CN1720136A - Laminate, printed wiring board and method for manufacturing them - Google Patents

Laminate, printed wiring board and method for manufacturing them Download PDF

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CN1720136A
CN1720136A CN 200380105189 CN200380105189A CN1720136A CN 1720136 A CN1720136 A CN 1720136A CN 200380105189 CN200380105189 CN 200380105189 CN 200380105189 A CN200380105189 A CN 200380105189A CN 1720136 A CN1720136 A CN 1720136A
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laminated body
metal level
thermoplastic polyimide
layer
polyimide layer
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西中贤
伊藤卓
田中滋
村上睦明
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Kaneka Corp
Kanegafuchi Chemical Industry Co Ltd
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Kaneka Corp
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Abstract

The invention provides a laminate which can be used for forming a high density circuit thereon, with good resistance to further processing such as decontamination and excellent adhesion, and excellent adhesion reliability in a high temperature atmosphere, as well as a print circuit wiring board, that is, the invention relates to a laminate and a print circuit wiring board, comprising a thermoplastic polyimide film layer and a metal layer which are formed on one side or two sides thereof or a non-thermoplastic polyimide film layer.

Description

Laminated body, printed circuit board and their manufacture method
Technical field
The present invention relates to a kind of be widely used in electric and electronic etc., form the laminated body of copper metal layer on the macromolecule membrane of smooth surface and use this laminated body and the manufacture method of the printed circuit board that forms having.Particularly relate to the metal-containing layer/polyimide film layer of the most suitable circuit substrate manufacturing 2 layers of structure laminated body, comprise the laminated body of the 3-tier architecture of metal level/polyimide film layer/metal level, metal level/polyimide film layer/copper foil layer or metal level/polyimide film layer/adhesive linkage.In more detail, relate to and to use through hole to form operation, and the manufacturing process of common printed circuit board such as decontamination operation, cementability and environmental stability excellence, and can be used in the high density flexible printed circuit board, the multi-layer flexible printed circuit board of lamination flexible printed circuit board, the flexible rigid circuit wiring plate of lamination flexible printed circuit board and rigid printed circuit wiring plate, the combinational circuit wiring plate, TAB (Tape Automated Bonding) is with being with, COF (the Chip On film) substrate of semiconductor element directly is installed at printed circuit board, and the printed circuit board and the manufacture method thereof of MCM (Multi ChipModule) substrate etc.
Background technology
Printed circuit board at circuit forming surface is widely used in installing electronic component and semiconductor element etc.Be accompanied by the miniaturization of e-machine in recent years and the requirement of multifunction, expect such densification of printed circuit board circuit and slimming strongly.Particularly the establishment that is spaced apart the fine circuits formation method below 25 μ m/25 μ m or the 25 μ m/25 μ m of line/distance (L/S) is the important topic in printed circuit board field.
Usually, in printed circuit board, be to realize by the concave-convex surface that is called as anchoring effect as bonding between the macromolecule membrane of substrate and the circuit.Therefore, the operation of roughening film surface generally is set all, usually, is provided with on its surface and is scaled concavo-convex about 3～5 μ m with the Rz value.Such substrate surface is concavo-convex, the L/S value of the circuit that forms is no problem under 30 μ m/30 μ m or the situation more than the 30 μ m/30 μ m, but at 30 μ m/30 μ m or below the 30 μ m/30 μ m, particularly the circuit of the wire spoke below 25 μ m/25 μ m or the 25 μ m/25 μ m forms but becomes great problem.Its reason is, and is so highdensity and be the circuit line of fine rule, is subjected to the concavo-convex influence on aforesaid substrate surface.Therefore, forming L/S value is that the formation of the circuit below 25 μ m/25 μ m or the 25 μ m/25 μ m need be for the circuit formation technology of the high polymeric substrate of surface smoothing.This flatness converts with the Rz value, is 2 μ m or below the 2 μ m, more preferably 1 μ m or below the 2 μ m.Certainly, at this moment, can't realize, therefore, be necessary to develop other adhering method as the above-mentioned anchoring effect of bonding force.
On the other hand, on circuit substrate, when requiring more highdensity fine wiring, require in the hot and humid grade stability under the rigorous environment more.Particularly, for the cementability of macromolecule membrane and wiring, also require the environment of withstand high temperatures high humidity.
Having, is indispensable at the through hole that forms circuit between conductting layer on circuitron wiring plate and the multilayer printed wiring board again.Therefore, above-mentioned printed circuit board usually adds the operation etc. of operation and enforcement electroless plating copper through operation, decontamination operation, the catalyst that is formed through hole by laser and carries out circuit and form.Here, be extensive use of permanganate, carry out as big soups of carrying capacity of environment such as widely-used formaldehyde of electroless plating or EDTA in addition as the decontamination operation.But, need not use the operation of these soups along with the raising of environment in recent years consciousness.
As the operation that realizes these, the manufacture method of the printed circuit board of the vapour deposition method that uses physics such as sputter is studied.As this technology, disclose form on the circuit comprise the insulating barrier and through hole of polyimide resin after, carry out comprehensive sputter, make the insulating barrier that comprises polyimide resin and the method for through hole conductionization.But employed polyimide resin is the non-thermal plasticity polyimides, can not expect that sufficient cementability is arranged (spy opens flat 5-251626 communique).
Have again, circuit is formed with the occasion (spy opens the 2000-198907 communique) of being undertaken by etching, so-called subraction and carries out the occasion that the so-called half add of the etching work procedure of the operation of electrolytic copper plating, the operation of removing etchant resist and unnecessary electroless plating copper sheet film is made by the part that comprises the operation that forms etchant resist, expose to the electroless plating film.Therefore, the cementability between wired circuit and the macromolecule membrane, it is self-evident must be able to standing these operations.
About improving the cementability between Kapton and the wiring, attempted multiple research so far.For example disclose, by in Kapton, adding titanium class organic compound, improve technology (patent 1,948, No. 445 communique (United States Patent (USP)s the 4th of cementability, 742, No. 099 specification)) or, apply by the slaine that comprises Sn, Cu, Zn, Fe, Co, Mn or Pd, (spy opens flat 6-73209 communique (United States Patent (USP) the 5th to improve the polyimides etc. of surperficial bonding force, 227, No. 224 specifications)).In addition, disclose behind coating hear resistance inorganic agent on the polyamic acid cured film, the Kapton of imidizate carries out the method (United States Patent (USP) the 5th, 130, No. 192 specifications) of metallising.Have again, disclose the method (spy opens flat 11-71474 communique) that makes titanium elements be present in the Kapton surface.In addition, disclose on TPI surface by present inventors and to have formed conductor layer by the dry type plating method, it is pressurizeed and heat treatment makes it melting adhered, strengthen the method (spy opens the 2002-113812 communique) of the bonding strength of polyimides and adhesive linkage.
Also have, the research as the cementability of being devoted to metal forming improves discloses metal forming and the bonding method (spy opens flat 8-230103 communique) of TPI of making.
On these Kapton surfaces, compare with the metal level that forms on common Kapton surface with the metal level that physical methods such as evaporation form, have excellent adhesive strength.But, form the operation of through hole and the situation that the decontamination operation is peeled off with Kapton/intermetallic being bonded with of these inventive method manufacturings by laser.
In addition, disclose, carried out the method (spy opens flat 5-90737 communique) that electroless plating covers processing after the Kapton hydrophilicity-imparting treatment.Have again, disclose after implementing electroless plating on the Kapton after the hydrophiling and covering, under active gas environment not, implement heat treated technology (spy opens flat 8-31881 communique).But, these methods with the processing of non-thermal plasticity polyimide resin as prerequisite and above-mentioned same low for the tolerance of decontamination operation.
Summary of the invention
The present invention makes for improving the problems referred to above point, purpose is to provide a kind of printed circuit board, this printed circuit board is, (1) fine circuits that forms strong bond on the Kapton of surface smoothing excellence connects up, (2) realize standing cementability from the operation that formed through hole by laser and decontamination operation to final circuit-formed printed circuit board manufacturing process, (3) are at normality and the printed circuit board that has excellent bonding stability hot and humid time.
In addition, have, other purposes of the present invention are that for environmental consideration, the heavy wet type electroless plating of environment for use load does not cover (4) again.
Present inventors are for addressing the above problem the result who a little scrutinizes repeatedly, developed the 2 layers of structure that comprise metal level/polyimide film layer that satisfy these conditions laminated body, comprise the laminated body of the 3-tier architecture of metal level/polyimide film layer/metal level, metal level/polyimide film layer/copper foil layer or metal level/polyimide film layer/adhesive linkage, so finished the present invention.
