 ℃ storage elastic modulus
8To 2 * 10
9Pa, glass transition temperature are formed by 300 to 400 ℃ high resiliency resin bed; And the resin bed except that the high resiliency resin bed, having one deck linear expansion coefficient at least is 20 * 10
-6The low heat expansion resin bed that/K is following, and the high resiliency resin layer thickness ratio of insulating resin layer is in 3 to 45% scopes.
Wherein, by satisfy following important document any one or more than, can form better flexible laminose plate: 1) both sides of low heat expansion resin bed are the high resiliency resin bed; 2) formation is to use by pyromellitic acid anhydride and diamines obtained with the polyimide resin of the high resiliency resin bed of metal forming adjacency, diamines be to use contain 5 to 80 moles of % be selected from 2, two [4-(the 4-amido phenoxy group) phenyl] propane, 1 of 2-, two (the 4-amido phenoxy group) benzene, 1 of 4-, at least a diamines person in two (the 4-amido phenoxy group) benzene of 3-, 4,4 ＇-two (the 4-amido phenoxy group) biphenyl; Or 3) with the surface roughness (Rz) of the metal foil surface of polyimide resin layer adjacency in 0.6 to 1.0 mu m range.
Moreover the manufacture method of flexible laminose plate of the present invention is made of one deck metal forming at least and two layers of polyimide resin at least; Include following step: 1) on the metal foil surface of surface roughness (Rz) in 0.6 to 1.0 mu m range, the storage elastic modulus that is coated on 350 ℃ is 1 * 10
8To 2 * 10
9Pa, glass transition temperature are the step of polyimides predecessor resin of 300 to 400 ℃ high resiliency resin bed; 2) on above-mentioned polyimides predecessor resin bed, the coating line coefficient of expansion is 20 * 10
-6The step of the polyimides predecessor resin of the low heat expansion resin bed that/K is following; And 3) under the state that multilayer polyimide predecessor resin bed is set on the metal forming, implement the step that thermmohardening is handled.
Below, relevant flexible laminose plate of the present invention is described in detail in detail.
Flexible laminose plate of the present invention is made of insulating resin layer and metal forming, has metal forming on the single or double of insulating resin layer.Wherein, insulating resin layer is made of the multilayer polyimide resin, with at least one strata imide resin layer of metal forming adjacency, is to be 1 * 10 at 350 ℃ of storage elastic modulus
8To 2 * 10
9Pa, the high resiliency resin bed of glass transition temperature in 300 to 400 ℃ of scopes form.In addition, in insulating resin layer, the thickness ratio of this high resiliency resin bed must be in 3 to 45% scopes.In addition, the high resiliency resin bed is preferably in abutting connection with the both sides that are arranged at the low heat expansion resin bed.
Polyimide resin used in the present invention be suitably select for use known diamino compound, with tetrabasic carboxylic acid or its acid anhydrides, with its combination after, in organic solvent, react, can be fit to constitute each layer of insulating resin layer characteristic person.Among the present invention, when claiming " polyimide resin ", be meant that polyimide resin or polyamide-imide resin to have the acid imide bond in the molecule are principal component, may not be single polyimide resin, also can be mixture with other resin according to situation.When with the situation of other resin resulting mixture, other resin is to contain below 30%, is preferably in below 20%.In addition, if more a spot of words, though also adjustablely allocate inorganic filling material into, these prescriptions probably will undermine folding resistance and the circuit fabrication that flexible laminose plate of the present invention has, thereby preferably keep micro-state.Essence, insulating resin layer preferably is made of polyimide resin layer.
Among the present invention, constitute 350 ℃ of storage elastic modulus 1 * 10
8To 2 * 10
9The polyimide resin (hereinafter to be referred as " high resiliency polyimide resin ") of the high resiliency resin bed (hereinafter to be referred as " high resiliency resin bed ") in Pa, 300 to 400 ℃ of scopes of glass transition temperature, there is no particular restriction under the prerequisite of its characteristic satisfying, but be preferably the polyimide resin with structural units shown in the following general expression (I).
[changing 1]
In the general expression (I), Ar
1, Ar
3Be the divalent aromatic residue of carbon number more than 12; Ar
2Be the 4 valency aromatic residues of carbon number more than 6; Each component unit molar ratio when k, 1 is meant k+1=100, k are 20 to 95,1 to be 80 to 5 numerical value.