Find in addition, the surface treatment of the processing more than a kind or a kind that combination is selected from surface treatment, flame treatment and the hydrophilicity-imparting treatment of ion gun processing, plasma treatment, sided corona treatment, coupling agent processing, permanganate processing, ultraviolet treatment with irradiation, electron ray treatment with irradiation, projected at high velocity grinding agent has the effect that improves metal bonding layer power.
Find that in addition when the deposit element formed metal level on thermoplastic polyimide layer, it was effective that thermoplastic polyimide resin is heated this very easy method.
That is, the present invention relates to comprise the laminated body of the metal level on thermoplastic polyimide layer and thermoplastic polyimide layer surface.
Above-mentioned thermoplastic polyimide layer preferably makes up the processing of selecting more than a kind or a kind and carried out the surface-treated layer from surface treatment, flame treatment and the hydrophilicity-imparting treatment of plasma treatment, sided corona treatment, coupling agent processing, permanganate processing, ultraviolet treatment with irradiation, electron ray treatment with irradiation, projected at high velocity grinding agent.
Above-mentioned thermoplastic polyimide layer is preferably handled by ion gun and is carried out the surface-treated layer.
Above-mentioned ion gun is handled the processing of preferably being undertaken by argon ion.
The preferred limit of above-mentioned metal level heating thermoplastic polyimide layer limit deposit element and the layer that forms.
The heating-up temperature of thermoplastic polyimide layer is preferred more than 100 ℃ or 100 ℃.
Above-mentioned metal level is preferably electroless plating.
The layer that the above-mentioned metal level method of passing through to select from sputtering method, vacuum vapour deposition, ion plating method, electron beam evaporation plating method and chemical vapor deposition method more than a kind or a kind preferably forms.
Above-mentioned metal level preferably comprises the 1st metal level and the 2nd metal level.
Above-mentioned the 1st metal level preferably comprises nickel, cobalt, chromium, titanium, molybdenum, tungsten, zinc, tin, indium, gold or their alloy.
Above-mentioned the 2nd metal level preferably comprises copper or its alloy.
The present invention relates to a kind of laminated body, at least one bread of this laminated body contains non-thermal plasticity polyimide layer with thermoplastic polyimide layer and the metal level that forms on the one side at least on above-mentioned thermoplastic polyimide layer surface.
The present invention relates to a kind of laminated body, the metal level that has thermoplastic polyimide layer and be formed on above-mentioned thermoplastic polyimide layer surface on this laminated body one side, another side has adhesive linkage.
The present invention relates to a kind of laminated body, the metal level that has thermoplastic polyimide layer and be formed on above-mentioned thermoplastic polyimide layer surface on this laminated body one side, another side has Copper Foil.
Above-mentioned thermoplastic polyimide layer preferably makes up the processing of selecting more than a kind or a kind and carries out the surface-treated layer from surface treatment, flame treatment and the hydrophilicity-imparting treatment of plasma treatment, sided corona treatment, coupling agent processing, permanganate processing, ultraviolet treatment with irradiation, electron ray treatment with irradiation, projected at high velocity grinding agent.
Above-mentioned thermoplastic polyimide layer is preferably handled by ion gun and is carried out the surface-treated layer.
Above-mentioned ion gun is preferably handled by argon ion.
Above-mentioned metal level is limit heating thermoplastic polyimide layer limit deposit element and forming preferably.Layer
The heating-up temperature of thermoplastic polyimide layer is more than 100 ℃ or 100 ℃.
In addition, the present invention relates to a kind of laminated body, this laminated body comprises the laminated body of Kapton and metal level, above-mentioned Kapton is to comprise the non-thermal plasticity polyimide layer and at least 2 layers of structure of the thermoplastic polyimide layer that forms on the one side at least at the non-thermal plasticity polyimide layer, and above-mentioned metal level comprises the 1st metal level of the nickel, cobalt, chromium, titanium, molybdenum, tungsten, zinc, tin, indium, gold or their alloy that contain the thermoplastic polyimide layer surface and the 2nd metal level that contains copper or its alloy on the 1st metal level.
Above-mentioned thermoplastic polyimide layer preferably comprises with following general formula (1)
Figure A20038010518900111
General formula (1)
(in the formula, A is the 4 valency organic groups of selecting from following formula group (2), can be the same or different, and X is the divalent organic group of selecting from following formula group (3), can be the same or different.B is 4 valency organic groups outside enumerating in the following formula group (2), can be the same or different, and Y is the divalent organic group outside enumerating in the following formula group (3), and can be the same or different m: n is 100: 0～50: 50)
Group (2)
Figure A20038010518900121
Group 3
Figure A20038010518900122
Figure A20038010518900141
The TPI that the polyamic acid dehydration ring closure of expression obtains.
The thickness of above-mentioned thermoplastic polyimide layer is preferably 0.01～10 μ m, and is thinner than non-thermal plasticity polyimide layer.
The thermoplastic polyimide film that the present invention relates to is the processing more than a kind or a kind selected from surface treatment, flame treatment and the hydrophilicity-imparting treatment of plasma treatment, sided corona treatment, coupling agent processing, permanganate processing, ultraviolet treatment with irradiation, electron ray treatment with irradiation, projected at high velocity grinding agent of combination and carry out surface-treated.
In addition, the present invention relates to a kind of manufacture method of printed circuit board, this method comprises following operation forms the thermoplastic polyimide resin layer on non-thermal plasticity Kapton one side operation, forms the operation, this adhesive linkage is relative with the circuit face of the wiring plate of formation circuit of adhesive linkage at the another side of this non-thermal plasticity Kapton, and the method that adopts heating and/or accompany by pressurization carries out the operation of lamination, and the surface of the thermoplastic polyimide layer behind lamination is by the operation of the vapour deposition method plate plating of physics.
Have again, the present invention relates to a kind of manufacture method of printed circuit board, this method comprises following operation: on non-thermal plasticity Kapton one side, form the thermoplastic polyimide resin layer operation, the another side of this non-thermal plasticity Kapton is passed through adhesive sheet, adopt heating and/or accompany by the method for pressurization, be laminated to the plate plating is carried out on operation on the wiring plate that forms circuit and the thermoplastic polyimide layer surface behind lamination by the vapour deposition method of physics operation.
The simple declaration of accompanying drawing
Fig. 1 is the figure that structure example of the present invention is shown.
Fig. 2 is the figure that structure example of the present invention is shown.
Fig. 3 is the figure that structure example of the present invention is shown.
Fig. 4 is the figure that structure example of the present invention is shown.
The preferred plan that carries out an invention
Thermoplastic polyimide layer and metal level that laminated body of the present invention comprises thermoplastic polyimide layer and metal level or non-thermal plasticity polyimide film layer, forms on its one side or two sides.
The TPI that uses in the present invention is introduced.As TPI, preferably use following general formula (1)
General formula (1)
(in the formula, A is the 4 valency organic groups of selecting from following formula group (2), can equally also can be different, and X is the divalent organic group of selecting from following formula group (3), can equally also can difference.B is 4 valency organic groups outside enumerating in the following formula group (2), can be the same or different, Y is the divalent organic group outside enumerating in the following formula group (3), can be the same or different) TPI that obtains of polyamic acid dehydration ring closure of expression.
Group (2)
Group 3
Figure A20038010518900171
Here, m: n is 100: 0～50: 50, preferred 100: 0～70: 30, is more preferably 100: 0～90: 10.
For obtaining the TPI that the present invention uses, when use provides the carboxylic acid dianhydride of the carboxylic acid dianhydride residue of enumerating in above-mentioned group (2), can also use other carboxylic acid dianhydride compositions that B represents in the general formula (1) with 4 valency organic groups, as such carboxylic acid dianhydride, for example can enumerate 2,2 ', 3,3 '-biphenyl tetracarboxylic dianhydride, two (2,3-two carboxy phenyls) methane dianhydride, two (3,4-two carboxy phenyls) methane dianhydride, 1, two (2,3-two carboxy phenyls) the ethane dianhydrides of 1-, 1,1-two (3,4-two carboxy phenyls) ethane dianhydride, 1, two (3,4-two carboxy phenyls) the ethane dianhydrides of 2-, 2,2-two (3,4-two carboxy phenyls) propane dianhydride, 1, two (3,4-two carboxy phenyls) the propane dianhydrides of 3-, 1,2,5,6-naphthalene tetracarboxylic acid dianhydride, 2,3,6,7-naphthalene tetracarboxylic acid dianhydride, 3,4,9,10-perylene tetracarboxylic dianhydride, to benzene two (trimellitic acid monoesters acid anhydrides), or to aromatic tetracarboxylic acid's dianhydrides such as benzene two phthalate anhydrides.
In addition, for obtaining these TPIs, can be when use brings the diamines of the diamines residue of enumerating in above-mentioned group (3), also to use other two amine components that Y represents in the general formula (1) with divalent organic group, as such diamines, for example can enumerate, 1, the 2-diaminobenzene, benzidine, 3,3 '-dichloro-benzidine, 3,3 '-dimethoxy benzidine, 1, the 5-diaminonaphthalene, 4,4 '-diamino-diphenyl diethylsilane, 4,4 '-diamino-diphenyl silane, 4,4 '-diamino-diphenyl ethyl phosphine oxide, 4,4 '-diamino-diphenyl-N-methyl amine, 4,4 '-diamino-diphenyl-N-phenyl amine, 3,3 '-diamino-diphenyl ether, 4,4 '-diamino-diphenyl thioether, 3,4 '-diamino-diphenyl thioether, 3,3 '-diamino-diphenyl thioether, 3,3 '-diaminodiphenyl-methane, 3,4 '-diaminodiphenyl-methane, 3,4 '-diamino diphenyl sulfone, 3,3 '-diamino diphenyl sulfone, 4,4 '-diamino-N-benzanilide, 3,4 '-diamino-N-benzanilide, 3,3 '-diamino-N-benzanilide, 4,4 '-diaminobenzophenone, 3,4 '-diaminobenzophenone, 3,3 '-diaminobenzophenone, two [4-(3-amino-benzene oxygen) phenyl] methane, two [4-(4-amino-benzene oxygen) phenyl] methane, 1, two [4-(3-amino-benzene oxygen) phenyl] ethane of 1-, 1, two [4-(4-amino-benzene oxygen) phenyl] ethane of 1-, 1, two [4-(3-amino-benzene oxygen) phenyl] ethane of 2-, 1, two [4-(4-amino-benzene oxygen) phenyl] ethane of 2-, 2, two [4-(3-amino-benzene oxygen) phenyl] propane of 2-, 2, two [4-(3-amino-benzene oxygen) phenyl] butane of 2-, 2, two [3-(3-amino-benzene oxygen) phenyl]-1 of 2-, 1,1,3,3, the 3-HFC-236fa, 1, two (3-amino-benzene oxygen) benzene of 4-, 4,4 '-two (3-amino-benzene oxygen) biphenyl, two [4-(3-amino-benzene oxygen) phenyl] ketone, two [4-(4-amino-benzene oxygen) phenyl] ketone, two [4-(3-amino-benzene oxygen) phenyl] thioether, two [4-(4-amino-benzene oxygen) phenyl] thioether, two [4-(3-amino-benzene oxygen) phenyl] ether, two [4-(4-amino-benzene oxygen) phenyl] ether, 1, two [4-(3-amino-benzene oxygen) benzoyl] benzene of 4-, 1, two [4-(3-amino-benzene oxygen) benzoyl] benzene of 3-, 4,4 '-two [3-(4-amino-benzene oxygen) benzoyl] diphenyl ether, 4,4 '-two [3-(3-amino-benzene oxygen) benzoyl] diphenyl ether, 4,4 '-two [4-(4-amino-α, α-Er Jiajibianji) phenoxy group] benzophenone, 4,4 '-two [4-(4-amino-α, α-Er Jiajibianji) phenoxy group] diphenyl sulfone, two [4-{4-(4-amino-benzene oxygen) phenoxy group } phenyl] sulfone, 1, two [the 4-(4-amino-benzene oxygen)-α of 4-, α-Er Jiajibianji] benzene, 1, two [the 4-(4-amino-benzene oxygen)-α of 3-, α-Er Jiajibianji] benzene, 4,4 '-diamino-diphenyl ethyl phosphine oxide and their analog.
As being the above-mentioned carboxylic acid dianhydride that obtains the TPI that the present invention uses and the combination of diamine compound, the preferably combination of at least a carboxylic acid dianhydride of from the carboxylic acid dianhydride that the cited carboxylic acid dianhydride residue of structural formula group (2) can be provided, selecting and at least a diamines of from the diamines that the cited diamines residue of structural formula group (3) can be provided, selecting.Wherein as carboxylic acid dianhydride, 2,3,3 ' 4 '-biphenyl tetracarboxylic dianhydride, 3,3 ', 4,4 '-biphenyl tetracarboxylic dianhydride, hydroxyl two phthalate anhydrides, di-2-ethylhexylphosphine oxide (trimellitic acid monoesters acid anhydrides), bisphenol-A two (trimellitic acid monoesters acid anhydrides), to benzene two (trimellitic acid monoesters acid anhydrides), perhaps 4,4 '-(4,4 '-isopropylidene, two phenoxy groups) two (phthalate anhydrides), as diamines, 1, the 3-diaminobenzene, 3,4 '-diamino-diphenyl ether, 4,4 '-diamino-diphenyl ether, 1, two (3-amino-benzene oxygen) benzene of 3-, 1, two (4-amino-benzene oxygen) benzene of 3-, 1,4 '-two (4-amino-benzene oxygen) benzene, 2, two [4-(4-amino-benzene oxygen) phenyl] propane of 2-, 4,4 '-two (4-amino-benzene oxygen) biphenyl, two [4-(4-amino-benzene oxygen) phenyl] sulfone, and two [4-(3-amino-benzene oxygen) phenyl] sulfone makes easily industrial, it is low that the TPI that obtains in addition has a water absorption rate, dielectric constant is little, the little characteristic that waits excellence of dielectric loss tangent also finds to have the effect of raising as the adhesive strength of effect of the present invention, so more preferred.
As more preferably combination, can list, for example, bisphenol-A two (trimellitic acid monoesters acid anhydrides) and 2, the combination, 3 of two [4-(4-amino-benzene oxygen) phenyl] propane of 2-, 3 ', 4,4 '-biphenyl tetracarboxylic dianhydride and di-2-ethylhexylphosphine oxide (trimellitic acid monoesters acid anhydrides) and 2, the combination of two [4-(4-amino-benzene oxygen) phenyl] propane of 2-, to benzene two (trimellitic acid monoesters acid anhydrides) and 4, the combination of 4 '-diamino-diphenyl ether, 4,4 '-(4,4 '-isopropylidene, two phenoxy groups) two (phthalate anhydrides) and 1, the combination of two (3-amino-benzene oxygen) benzene of 3-etc.
The TPI that uses among the present invention can obtain with the polyamic acid imidizate of above-mentioned general formula (1) expression.Above-mentioned imidizate uses any in heat treating process and the method for chemical treatment.Heat treating process is without effects such as dehydration ring closures, only just can carry out the method for imidization reaction by heating.In addition, method of chemical treatment is in the polyamic acid organic solvent solution, and making acid anhydrides such as acetic anhydride is that the chemical converting agent (dehydrating agent) of representative is the method for the catalyst action of representative with tertiary amines such as isoquinolin, beta-picoline, pyridines.Certainly, also can be in method of chemical treatment and use heat treating process, the condition of imidizate can change according to the selection of thickness, heat treating process and/or the method for chemical treatment of the kind of polyamic acid, film etc.
When carrying out imidizate by chemical treatment method, as the chemical converting agent that in polyamic acid composition, adds, can list, for example, aliphatic anhydride, aromatic anhydride, N, the mixture more than 2 kinds or 2 kinds of N '-dialkyl group carbodiimides, lower aliphatic halide, halogenated lower aliphatic halide, halogenated lower aliphatic anhydride, arylphosphonic acid dihalide, thionylhalides or these compounds.In these, preferably use the mixture more than 2 kinds or 2 kinds of aliphatic anhydride such as acetic anhydride, propionic andydride, butyric anhydride or these compounds.These chemical converting agents with respect to 1～10 times of amount of molal quantity interpolation at the polyamic acid position in the polyamic acid solution, preferably add 1～7 times of amount, are more preferably and add 1～5 times of amount.In addition, for imidizate effectively carries out, preferably in chemical converting agent, use catalyst simultaneously.As catalyst, can use aliphatic tertiary amine, aromatic nitrile base or heterocycle tertiary amine etc.Wherein, preferred especially heterocycle tertiary amine specifically is quinoline, isoquinolin, beta-picoline or pyridine etc.These catalyst with respect to the molal quantity of chemical converting agent, add 1/20～10 times of amount, preferably add 1/15～5 times of amount, are more preferably to add 1/10～2 times of amount.Above-mentioned chemical converting agent and catalyst, if the tendency that amount has imidizate effectively not carry out at least, on the contrary, crossing has the meeting imidizate too fast at most, the tendency of operating difficulties.