Wherein, Ar
1Be preferably suc as formula divalent base shown in (a).
[changing 2]
Moreover, Ar
2Be preferably suc as formula 4 valency bases shown in (b).
[changing 3]
Ar
3Be preferably wantonly more than 1 suc as formula in the divalent base shown in (c) to (g), wantonly with (e), (f) and (g) is good more than 1 especially.
[changing 4]
The high resiliency polyimide resin must be 1 * 10 at 350 ℃ storage elastic modulus
8To 2 * 10
9In the Pa scope, especially with 1 * 10
8To 1 * 10
9The Pa scope is good.If this numerical value is lower than 1 * 10
8Pa for example when high temperature is down installed semiconductor subassembly, installs in temperature in this, will be flow regime with the insulating resin layer of metal forming adjacency, causes taking place easily metal wiring depression situation.Otherwise the storage elastic modulus of high resiliency resin surpasses 2 * 10
9Pa, though with regard to thermal characteristics viewpoint under the high temperature of the object of the invention, will belong to preferable situation, the flexibility that highlights the flexible laminose plate flexural property probably will reduce.In addition, the high resiliency resin bed is that glass transition temperature (Tg) must be in 300 to 400 ℃ of scopes, preferably with in 325 to 380 ℃ of scopes, more preferably in 350 to 380 ℃ of scopes.If the glass transition temperature is lower than 300 ℃, will the situation of metal wiring depression take place easily as above-mentioned, and the scolding tin hear resistance of flexible laminose plate also will worsen.Otherwise,, can't obtain good adherence between polyimide layer and metal forming if the glass transition temperature surpasses 400 ℃.
The insulating resin layer of flexible laminose plate of the present invention is made of multilayer, except that above-mentioned high resiliency resin bed, still has linear expansion coefficient 20 * 10
-6Below/the K, best 1 * 10
-7/ K to 20 * 10
-6The low heat expansion resin bed of/K.Constitute the polyimide resin (following also claim " low heat expansion polyimide resin ") of low heat expansion resin bed, there is no particular restriction under the prerequisite of its characteristic satisfying, but be preferably the polyimide resin with structural units shown in the following general expression (II).
[changing 5]
Wherein, R
1, R
2Be meant and can be the identical low alkyl group that also can be inequality; Q, r are respectively 0 to 4 numerical value.Ar
4Be preferably following formula (h) with (i) shown in 4 valency bases more than 1.In addition, in formula (1), X is meant SO
2, CO, O or direct bond.
[changing 6]
In the unit structure, be preferably structural units shown in the following formula (III) shown in the above-mentioned general expression (II).
[changing 7]
General expression (II) or (III) shown in structural units, 50 moles of total polyimide structures unit that can contain the low heat expansion polyimide resin are more than the %.
Metal forming used in the present invention has Copper Foil, stainless steel foil, Alloy Foil etc.Wherein, so-called " Alloy Foil " is meant and must contains Copper Foil, and contain at least a above metal forming in the elements such as chromium, nickel, zinc, silicon, the metal forming of copper containing ratio more than 90%.When the situation of using metal forming, also can utilize zinc-plated, nickel plating, silane coupling agent etc. to implement surface treatment.
Along with the ultra fine-pitchization of metal wiring, preferably use thin metal forming.With regard to viewpoint from then on, best metal paper tinsel thickness is 5 to 35 μ m, and the scope with 8 to 18 μ m is good especially.In addition, to be preferably in the surface roughness (Rz) with adjacent of polyimide resin be 0.6 to 1.0 mu m range to employed metal forming.When surface roughness (Rz) is lower than 0.6 μ m, can't keep the adherence between metal forming and polyimide resin layer, otherwise, the situation more than 1.0 μ m, the transparency of Kapton will reduce, and will hinder the installation of semiconductor subassembly.In addition, be set in the above-mentioned scope by the surface roughness (Rz) with metal forming, the metal ingredient that will be taken place in the time of can reducing circuit fabrication remains in the situation of polyimide resin layer.As above-mentioned, the metal forming of surface roughness (Rz) in above-mentioned scope will quite be suitable for the ultra fine-pitchization of metal wiring.
Flexible laminose plate of the present invention is the multi-ply construction that insulating resin layer constituted that is formed by the multilayer polyimide resin, and by will with at least one strata imide resin layer of metal forming adjacency, be set at the above-mentioned high resiliency resin bed of specific thicknesses scope, just can form the flexible laminose plate that can bear the high temp/high pressure mounting condition.Wherein, be set at above-mentioned scope by thickness and surface roughness (Rz), then especially applicable to the high-density installation purposes with metal forming.
Flexible laminose plate of the present invention is the multi-ply construction that insulating resin layer constituted that is formed by the multilayer polyimide resin, but best layer structure illustration is as following 1) to 5) shown in layer structure.Wherein, M is a metal forming, and H is the high resiliency polyimide resin, and L is the low heat expansion polyimide resin, and P can not satisfy the storage elastic modulus of H or L or other polyimide resin of linear expansion coefficient.
1)M/H/L、2)M/H/L/H/M、3)M/H/L/H、4)M/H/L/P/M、5)M/H/L/P、
And the shared thickness ratio of the H in the insulating resin layer is 3 to 45%, is preferably in 5 to 20% scopes.Other polyimide resin P when being provided with for situation such as the warpage after controlling the metal forming etching, preferably uses the resin of the approximate H of physical characteristic, especially with and H between the linear expansion coefficient difference 10 * 10
-6/ K is good with interior person.In order to be formed on the flexible laminose plate that insulating resin layer has metal forming on two-sided, to be more favourable way thereafter metal forming being implemented the method add thermo-compressed, institute in this case, the polyimide resin P of and lamination adjacent with L is preferably linear expansion coefficient 30 * 10
-6The thermoplasticity polyimide resin that/K is above.
Secondly, though the manufacture method of bright flexible laminose plate of the present invention, just identical content is put in order simple declaration in the flexible laminose plate that has illustrated.
Flexible laminose plate of the present invention is on metal forming, and coating polyimides predecessor resin after drying, is implemented thermmohardening and handled, and just can be formed on the laminated plates that lamination on the metal forming single face polyimide resin layer.The polyimides predecessor resin that is coated with on metal forming is preferably solution state, normally is coated with according to the state that is dissolved in the appropriate solvent.The metal foil surfaces that polyimides predecessor resin is coated with, surface roughness (Rz) is preferably in 0.6 to 1.0 mu m range.In the manufacture method of flexible laminose plate of the present invention, the direct polyimides predecessor resin of coating on metal forming is sclerosis back at 350 ℃ storage elastic modulus 1 * 10
8To 2 * 10
9Pa, glass transition temperature are 300 to 400 ℃ high resiliency resin bed.With constituting the predecessor resin of this high resiliency resin bed, directly coat on the metal forming, just can obtain the stable adhesion strength of metal-polyimide resin.The means and without particular limitation of coating, can suitably select to adopt as: rod is coated with mode, plate gravure coating method, print roll coating mode, die head coating method isoperimetric perception method.
The polyimides predecessor resin bed that metal forming was coated with when the situation that contains solvent, just is dried to proper range.The baking temperature of this moment is preferably under the temperature that polyimides predecessor resin bed do not carry out imidization reaction and implements, particularly, is preferably in below 150 ℃, and be good with 110 to 140 ℃ of scopes especially.In addition, utilize this drying steps, contained quantity of solvent in the polyimides predecessor resin bed preferably is equivalent to below 50 weight portions of polyimides predecessor resin 100 weight portions with formation.
Flexible laminose plate of the present invention except that the polyimide resin layer of above-mentioned high resiliency resin bed, still has linear expansion coefficient 20 * 10
-6The polyimide resin layer of the low heat expansion resin bed that/K is following.The low heat expansion resin bed is best, as above-mentioned on the polyimides predecessor resin bed of the formation high resiliency resin bed that forms, be coated with and form with its predecessor state.The predecessor resin of this low heat expansion resin preferably also is to be coated with solution state, when situation about being coated with the state that contains solvent, preferably carries out drying as above-mentioned condition.