In addition, the TPI that uses among the present invention can be by known method, add plasticizer and antioxidants such as inorganic or organic filler, organic phosphorus compound, also can blending epoxy, thermosetting resin such as cyanate ester resin and phenolic resins.
The non-thermal plasticity Kapton that uses among the present invention can be with known method manufacturing.That is, with the polyamic acid curtain coating or coat on the support, obtain by imidizate chemistry or heat.From the viewpoint of toughness, fracture strength and the productivity ratio of film, the imidizate of preferred chemistry.
As the polyamic acid of the precursor of the non-thermal plasticity polyimides that uses among the present invention, all known basically polyamic acids are all applicable.Polyamic acid is dissolved in a kind of at least a and diamines of aromatic carboxylic acid dianhydride the polyamic acid organic solvent solution that obtains in the organic solvent of equimolar amounts in fact usually at least, under the condition of control temperature, above-mentioned carboxylic acid dianhydride and diamines are stirred to polymerization finish and make.Polyimides is the same with TPI in addition, and the imidizate by polyamic acid makes.
Can enumerate as using the synthetic suitable acid anhydrides of non-thermal plasticity polyimides in the present invention, from pyromellitic acid dianhydride, 3,3 ', 4,4 '-benzophenone tetracarboxylic dianhydride, two (3,4-two carboxy phenyls) sulfonic acid dianhydride, 2,2 ', 3,3 '-biphenyl tetracarboxylic dianhydride, 3,3,3 ' 4 '-biphenyl tetracarboxylic dianhydride, xenol dioctyl phthalate dianhydride, two (2,3-two carboxy phenyls) methane dianhydride, two (3,4-two carboxy phenyls) methane dianhydride, 1,1-two (2,3-two carboxy phenyls) ethane dianhydride, 1, two (3,4-two carboxy phenyls) the ethane dianhydrides of 1-, 1,2-two (3,4-two carboxy phenyls) ethane dianhydride, 2, two (3,4-two carboxy phenyls) the propane dianhydrides of 2-, 1,3-two (3,4-two carboxy phenyls) propane dianhydride, 4,4 '-hexafluoroisopropyli,ene, two phthalic acid dianhydrides, 1,2,5,6-naphthalene tetracarboxylic acid dianhydride, 2,3,6,7-naphthalene tetracarboxylic acid dianhydride, 3,4,9,10-perylene tetracarboxylic dianhydride, to benzene two (trimellitic acid monoesters acid anhydrides), ethylenebis (trimellitic acid monoesters acid anhydrides), bisphenol-A two (trimellitic acid monoesters acid anhydrides), 4,4 '-(4,4 '-isopropylidene, two phenoxy groups) two (phthalic anhydrides), to aromatic tetracarboxylic acid or their analogs such as benzene two phthalate anhydrides.
Wherein, preferred pyromellitic acid dianhydride, xenol dioctyl phthalate dianhydride, 3,3 ', 4,4 '-benzophenone tetracarboxylic dianhydride, 3,3,3 ' 4 '-biphenyl tetracarboxylic dianhydride or to benzene two (trimellitic acid monoesters acid anhydrides) can also can be used their independent uses the mixture that mixes with arbitrary proportion.
Can enumerate as being used in the synthetic suitable diamines of non-thermal plasticity polyimides in the present invention, 1,4-diaminobenzene (p-phenylenediamine (PPD)), 1, the 3-diaminobenzene, 1, the 2-diaminobenzene, benzidine, 3,3 '-dichloro-benzidine, 3,3 '-dimethylbenzidine, 3,3 '-dimethoxy benzidine, 3,3 '-dihydroxybiphenyl amine, 3,3 ' 5,5 '-tetramethyl benzidine, 4,4 '-diamino-diphenyl propane, 4,4 '-diamino-diphenyl HFC-236fa, 1, the 5-diaminonaphthalene, 4,4 '-diamino-diphenyl diethylsilane, 4,4 '-diamino-diphenyl silane, 4,4 '-diamino-diphenyl ethyl phosphine oxide, 4,4 '-diamino-diphenyl-N-methyl amine, 4,4 '-diamino-diphenyl-N-phenyl amine, 4,4 '-diamino-diphenyl ether, 3,4 '-diamino-diphenyl ether, 3,3 '-diamino-diphenyl ether, 4,4 '-diamino-diphenyl thioether, 3,4 '-diamino-diphenyl thioether, 3,3 '-diamino-diphenyl thioether, 3,3 '-diaminodiphenyl-methane, 3,4 '-diaminodiphenyl-methane, 4,4 '-diaminodiphenyl-methane, 4,4 '-diamino diphenyl sulfone, 3,4 '-diamino diphenyl sulfone, 3,3 '-diamino diphenyl sulfone, 4,4 '-diamino-N-benzanilide, 3,4 '-diamino-N-benzanilide, 3,3 '-diamino-N-benzanilide, 4,4 '-diaminobenzophenone, 3,4 '-diaminobenzophenone, 3,3 '-diaminobenzophenone, two [4-(3-amino-benzene oxygen) phenyl] methane, two [4-(4-amino-benzene oxygen) phenyl] methane, 1, two [4-(3-amino-benzene oxygen) phenyl] ethane of 1-, 1, two [4-(4-amino-benzene oxygen) phenyl] ethane of 1-, 1, two [4-(3-amino-benzene oxygen) phenyl] ethane of 2-, 1, two [4-(4-amino-benzene oxygen) phenyl] ethane of 2-, 2, two [4-(3-amino-benzene oxygen) phenyl] propane of 2-, 2, two [4-(4-amino-benzene oxygen) phenyl] propane of 2-, 2, two [4-(3-amino-benzene oxygen) phenyl] butane of 2-, 2, two [3-(3-amino-benzene oxygen) phenyl]-1,1 of 2-, 1,3,3, the 3-HFC-236fa, 2, two [4-(4-amino-benzene oxygen) phenyl]-1 of 2-, 1,1,3,3, the 3-HFC-236fa, 1, two (3-amino-benzene oxygen) benzene of 3-, 1, two (3-amino-benzene oxygen) benzene of 4-, 1, two (4-amino-benzene oxygen) benzene of 4-, 4,4 '-two (4-amino-benzene oxygen) biphenyl, 4,4 '-two (3-amino-benzene oxygen) biphenyl, two [4-(3-amino-benzene oxygen) phenyl] ketone, two [4-(4-amino-benzene oxygen) phenyl] ketone, two [4-(3-amino-benzene oxygen) phenyl] thioether, two [4-(4-amino-benzene oxygen) phenyl] thioether, two [4-(3-amino-benzene oxygen) phenyl] sulfone, two [4-(4-amino-benzene oxygen) phenyl] sulfone, two [4-(3-amino-benzene oxygen) phenyl] ether, two [4-(4-amino-benzene oxygen) phenyl] ether, 1, two [4-(3-amino-benzene oxygen) benzoyl] benzene of 4-, 1, two [4-(3-amino-benzene oxygen) benzoyl] benzene of 3-, 4,4 '-two [3-(4-amino-benzene oxygen) benzoyl] diphenyl ether, 4,4 '-two [3-(3-amino-benzene oxygen) benzoyl] diphenyl ether, 4,4 '-two [4-(4-amino-α, α-Er Jiajibianji) phenoxy group] benzophenone, 4,4 '-two [4-(4-amino-α, α-Er Jiajibianji) phenoxy group] diphenyl sulfone, two [4-{4-(4-amino-benzene oxygen) phenoxy group } phenyl] sulfone, 1, the two [4-(4-amino-benzene oxygen)-α of 4-, α-Er Jiajibianji] benzene, 1, two [4-(4-amino-benzene oxygen)-α, the α-Er Jiajibianji] benzene of 3-, 4,4 '-diamino-diphenyl ethyl phosphine oxide or their analog.
Wherein, preferred 4,4 '-diamino-diphenyl ether, 4,4 '-diamino-N-benzanilide, p-phenylenediamine (PPD) and their mixture.
As being combined as of preferred carboxylic acid dianhydride and two amines, pyromellitic acid dianhydride and 4, the combination of 4 '-diamino-diphenyl ether, pyromellitic acid dianhydride and 4, the combination of 4 '-diamino-diphenyl ether and p-phenylenediamine (PPD), pyromellitic acid dianhydride and to benzene two (trimellitic acid monoesters acid anhydrides) and 4, the combination of 4 '-diamino-diphenyl ether and p-phenylenediamine (PPD), p-phenylenediamine (PPD) and 3,3 ', 4, the combination of 4 '-biphenyl tetracarboxylic dianhydride, pyromellitic acid dianhydride, to benzene two (trimellitic acid monoesters acid anhydrides) and 3,3 ', 4,4 '-biphenyl tetracarboxylic dianhydride and 4, the combination of 4 '-diamino-diphenyl ether and p-phenylenediamine (PPD).These monomers are made up synthetic non-thermal plasticity polyimides, demonstrate excellent characteristic such as suitable elastic modelling quantity, dimensional stability, low water absorption, be applicable to various laminated body of the present invention.