On metal forming, coating constitutes the predecessor resin bed of high resiliency resin bed and low heat expansion resin bed respectively one by one, after drying, in order to control warpage situation after the metal forming etching etc., one deck polyimides predecessor resin bed is set preferably again.Wherein, preferably identical with above-mentioned high resiliency resin bed or the physical characteristic of layer of institute's lamination is approximate, especially with the difference of high resiliency resin bed and linear expansion coefficient 10 * 10
-6/ K is good with interior person.In order to be formed on the flexible laminose plate that has metal forming on insulating resin layer two-sided, thereafter by being implemented the method that adds thermo-compressed, metal forming will be favourable way, the institute in this case, the polyimide layer of institute's lamination on the low heat expansion resin bed, preferably linear expansion coefficient is 30 * 10
-6The thermoplasticity polyimide resin that/K is above.The polyimide resin layer that is provided with arbitrarily in the flexible laminose plate of the present invention also as the formation method of above-mentioned two polyimide layers, just can form through coating, drying.
As above-mentioned, if on metal forming, the polyimides predecessor resin bed 2 or 3 or more is implemented after coating, the drying, again to the execution heat treated of the multilayer polyimide predecessor resin bed on the metal forming and thermmohardening.Heat treated is preferably implemented by most hardening cabinets, in the case, according to plural number section, stage intensification, finally is heated to more than 250 ℃ near 150 ℃, preferably reaches more than 300 ℃ and imidizate.If imidizate and to implement the maximum heating temperature of heating too high, resin probably will decompose, thereby had better not be heated to than kick off temperature and hang down more than 20 ℃ the temperature.In addition, this heat treated also can be followed after the above-mentioned drying steps, continues to adopt same apparatus to implement.By this step, but the just imidizate of essence of polyimides predecessor resin.
Finish on the resin bed of imidizate, cooperating necessity lamination metal forming again.The lamination method be will be predetermined metal forming under heating between punching press or roller, pressurization and the method implemented is comparatively easy.Wherein, heating-up temperature is preferably in more than the glass transition temperature with the adjacent polyimide resin layer of institute lamination metal forming.In addition, can be in the metal forming of this lamination as above-mentioned metal forming, when utilizing the heating pressurized treatments to implement the situation of lamination, for can keep and polyimides between adhesion strength, Rz is with comparatively favourable greater than 1.0 μ m.
The polyimide resin of metal level of the present invention institute adjacency because have up to now the adherence polyimide resin inaccessiable high Tg, at 350 ℃ high storage elastic modulus, therefore will keep and metal forming between high adhesion.So therefore flexible laminose plate of the present invention quite is suitable for when being the high temperature installation of semiconductor subassembly because the heat-resistant quality of insulating resin layer is superior, the COF that is adopted (membrane of flip chip) (Chip On Film) uses flexible laminose plate.In addition, flexible laminose plate of the present invention is made of the multilayer insulation resin bed, not only the polyimide resin thermal characteristics of its insulating resin layer is higher, and the needed high bendability of sweep with mobile phone etc., therefore can be used in miniature electric machine contexts such as mobile phone, belong to invention with industrial value.
The specific embodiment
Below, describe at one embodiment of the invention.In addition, each film physics value is to measure according to following method.
1) storage elastic modulus of glass transition temperature (Tg), high-temperature area (350 ℃), it is polyimides predecessor Kapton that resin obtains with each synthesis example, utilize the Measurement of Dynamic Viscoelasticity device of PheometricScientific corporate system, measure according to 5 ℃/ dynamic viscoelastic when min heats up, ask for the storage elastic modulus of Tg (maximum of tan δ) and 350 ℃.
2) thermal coefficient of expansion is the TMA100 type thermo-mechanical analysis device that adopts Seiko industrial group system, according to 20 ℃/min programming rate, 5 ℃/min cooling rate, and the change in size when asking for cooling between from 100 ℃ to 240 ℃.
3) and the adhesion strength between steel foil, be to adopt Japan smart device system Strograph R-1, at normal temperatures,, spend direction stretching Copper Foils towards 180 according to load measuring gauge 2kg, chuck speed 50mm/min, try to achieve after measured.The assessment benchmark is to cooperate adhesion strength, according to following the evaluation.
Zero: more than the adhesion strength 0.8kN/m
△: adhesion strength 0.5kN/m is above, be lower than 0.8kN/m
*: adhesion strength is lower than 0.5kN/m
4) surface roughness of metal forming (Rz) is according to JIS B 0651, uses high sensitivity surface distributed instrument (KLA-Tencor corporate system P-15), measures according to the condition of finding speed 0.02mm/sec, radius of curvature 2 μ m.
5) the scolding tin hear resistance of flexible laminose plate be in the solder bath of institute's fixed temperature 10 seconds of dipping, peel off in unlikely generation metal forming, in the temperature of phenomenon such as resin expansion, maximum temperature be considered as the scolding tin heat resisting temperature.
Code name explanation among the embodiment.
DMAc:N, N ＇-dimethylacetylamide
PMDA: pyromellitic acid anhydride
BPDA:3,3 ＇, 4,4 ＇-biphenyl tetracarboxylic dianhydride
DSDA: hexichol sulfo group-3,4,3 ＇, 4 ＇-tetracarboxylic dianhydride
BTDA: benzophenone-3,4,3 ＇, 4 ＇-tetracarboxylic dianhydride
BAPP:2, two [4-(the 4-amido phenoxy group) phenyl] propane of 2-
BAPB:4,4 ＇-two (4-amido phenoxy group) biphenyl
TPE-Q:1, two (the 4-amido phenoxy group) benzene of 4-
TPE-R:1, two (the 4-amido phenoxy group) benzene of 3-
M-TB:2,2 ＇-dimethyl-4,4 ＇-benzidine
Synthesis example 1 to 3
Be supplied among the DMAc BAPP and BAPB and dissolving, then supply PMDA again, stir about is 3 hours in room temperature, just modulates at constituent constituted shown in the table 1 polyimides predecessor resin solution.
In addition, in all synthesis examples, the ratio of tetracarboxylic dianhydride's composition and two amine components is set at about 100 moles of % stoichiometries.In addition, the numerical value of the composition of the resin raw material in the table 1 field is meant molar ratio.
The polyimides predecessor resin solution of gained is coated on the Copper Foil, in the temperature below 140 ℃, the predecessor resin layer surface is dried to tack-free state, in 150 to 360 ℃ of temperature ranges, separately count the heating that heats up in stage then, just form the Kapton of thickness 25 μ m through imidizate.At this Kapton, be determined at 350 ℃ storage elastic modulus, glass transition temperature (Tg), reach linear expansion coefficient.The result is as shown in table 1.
Synthesis example 4,5
Be supplied among the DMAc BAPP and TPE-Q and dissolving, then supply PMDA again, stir about is 3 hours in room temperature, just modulates at constituent constituted shown in the table 1 polyimides predecessor resin solution.This polyimides predecessor resin solution is handled according to synthesis example 1 identical method, and forms Kapton, and assesses its rerum natura.The result is as shown in table 1.
Synthesis example 6,7
Be supplied among the DMAc BAPP and TPE-R and dissolving, then supply PMDA again, stir about is 3 hours in room temperature, just modulates at constituent constituted shown in the table 1 polyimides predecessor resin solution.This polyimides predecessor resin solution is handled according to synthesis example 1 identical method, and forms Kapton, and assesses its rerum natura.The result is as shown in table 1.
Synthesis example 8
BAPP is supplied among the DMAc and dissolving, then supplies PMDA, DSDA more in regular turn, stir about is 3 hours in room temperature, just modulates at constituent constituted shown in the table 1 polyimides predecessor resin solution.This polyimides predecessor resin solution is handled according to synthesis example 1 identical method, and forms Kapton, and assesses its rerum natura.The result is as shown in table 1.
Synthesis example 9
BAPP is supplied among the DMAc and dissolving, then supplies PMDA, BTDA more in regular turn, stir about is 3 hours in room temperature, just modulates at constituent constituted shown in the table 1 polyimides predecessor resin solution.This polyimides predecessor resin solution is handled according to synthesis example 1 identical method, and forms Kapton, and assesses its rerum natura.The result is as shown in table 1.
Synthesis example 10
BAPP is supplied among the DMAc and dissolving, then supplies PMDA again, stir about is 3 hours in room temperature, just modulates at constituent constituted shown in the table 1 polyimides predecessor resin solution.This polyimides predecessor resin solution is handled according to synthesis example 1 identical method, and forms Kapton, and assesses its rerum natura.The result is as shown in table 1.