For the synthetic preferred solvent of above-mentioned polyamic acid is an amide solvent, i.e. N, dinethylformamide, N, N-dimethylacetylamide, N-N-methyl-2-2-pyrrolidone N-etc. especially preferably use N, dinethylformamide.
Form the method for thermoplastic polyimide layer on the surface of non-thermal plasticity Kapton, representational have, after the one or both sides curtain coating of non-thermal plasticity Kapton or coating are as the polyamic acid of the precursor of TPI, the polyamic acid shown in for example general formula (1), with method or chemical method imidizate and the drying of this polyamic acid, obtain the method for Kapton with heat.In addition, when TPI can be dissolved in the solvent, can with this solution coat after on the non-thermal plasticity polyimides, obtain by drying.Perhaps, make the TPI sheet, the method for heat bonding on the non-thermal plasticity Kapton also is fit to.
The Kapton that obtains with above-mentioned the whole bag of tricks also can add plasticizer and antioxidants such as inorganic or organic filler, organic phosphorus compound by known method.
And the thickness of the thermoplastic polyimide layer during with non-thermal plasticity polyimide layer and thermoplastic polyimide layer is preferably 0.01～10 μ m, preferred especially 0.1～5 μ m.If thermoplastic polyimide layer is thin excessively, the tendency that weakens as the expression effect of the cementability of effect of the present invention is arranged then.On the other hand, blocked up, rerum naturas such as the hear resistance of circuit substrate and thermal expansion character will be by the rerum natura decision of TPI.Therefore, as circuit substrate, for generation has the rerum natura of the non-thermal plasticity Kapton of excellent specific property, the thickness of thermoplastic polyimide layer is preferably thin than non-thermal plasticity Kapton.More the thickness of preferred thermoplastic polyimide layer is below 1/2 or 1/2 of non-thermal plasticity polyimide layer, below preferred especially 1/5 or 1/5.
10 mean roughness on above-mentioned thermoplastic polyimide layer surface (below, be called Rz) preferred 2 μ m or below the 2 μ m, more preferred 1 μ m or below the 1 μ m, surface smoothing, being suitable for forming L/S is 25 μ m/25 μ m or the following high-density circuit of 25 μ m/25 μ m, in addition from can also not being suitable aspect generation etching vestiges in resin surface concavo-convex etching work procedure.Rz is by the relevant prescribed by standard of surface configurations such as JISB0601, and its mensuration can be used the contact pin type rough surface meter of JIS B0651 or the optical interference formula rough surface meter of B0652.In the present invention, use optical interference formula rough surface meter (system New View5030 system of ZYGO society), measure 10 mean roughness on above-mentioned thermoplastic polyimide layer surface.
On the other hand, the preferred 2 μ m of the thickness of above-mentioned non-thermal plasticity Kapton～125 μ m are more preferably 5 μ m～75 μ m.If thinner than this scope, the rigidity deficiency of laminated body so has the become tendency of difficulty of the processing of film, is difficult to bring into play the advantage of non-thermal plasticity polyimide layer.In addition, film is blocked up, then when making printed circuit board, from the impedance Control aspect, the circuit amplitude is broadened, and runs in the opposite direction with the miniaturization of printed circuit board, the requirement of densification.
The metal level that the present invention relates to is from the cementability of raising with TPI, preferably copper, nickel, cobalt, chromium, titanium, molybdenum, tungsten, zinc, tin, indium, gold or their alloy.Particularly nickel, cobalt or their alloy are effective, and industrial ratio is easier to obtain.Therefore preferred.
As the formation method of metal level, can enumerate the vapour deposition method of physics such as vacuum vapour deposition, ion plating method, sputtering method and EB vapour deposition method and electroless plating coated with and chemical method such as chemical vapor deposition method.In the vapour deposition method of physics, judge preferred sputtering method by simplicity, the productivity ratio of equipment and the cementability of conductor layer that obtains and film etc. are comprehensive.In addition, the preferred 5～500nm of metal layer thickness.
And, if use above-mentioned sputtering method, can good, the even metal film of the accuracy of manufacture.But general copper or the copper alloy thin films that is formed by sputtering method on the non-thermal plasticity Kapton of surface plane excellence, can not form firm bonding.In our research, on Rz value 3 μ m or the prima facie non-thermal plasticity Kapton below the 3 μ m, can not reach the cementability of 2N/cm or the above intensity of 2N/cm.But, using the laminated body of thermoplastic polyimide layer of the present invention, cementability shows big improvement, can reach the cementability of 5N/cm.
When using sputter, can use known method, that is, the DC magnetron sputtering, RF sputter or by these methods method of various improvement in addition adapts to various requirement, can suitablely use.Be the conductor of sputter nickel or copper etc. efficiently, preferred DC magnetron sputtering.In addition, for reaching purposes such as preventing from film, to sneak into sputter gas, when in high vacuum, carrying out sputter, suitablely use that RF is low-priced to be penetrated.
About the DC magnetron sputtering, at first Kapton is installed in the vacuum chamber as substrate, vacuumize.Usually, combination is evacuated to 6 * 10 by slightly vacuumizing and diffusion pump or cryogenic pump that rotary pump carries out -4Pa or 6 * 10 -4Below the Pa.Then, import sputter gas, vacuum indoor pressure is decided to be 0.1～10Pa, preferred 0.1～1Pa.Then, on metallic target, apply dc voltage, cause plasma discharge.At this moment, on target, form magnetic field, be enclosed in the magnetic field, improve the sputtering yield of article on plasma body target by the plasma that will generate.When not bringing the influence of plasma and sputter to Kapton, under the state that generates plasma, keep several minutes to a few hours, remove metallic target surface oxide layer (being called pre-sputter).After pre-sputter finishes, open air door, Kapton is carried out sputter.The scope of the preferred 100～1000W of discharge power during sputter.In addition, the shape of the sample of sputter is optionally used batch mode sputter or cylinder sputter.The sputter gas that imports uses inert gases such as argon usually, but also can use mist and other gases that contain minor amounts of oxygen.
In addition, as the method that electroless plating covers, can use known technology.It is commercially available that various electroless platings cover the use of processing soup, and in the various treatment process, the manufacturer that various electroless platings cover soup discloses the recommendation condition.But the soup that various electroless platings cover is for various suitable resins, generally reasonably the liquor strength of use experience, treatment temperature and processing time etc.Table 1 shows thermoplastic polyimide resin of the present invention is carried out the example that electroless plating covers the treatment process condition.
Table 1
Operation Prescription for the treatment of liquid Treatment conditions
1 Do special (Network リ one Na one セ キ ユ リ ガ Application ト) 902 (※) Ke Linayadetebo (Network リ one Na one ア デ イ テ イ) 902 (※) NaOH in the Ke Linake 40ml/l 3ml/l 20g/l 60 ℃ 5 minutes
(washing)
2 Pu Lidepuneiao does special (プ リ デ イ プ ネ オ ガ Application ト) B (※) sulfuric acid 20ml/l 1mL/l Room temperature 1 minute
3 (※) the NaOH boric acid of special (ア Network チ ベ one one ネ オ ガ Application ト) 834 elder brothers grams (ユ Application Network) of doing difficult to understand in the Ya Keqi beta 40ml/l 4g/l 5g/l 40 ℃ 5 minutes
(washing)
4 In excellent Sha Neiao does special (リ デ ユ one サ one ネ オ ガ Application ト) (※) NaOH 1g/l 5g/L Room temperature 2 minutes
(washing)
5 The excellent effect of Bei Xikesuoli An Pulinte does dried special (the カ Star パ one ソ リ ユ one シ ヨ Application プ リ Application ト ガ Application ト) MSK (※) of spy (ベ one シ Star Network ソ リ ユ one シ ヨ Application プ リ Application ト ガ Application ト) the excellent effect of MSK-DK (※) Ka Pasuoli An Pulinte, and this reaches inner excellent Sha (リ デ ユ one サ one) copper (※) that gets than dried special (the ス PVC ラ イ ザ one プ リ Application ト ガ Application ト) MSK-DK (※) of Rye Zha Pulinte 80ml/l 40ml/l 3ml/l 14ml/l 35 ℃ 15 minutes
(washing)
(※) (Ya Tedekejiapaen (ア ト テ Star Network ジ ヤ パ Application) Co., Ltd.'s system)
The thermoplastic polyimide resin that uses among the present invention can be bonded on the non-electrolytic copper plating layer well.The thickness of coating can suitably be selected according to the purposes of laminated body, the scope about general preferred 0.1～10 μ m.Thickness of coating is thin than this, and coating surface has the inhomogeneous tendency of separating out.In addition, blocked up, not only the plating processing time long, and the tendency that is unfavorable for forming fine line circuitry is arranged.Particularly, being decided to be the thickness of 0.2～1 μ m, is suitable to the reliability of coating and the formation of fine line circuitry.Therefore, in the condition of above-mentioned table 1, thickness is 0.3 μ m.In addition, when non-electrolytic nickel of plating or cobalt, have to prevent the effect to the diffusion of TPI resin bed such as copper.