Synthesis example 11
BAPB is supplied among the DMAc and dissolving, then supplies PMDA again, stir about is 3 hours in room temperature, just modulates at constituent constituted shown in the table 1 polyimides predecessor resin solution.This polyimides predecessor resin solution is handled according to synthesis example 1 identical method, and forms Kapton, and assesses its rerum natura.The result is as shown in table 1.
Table 1
Synthesis example 12
M-TB is supplied among the DMAc and dissolving, then supplies PMDA again, stir about is 3 hours in room temperature, just modulate polyimides predecessor resin solution.This polyimides predecessor resin solution is handled according to synthesis example 1 identical method, and forms Kapton, linear expansion coefficient after measured, and the result is 2.5ppm.
Embodiment 1
At thickness 12 μ m, surface roughness Rz is on the Copper Foil of 0.7 μ m, with synthesis example 1 modulate polyimides predecessor resin solution, be that the mode of 6 μ m is coated with according to the thickness after the sclerosis, and in being lower than 140 ℃ temperature, carry out 5 minutes dryings.Above this, the polyimides predecessor resin solution that synthesis example 12 is modulated is that the mode of 29 μ m is coated with according to the thickness after the sclerosis, and carries out 15 minutes dryings in being lower than 140 ℃ temperature.More on these two-layer polyimides predecessor resin beds, the polyimides predecessor resin solution that synthesis example 1 is adjusted, according to the thickness after the sclerosis is that the mode of 6 μ m is coated with, and in being lower than 140 ℃ temperature, carry out 5 minutes dryings, in 150 to 360 ℃ temperature range, separately count the stage, interim intensification heating 15 minutes can make the flexible laminose plate that has Copper Foil on the insulating resin layer single face.
Copper Foil to the acquisition flexible laminose plate utilizes etch processes, be processed as decide circuit.At this flexible laminose plate, the adherence between assessment and Copper Foil, and assessment scolding tin hear resistance, result demonstrate and Copper Foil between adherence reach more than the 0.8kN/m, the scolding tin heat resisting temperature reaches the good result more than 400 ℃.Assessment result is as shown in table 2.
Embodiment 2 to 7
In embodiment 1,, change into prepared resin bed in the synthesis example 2 to 7, and make flexible laminose plate forming the polyimides predecessor resin bed kind of the high resiliency resin bed of ground floor and the 3rd layer.At the high resiliency resin aspect of this flexible laminose plate, assess and Copper Foil between adherence, scolding tin hear resistance.Assessment result is as shown in table 2.
Comparative example 1 to 4
In embodiment 1,, change into prepared resin bed in the synthesis example 8 to 11, and make flexible laminose plate forming the polyimides predecessor resin bed kind of the high resiliency resin bed of ground floor and the 3rd layer.At this flexible laminose plate the ground floor resin is used as assessment face, assess and Copper Foil between adherence, scolding tin hear resistance.Assessment result is as shown in table 2.
(table 2)
| The polyimides predecessor resin bed kind of ground floor and the 3rd layer | And the adherence between Copper Foil | The scolding tin heat resisting temperature (℃) | |
| Embodiment 1 | Synthesis example 1 | ○ | ≥400 |
| Embodiment 2 | Synthesis example 2 | ○ | ≥400 |
| Embodiment 3 | Synthesis example 3 | ○ | ≥400 |
| Embodiment 4 | Synthesis example 4 | ○ | ≥400 |
| Embodiment 5 | Synthesis example 5 | ○ | ≥400 |
| Embodiment 6 | Synthesis example 6 | ○ | ≥400 |
| Embodiment 7 | Synthesis example 7 | ○ | ≥400 |
| Comparative example 1 | Synthesis example 8 | ○ | 370 |
| Comparative example 2 | Synthesis example 9 | △ | 360 |
| Comparative example 3 | Synthesis example 10 | ○ | 390 |
| Comparative example 4 | Synthesis example 11 | × | ≥400 |
Claims (3)
1. a flexible laminose plate is the flexible laminose plate that has metal forming on the single or double of insulating resin layer; It is characterized in that: insulating resin layer is made of the multilayer polyimide resin, wherein with the polyimide resin of one deck at least of the metal forming adjacency of surface roughness in 0.6 to 1.0 mu m range, is to be 1 * 10 by the storage elastic modulus at 350 ℃
8To 2 * 10
9Pa, glass transition temperature are formed by 325 to 380 ℃ the high resiliency resin bed with polyimide resin of structural units shown in the following general expression (I); Resin bed beyond the high resiliency resin bed, having one deck at least is that linear expansion coefficient is 20 * 10
-6The low heat expansion resin bed that/K is following, and the high resiliency resin layer thickness ratio of insulating resin layer is in 3 to 45% scopes;
In the general expression (I), Ar
1Be the divalent aromatic residue shown in the formula (a), Ar
3Be the wantonly more than 1 of the divalent aromatic residue shown in the formula (c) to (g), Ar
2Be 4 valency aromatic residues shown in the formula (b); K, each the component unit molar ratio when l is meant k+l=100, k are 20 to 95, l is 80 to 5 numerical value.
2. flexible laminose plate as claimed in claim 1, it is characterized in that: the polyimide resin of the high resiliency resin bed of formation and the metal forming adjacency of surface roughness in 0.6 to 1.0 mu m range, be to use by pyromellitic acid anhydride and diamines obtained, and diamines be to use contain 5 to 80 moles of % be selected from 2, two [4-(the 4-amido phenoxy group) phenyl] propane, 1 of 2-, two (the 4-amido phenoxy group) benzene, 1 of 4-, two (4-amido phenoxy group) benzene of 3-, and 4,4 '-at least a in two (4-amido phenoxy group) biphenyl.
3. the manufacture method of a flexible laminose plate is made of one deck metal forming at least and two layers of polyimide resin at least, it is characterized in that: comprise following steps:
1) on the metal foil surface in surface roughness is 0.6 to 1.0 mu m range, coating constitutes the step of the polyimides predecessor resin of high resiliency resin bed, and wherein this high resiliency resin bed is to be 1 * 10 by the storage elastic modulus at 350 ℃
8To 2 * 10
9Pa, glass transition temperature are formed by 325 to 380 ℃ the high resiliency resin bed with polyimide resin of structural units shown in the following general expression (I);
2) on this polyimides predecessor resin bed, coating constitutes linear expansion coefficient 20 * 10
-6The step of the polyimides predecessor resin of the low heat expansion resin bed that/K is following; And
3) under the state that multilayer polyimide predecessor resin bed is set on the metal forming, carry out the step that thermmohardening is handled;
In the general expression (I), Ar
1Be the divalent aromatic residue shown in the formula (a), Ar
3Be the wantonly more than 1 of the divalent aromatic residue shown in the formula (c) to (g), Ar
2Be 4 valency aromatic residues shown in the formula (b); K, each the component unit molar ratio when l is meant k+l=100, k are 20 to 95, l is 80 to 5 numerical value.
Applications Claiming Priority (6)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2004-206016 | 2004-07-13 | ||
| JP2004206016 | 2004-07-13 | ||
| JP2004206016 | 2004-07-13 | ||
| JP2005149069A JP4619860B2 (en) | 2004-07-13 | 2005-05-23 | Flexible laminate and method for manufacturing the same |
| JP2005-149069 | 2005-05-23 | ||
| JP2005149069 | 2005-05-23 |
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| CN1733473A CN1733473A (en) | 2006-02-15 |
| CN1733473B true CN1733473B (en) | 2010-10-13 |
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| JP (1) | JP4619860B2 (en) |
| KR (1) | KR101258569B1 (en) |
| CN (1) | CN1733473B (en) |
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| KR100926884B1 (en) * | 2006-04-27 | 2009-11-16 | 에스케이에너지 주식회사 | Flexible Metal Foil Laminate |
| JP4777206B2 (en) * | 2006-09-29 | 2011-09-21 | 新日鐵化学株式会社 | Method for producing flexible copper-clad laminate |
| JP4823953B2 (en) * | 2007-03-27 | 2011-11-24 | 新日鐵化学株式会社 | Method for producing flexible laminate |
| KR101550005B1 (en) * | 2007-08-03 | 2015-09-03 | 가부시키가이샤 가네카 | Multilayer polyimide film, laminate and metal-clad laminate |
| CN101724266B (en) * | 2008-10-20 | 2012-07-04 | 比亚迪股份有限公司 | Polyimide material, preparation method thereof, metal laminated plate containing same and preparation method thereof |