In addition, behind the relative lamination of adhesive linkage on the non-thermal plasticity Kapton with the circuit face of circuit-formed internal layer wiring plate, in the manufacture method of the printed circuit board of the dull and stereotyped plating that the vapour deposition method by above-mentioned physics carries out, because physical vapor deposition is the dry type operation, do not exist the electroless plating of original wet type to cover problem of environmental pollution in the method.In addition, by the dull and stereotyped coating that the vapour deposition method of this physics makes, layer that must be the most surperficial at least has electric conductivity.This is because in the electrolytic coating operation when making printed circuit board, this flat board coating is power supply layer.In addition, in the electrolytic coating operation, must contain whole working regions of printed circuit board.The coating that also needs to form uniform thickness in the part of necessity.For this reason, require the resistance of power supply layer low, therefore, be necessary to form the dull and stereotyped coating of suitable thickness.In this manufacture method,, be more preferably 50～1500nm as the preferred 25～3000nm of the metal layer thickness of electro deposition power supply layer.Words than the thin thickness of 250nm, resistance can become greatly, the electrolytic film plating thickness underproof reason in face that forms when carrying out electrolytic coating after becoming, on the other hand, if thicker than 3000nm, the productivity ratio in the time of can lowering dull and stereotyped plating that the vapour deposition method by physics carries out and form metal level.
Have again,, preferably metal level is designed to 2 layers of structure for improving the cementability of metal level.That is, metal level is designed to the 2nd metal level that on the 1st metal level that forms on the thermoplastic polyimide layer and the 1st metal level, forms.
The preferred nickel of the metal species of the 1st metal level, cobalt, chromium, titanium, molybdenum, tungsten, zinc, tin, indium, gold or their alloy.Wherein, because nickel, cobalt, gold or titanium can improve the cementability with TPI more, be preferred therefore.Especially the alloy of nickel or nickel and cobalt is owing to having effective and industrial can the acquisition, more preferred.
The metal species of the 2nd metal level preferably comprises copper or its alloy.Copper or its alloy ratio are used for the metal species of the 1st metal level to be compared, and resistance is low.Therefore, with metal level be that single situation is compared, the metal level integral thickness can attenuation, the productivity ratio height when forming metal level helps industrial production.In addition, when copper or its alloy were used as the 2nd metal level, the cementability with the cathode copper layer improved afterwards, so be preferred.
By above-mentioned the 1st metal level and thermoplastic polyimide layer are set, can realize the firm cementability that 10N/cm or 10N/cm are above.Particularly not only after pressure boiling experiment, still have the adhesive strength of 5N/cm or the excellence more than the 5N/cm, and can fully hold out against operations such as decontamination and chemical plating.
The 1st metal layer thickness is preferably at 1nm～50nm, more preferred 3nm～20nm.If thinner, can cause improving the inadequate situation of cementability effect than this scope.On the other hand, if thicker, can produce the tendency that the productivity ratio when forming metal level descends than this scope.Preferred 10nm～the 1000nm of the 2nd metal layer thickness is more preferably 20nm～500nm, preferred especially 30nm～300nm.In addition, behind the relative lamination of circuit face of the adhesive linkage of above-mentioned non-thermal plasticity Kapton and the internal layer wiring plate that forms circuit, by the vapour deposition method of physics, the preferred 50nm～2500nm of the 2nd metal layer thickness when carrying out dull and stereotyped plating, more preferred 100nm～1000nm.If thin thickness has the tendency that can not give full play to the purpose that reduces resistance.On the other hand, if thickness is thick, have the tendency that the productivity ratio when forming metal level reduces.
These metal layer thickness sums, to pass through 1. economy, 2. remove the etching of the power supply layer when forming circuit by half add, etching when the printed circuit board that 3. has a through hole forms the circuit of 30 μ m or the following width of 30 μ m with subraction, and 4. comprehensively judge in the viewpoint of the essential thickness of the region-wide acquisition homogeneous thickness of flat board during electrolytic coating in making for obtaining printed circuit board.That is, 1.～3. viewpoint requires thin as far as possible, and on the other hand, 4. viewpoint requires thick.Therefore, should wait suitably from the width of anticipation circuit and dull and stereotyped whole size and select.Preferred 1000nm or below the 1000nm, more preferred 500nm or below the 500nm, especially preferably 300nm or below the 300nm.If thicker than 1000nm, above-mentioned etching variation has the tendency that is difficult to form the high-density circuit pattern.
Here, Fig. 1 is illustrated in the laminated body of the present invention that has thermoplastic polyimide layer 3 on the one side of non-thermal plasticity Kapton 4, forms the 1st metal level 2 and the 2nd metal level 1 in its surface.In addition, Fig. 2 is illustrated on the two sides of non-thermal plasticity Kapton 4 laminated body of the present invention that has thermoplastic polyimide layer 3, forms the 1st metal level 2 and the 2nd metal level 1 on each surface.
Method as the cementability of above-mentioned metal level of further raising and Kapton, the heating thermoplastic polyimide layer is arranged, and the method more than a kind or a kind of carrying out simultaneously selecting from sputtering method, vacuum vapour deposition, ion plating method, EB vapour deposition method and chemical vapor deposition method forms the method for metal level.Heating can be by the infrared lamp heater, with thermophore or use the heated roller of heating wire and carry out with electromagnetic wave eddy-current heating etc.Wherein, infrared lamp heater or have with the cylinder of thermophore or heating wire heating that it is simple in structure, small-sized such as relatively is easily mounted in the vacuum tank at characteristics, thereby preferred.Heating-up temperature is preferred more than 100 ℃ or 100 ℃, is more preferably 100～300 ℃.It is little that temperature below this adds thermal effect, in addition, if temperature is too high, can cause deterioration, distortion or the decomposition etc. of thermoplastic polyimide resin, so not preferred.Wherein, heat, the molecular motion of thermoplastic polyimide resin is come to life, improve the cementability with deposit in glass transition temperature or its above temperature of thermoplastic polyimide resin, therefore more preferred.
In addition, method as the cementability of above-mentioned metal level of further raising and Kapton, can list the surface treatment of the chemistry of the surface treatment of the physics that to implement that the ion bombardment is handled etc. known and primary coat processing etc., but this wherein, and the preferred ion rifle is handled, plasma treatment, sided corona treatment, coupling agent is handled, permanganate is handled, the ultraviolet ray treatment with irradiation, the electron ray treatment with irradiation, the surface treatment of projected at high velocity grinding agent, select the thermoplastic polyimide layer surface treatment method of treatment combination more than a kind or a kind in flame treatment and the hydrophilicity-imparting treatment.
In above-mentioned ion gun is handled, ion gun will import the gas ionization in the plasma discharge chamber, by 2 grids, be the screen-grid of the beam of focal zone positive electricity, and the accelerating grid electrode of drawing the primary ion beam that applies negative electricity is radiated at ion irradiation on the substrate.As concrete ion gun equipment, can use Yi Enteke (イ オ Application テ Star Network) society system filament cathode ion gun (sample name: 3-1500-100FC) with ion gun power supply (MPS3000).As above-mentioned gas, preferred argon gas.When using argon gas as above-mentioned gas, its operating condition is, the discharge voltage of ionization necessity is 30～60V, and preferred 35～40V, room pressure are 1 * 10 -3～1 * 10 -1Pa, preferred 2 * 10 -2～6 * 10 -2Pa, electron-beam voltage 200～1000V, preferred 300～600V, accelerating potential 200～1000V, preferred 300～600V.