| KR20100048474A (en) * | 2008-10-31 | 2010-05-11 | 에스케이에너지 주식회사 | Flexible metal-clad laminate and a method of manufacturing the same |
| JP5615253B2 (en) | 2010-12-20 | 2014-10-29 | エスケー イノベーション シーオー．， エルティーディー． | Method for producing thick film polyimide flexible metal laminate |
| KR101514221B1 (en) * | 2011-12-07 | 2015-04-23 | 에스케이이노베이션 주식회사 | manufacturing method of multi layer polyimide flexible metal-clad laminate |
| JP2013131423A (en) * | 2011-12-22 | 2013-07-04 | Hitachi Cable Ltd | Electrically insulated electric wire and coil |
| KR101416782B1 (en) * | 2012-04-24 | 2014-07-08 | 에스케이이노베이션 주식회사 | Flexilbe Metal Clad Laminate |
| CN104070772A (en) * | 2014-06-30 | 2014-10-01 | 铜陵浩荣华科复合基板有限公司 | Production process of high-thermal conductivity resin glued copper foil |
| JP7356243B2 (en) * | 2018-03-31 | 2023-10-04 | 日鉄ケミカル＆マテリアル株式会社 | Metal-clad laminates and circuit boards |
| JP7446741B2 (en) * | 2018-09-28 | 2024-03-11 | 日鉄ケミカル＆マテリアル株式会社 | Metal-clad laminates and circuit boards |
| JP7212515B2 (en) * | 2018-12-26 | 2023-01-25 | 日鉄ケミカル＆マテリアル株式会社 | Metal-clad laminates and circuit boards |
| JP7195530B2 (en) | 2019-01-11 | 2022-12-26 | エルジー・ケム・リミテッド | Film, metal-clad laminate, flexible substrate, method for producing film, method for producing metal-clad laminate, and method for producing flexible substrate |
| JP2022154637A (en) | 2021-03-30 | 2022-10-13 | 日鉄ケミカル＆マテリアル株式会社 | Polyimide, metal clad laminate sheet and circuit board |
| JP2023051810A (en) | 2021-09-30 | 2023-04-11 | 日鉄ケミカル＆マテリアル株式会社 | Metal-clad laminate, circuit board, electronic device and electronic apparatus |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0496334A1 (en) * | 1991-01-23 | 1992-07-29 | Chisso Corporation | A flexible base laminated with metal on both the surfaces and a process for producing same |
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| JPH01245586A (en) * | 1988-03-28 | 1989-09-29 | Nippon Steel Chem Co Ltd | Flexible printed board |
| JP4508441B2 (en) * | 2001-02-16 | 2010-07-21 | 新日鐵化学株式会社 | Laminated body and method for producing the same |
| TWI300744B (en) * | 2001-04-19 | 2008-09-11 | Nippon Steel Chemical Co | |
| JP4457542B2 (en) * | 2001-06-22 | 2010-04-28 | 宇部興産株式会社 | Multi-layer polyimide film with thermocompression bonding, heat-resistant copper-clad board |
| JP3976532B2 (en) * | 2001-09-28 | 2007-09-19 | 東レ・デュポン株式会社 | Multilayer polyimide film for polymer optical waveguide substrate, polyimide laminate for polymer optical waveguide substrate, and polymer optical waveguide |
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- 2005-05-23 JP JP2005149069A patent/JP4619860B2/en active Active
- 2005-06-30 TW TW094122032A patent/TWI344804B/en active
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0496334A1 (en) * | 1991-01-23 | 1992-07-29 | Chisso Corporation | A flexible base laminated with metal on both the surfaces and a process for producing same |
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| Publication number | Publication date |
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| TW200603687A (en) | 2006-01-16 |
| CN1733473A (en) | 2006-02-15 |
| JP2006051800A (en) | 2006-02-23 |
| TWI344804B (en) | 2011-07-01 |
| KR101258569B1 (en) | 2013-05-02 |
| KR20060050123A (en) | 2006-05-19 |
| JP4619860B2 (en) | 2011-01-26 |
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