In above-mentioned plasma treatment, in the gas importing apparatus for processing plasma with appropriate combination, keep the gas pressure of regulation.And it constitutes and satisfies when beginning to discharge, and produces plasma.At this moment, for accessing glow discharge, suitably select gas composition and gas pressure.Here there is no particular limitation to carry out the pressure of ambient gas of plasma treatment, but the pressure limit of preferred 10000～1000000Pa is carried out.Because not enough 10000Pa then needs vacuum equipment etc., surpass 1000000Pa and then discharge to become and be difficult to carry out.Particularly, owing to be under atmospheric pressure to carry out, so the operability of plasma treatment and productivity ratio are good, thereby preferred.In addition, there is no particular limitation in the gas composition of plasma treatment, but preferred discharge in 10000～1000000Pa is also for carrying out under the pure gas of the rare gas element of glow discharge or the mixed-gas environment.Preferred combination of gases is Ar/He/N 2Combination.In addition, preferred especially with the interior air state of above-mentioned rare gas element substitution device, but also can sneak into the air of the degree that does not hinder glow discharge.Handling density is by such processing, and resin surface is carried out chemical modification, can import the scope of hydrophily functional group (hydroxyl, carbonyldioxy or carbonyl etc.), can be 10～100000[W branch/m 2], preferred 100～10000[W branch/m 2].If under the density of this scope, handle, then can not make the resin deterioration and improve surface hydrophilicity.
About above-mentioned sided corona treatment, corona electrode should be shaped to and carry out the essential length of sided corona treatment, and in other words, should be shaped to roughly is the width of thermoplastic polyimide resin film.Thermoplastic polyimide resin film between the corona electrode of the cylinder of high-insulation and lines along the cylinder traveling.And, high-energy is acted on above-mentioned corona electrode, by causing corona discharge, can carry out Corona discharge Treatment to thermoplastic polyimide resin film.This moment, the discharge process density of corona discharge was 10～100000[W branch/m 2], be more preferably 100～10000[W branch/m 2], different according to the kind of resin with thickness, rule of thumb suitably set.In addition, there is no particular limitation for the material of electrode, can rule of thumb select, set.When carrying out Corona discharge Treatment, for preventing, after also can being stretched, carry out again 1 time or Corona discharge Treatment repeatedly along the wide direction of film owing to fold takes place in the film thermal expansion.In addition, Corona discharge Treatment and then also can blow the polarity that has static electrification on film or the ionized gas of reversed polarity ion to above-mentioned film.To eliminate static.
Handle about above-mentioned coupling agent,, for example can enumerate as the method for adhering to coupling agent solution, resin surface coating coupling agent, with coupling agent rub resin surface, blow coupling agent to resin surface, perhaps resin is immersed in the medium method of coupling agent solution.In addition,, can enumerate as the coupling agent that can use in the present invention, for example, coupling agents such as silanes, titanate ester, aluminium class or zirconium class.In these coupling agents, can use separately, also can multiple mixing use, can rule of thumb set.Wherein, preferably use silanes coupling agent, the coupling agent of preferred especially amino silane class.They can combine having with the reactive group (methoxyl group, ethyoxyl) of the associativity of the surface composition of TPI in the molecule and having with the reactive group (acrylic, amino, epoxy radicals) of the associativity of metal level composition, key (coupling) by film and metal level can improve compatibility between the two.If enumerate the coupling agent that relates to particularly; in the silanes coupling agent; the acrylic silanes can be enumerated, γ-methacryloxypropyl trimethoxy silane, γ-methacryloxypropyl triethoxysilane, γ-methacryloxypropyl methyl dimethoxysilane, γ-methacryloxypropyl methyldiethoxysilane, γ-acryloxy propyl trimethoxy silicane, γ-(acryloyl group) propyl group methyl dimethoxysilane etc.In addition, the amino silane class can be enumerated, the gamma-amino propyl trimethoxy silicane, γ-An Jibingjisanyiyangjiguiwan, gamma-amino propyl group methyl dimethoxysilane, gamma-amino propyl group methyldiethoxysilane, N-phenyl-gamma-amino propyl trimethoxy silicane, N-(phenyl methyl)-gamma-amino propyl trimethoxy silicane, N-methyl-gamma-amino propyl trimethoxy silicane, N, N, N-trimethyl-gamma-amino propyl trimethoxy silicane, N, N, N-tributyl-gamma-amino propyl trimethoxy silicane, N-β-(amino-ethyl)-gamma-amino propyl trimethoxy silicane, N-β-(amino-ethyl)-gamma-amino propyl group methyl dimethoxysilane, N-β-(amino-ethyl)-γ-An Jibingjisanyiyangjiguiwan, N-ω-(amino hexyl) gamma-amino propyl trimethoxy silicane, and N{N ' β-(amino-ethyl) }-β-(amino-ethyl) gamma-amino propyl trimethoxy silicane etc.The epoxy silane class can be enumerated, β-(3, the 4-epoxycyclohexyl) ethyl trimethoxy silane, γ-glycidoxypropyltrime,hoxysilane, γ-glycidoxy propyl-triethoxysilicane, γ-glycidoxy propyl group methyldiethoxysilane and γ-glycidoxy propyl group methyl dimethoxysilane etc.In addition, in the titanate ester coupling agent, can enumerate, isopropyl three isooctadecane acyl titanate esters, isopropyl three (dodecyl benzene sulfonyl) titanate esters, isopropyl three (dioctylphyrophosphoric acid ester) titanate esters, two (two (tridecane the phosphate)) titanate esters of four octyl groups, two (dioctyl phosphate) titanate esters of tetra isopropyl, four (2,2-two allyloxy methyl isophthalic acid-butyl) two (two tridecane) phosphate titanate esters, two (dioctylphyrophosphoric acid ester) glycolic acid titanate esters, two (dioctylphyrophosphoric acid ester) ethylidene titanate esters, isopropyl three-stearyl titanate esters, isopropyl dimethyl propylene thiazolinyl isooctadecane acyl titanate esters, isopropyl stearyl diallyl titanate esters, isopropyl three (dioctyl phosphate) titanate esters, isopropyl tri-isopropyl benzene base phenyl titanium acid esters, isopropyl three (N-amino-ethyl-amino-ethyl) titanate esters, diisopropylbenzyl glycolic acid titanate esters and two isooctadecane acyl ethylidene titanate esters etc.Other in aluminium class coupling agent, can enumerate alkyl acetoacetic ester-aluminum-diisopropoxide salt, can enumerate three butoxy zirconium stearates in the zirconium class coupling agent.In addition, above-mentioned coupling agent is dissolved in the solvent, use as solution, can enumerate methyl alcohol, ethanol, propyl alcohol, isopropyl alcohol or as their ketones solvent of alcohols solvent, acetone, MEK, 2 pentanone or propione etc. of Sormix (ソ Le ミ Star Network ス) etc. of mixed solvent and aromatic hydrocarbon solvent such as toluene, dimethylbenzene as solvent.These can use separately, also can multiple mixing use.In addition, also can use with water.Especially preferably use methyl alcohol.In addition, preferred 0.005～30 weight % of the concentration of coupling agent solution.Be more preferably 0.01～5 weight %.If the coupling agent excessive concentration is as seen inhomogeneous on the thermoplastic polyimide resin surface, and is undesirable in appearance, on the contrary, if the concentration of coupling agent is crossed the low tendency that can not show effect of sufficient that just has.Like this, by with coupling agent equably attached on the resin surface, the reaction of resin surface composition and coupling agent forms the epithelium of coupling agent at resin surface, can make the proterties homogenising of resin surface.Mode as coating, can enumerate with roll coating model that uses roller or the spreading machine mode of using scraper, the rice rod is coated with mode (マ イ ヤ one バ one コ テ イ Application グ), plate gravure coating method, reverse roll coating method, quick coating method, pneumatic blade coating (エ ア Block レ one ト) mode, spraying method, curtain formula coating method or dip coated mode etc. and other coating methods.Can by all coating method coatings.Then, by above-mentioned treatment process, coupling agent is applied, and the thermoplastic polyimide resin that surface texture is homogenized imports in the drying oven, carries out dry operation attached to the solution on the resin surface.Have no particular limits as drying condition, can rule of thumb suitably set.
In above-mentioned permanganate is handled, preferably use sodium permanganate or potassium permanganate as permanganate.Its concentration is preferably at 0.1mol/L or more than the 0.1mol/L.This is when being lower than 0.1mol/L because of concentration, except that the activation energy reduction, the processing time that have applied heat treated substrate surface are elongated thereupon, and the tendency that also has surface treatment evenly not carry out.In addition, the not special regulation of the upper limit of concentration, the concentration that can reach capacity, but from the surface-activation effect to thermoplastic polyimide resin, preferably use at alkaline range.
About above-mentioned ultraviolet treatment with irradiation, the surface treatment of carrying out with the ultraviolet ray irradiation has modification and two kinds of effects of washing.When being organic matter,, generate functional group with oxygen enrichment polarity by the ultraviolet ray irradiation as object of the present invention.Cooper-Hewitt lamp or PRK lamp etc. are suitable for surface treatment, but Cooper-Hewitt lamp is advantages such as low-temperature condition owing to having economy, the ultraviolet specificity of radiation and lamp tube wall, and be therefore preferred.The wavelength of Cooper-Hewitt lamp resonance line is 185nm and 254nm.Wavelength decomposes airborne oxygen molecule in the ultraviolet ray of 185nm, generates ozone, and this ozone absorbs the ultraviolet ray of 254nm and is decomposed into and excites oxygen atom, activates processed surface.In addition, ultraviolet ray deviates from the organic matter surface molecular, and light hydrogen atom is deviate from, and simultaneously owing to the existence that excites oxygen atom that generates, and generates hydrophilic radical.Can use the power output of selling on the market as Cooper-Hewitt lamp is about 25～400W.As treatment conditions, preferably at 1～30mW/cm 2Illumination under, shine 10 second～10 minute, from the intensity handled and the viewpoint of stability, more preferred illumination 10～20mW/cm 2, irradiation time 1～5 minute.
About above-mentioned electron ray treatment with irradiation, if the collision of electronics and organic molecule cause ionization or excite, in resin, produce free radical.And this free radical begins reaction, causes crosslinked.On the other hand, because the reaction between the free radical causes into long-chain inactivation etc., thereby cause stopping of growth or moving of active site.Like this, because the electron ray treatment with irradiation, number of free radical uprises, thus polymerization moment finish, obtain the material of aspect excellences such as crosslink density height, drug resistance and environmental resistance.Electron ray irradiation apparatus heat packs in high vacuum contains the negative electrode of tungsten filament, produces thermoelectron.Apply negative high voltage in this cathode filament portion, repel electronics thus, accelerate at a high speed.And this electronics is by the thin metal foil of earthing potential, is released in the atmosphere or not in the active gases.The electronics of this release can shine object being treated.Preferred 100～500kV the scope of the accelerating potential of electronics, stability and intensity from handling are more preferably 150～250kV.The scope of the preferred 10～500mA of electric current.The scope of the preferred 10～1000kGy of roentgen dose X from Treatment Stability and the reduction damage harmful to resin, is more preferably 100～500kGy.
About the surface treatment of above-mentioned projected at high velocity grinding agent, illustrate silica sand or other sand grains are blowed the blasting treatment of handling to resin surface by compressed air or centrifugal force.Blasting treatment is concavo-convex by forming at resin surface, increases the contact area of film and bonding agent, simultaneously, by WBL and the pollution layer of removing resin surface, improves the method for cementability.Blasting processing unit comprises and blows that sandblasting of grinding-material blows out nozzle, adjusts adjustment valve from the amount (sand amount) of nozzle ejection, the hopper of storage grinding-material, carries compressed-air actuated air chamber.In addition, the sandblast nozzle is variable, and can adjust with the angle of thermoplastic polyimide resin and (angle of sandblast and sandblast distance) at interval.And, sandblast amount, sandblast angle and sandblast distance can be set at appropriate condition the most, and constitute according to the condition that can carry out blasting treatment.In addition, by blowing out the configuration of nozzle, one side that not only can process resin, and can process resin two-sided.Like this, not only can grinding-material be blown into resin surface, and can tunk resin surface by the impeller of high speed rotating by compressed air.The treatment conditions of such blasting treatment must be that processing back grinding-material and grinding charge can not remain in the thermoplastic polyimide resin surface, in addition, can not reduce the intensity of thermoplastic polyimide resin, but the treatment conditions here can be set suitably rule of thumb.Particularly, can use husky or other grinding-materials of silicon as grinding-material, be 0.05～10mm but preferably use particle diameter, the silica sand of more preferred 0.1～1mm.In addition, the sandblast distance preferably is decided to be 100～300mm, and the sandblast angle is 45～90 degree, is more preferably 45～60 degree.In addition, the amount of sandblasting preferably is decided to be 1～10kg/ branch.This is that above-mentioned grinding-material and grinding charge can not remain in the thermoplastic polyimide resin surface because by blasting treatment, and further the degree of depth is ground in control.Have again, grind the degree of depth and concentrate on 0.01～0.1 μ m, mechanical strength of resin is reduced for well.In addition,, can use,, except that above-mentioned blasting treatment, also can use methods such as shot-peening, peening or liquid honing as the surface treatment of projection grinding-material than the high abrasive particle of TPI resin hardness as grinding-material.Shot-peening or peening are to replace as the sand of the grinding-material method with spherical solids (collision).Outside sandblast angle, sandblast distance, the sandblast amount, just can as long as the hardness of solids and granularity etc. are optimized.Liquid honing is with the method for these grinding-materials and liquid while high velocity jet in addition, when above-mentioned grinding-material is shot copper, it can be mixed in the water that has added antirust agent and uses.Handle same effect even also can obtain and sandblast by these methods.
In above-mentioned flame treatment, treatment facility be equipped with to the TPI resin surface blow flame flame treatment nozzle, the chill roll of the above-mentioned resin of cooling so that it can reduce the heat affecting of resin ground is carried out flame treatment.There is no particular limitation for the condition of flame treatment, selects the condition of resin deterioration is got final product.Such condition can rule of thumb suitably be selected, but preferably uses 1000～2000 ℃ flame, for reducing the heat affecting to mother metal, preferably is rolled onto on the chill roll and handles.Preferred 10～100 ℃ of the temperature of chill roll, more preferred 20～50 ℃.From the preferred 5～100mm of the length of flame of flame-thrower nozzle ejection, more preferred 10～50mm.The distance of film and flame treatment nozzle preferably is decided to be film and particularly handles 1/3 position in long from the flame tip to flame 1/2 position in addition.
About above-mentioned hydrophilicity-imparting treatment, hydrophilicity-imparting treatment is used and is contained 10～50 ℃ of aqueous solution that mix with the ratio of hydrazine hydrate 1～15mol/L, alkali metal hydroxide 0.5～5mol/L.Operable alkali metal is sodium, potassium and lithium etc.The aqueous solution that uses hydrazine hydrate and alkali metal hydroxide is because the fracture of the imine linkage by hydrazine hydrate and the hydrolysis that alkali metal hydroxide causes make thermoplastic polyimide resin surface possess hydrophilic property, adsorbs the catalyst core that electroless plating covers usefulness easily.The concentration ratio 1mol/L of hydrazine hydrate hour, the tendency that has the imine linkage fracture fully not carry out.In addition, hydrazine hydrate concentration can reduce the adhesive strength of electroless plating and polyimide resin film during greater than 15mol/L.Therefore, the concentration of hydrazine hydrate at 1mol/L～15mol/L for well.In addition, for the occasion of alkali metal hydroxide, alkali metal hydroxide concn was than 0.5mol/L hour, the inadequate tendency of hydrolysis is arranged, during greater than 5mol/L, the tendency that has adhesive strength to reduce, therefore, the concentration of alkali metal hydroxide at 0.5～5mol/L for well.Change according to differences such as conditions for reaching the needed processing time of hydrophiling, cannot treat different things as the same, usually about 30 second～5 minute.
Usually, after these are handled, in a single day film contacts with atmosphere, and Gai Liang surface can lose activity sometimes, and treatment effect significantly reduces.Therefore, these processing are preferably carried out in a vacuum, directly directly carry out continuous sputter then in a vacuum.
Laminated body of the present invention as shown in Figure 3, non-thermal plasticity Kapton 4 surfaces also can have copper foil layer 5.Above-mentioned copper foil layer 5 can form also and can in addition, form also passable by suitable bonding agent applying Copper Foil with forming the concavo-convex direct bonding formation of Copper Foil with the wet type plating method.By bonding agent the method for Kapton 4 and Copper Foil lamination can be used known methods such as lamination methods or hot pressurization.
In addition, laminated body of the present invention as shown in Figure 4, also can there be adhesive linkage 6 on non-thermal plasticity Kapton 4 surfaces.Above-mentioned adhesive linkage can form by common adhesive resin, so long as have suitable Resin Flow, can realize that the resin of firm cementability all can use known technology.As the resin that is used in this adhesive linkage, roughly can be divided into two kinds of the curing type bonding agents of hot melt adhesion bonding agent that uses thermoplastic resin and the curing reaction that utilizes heat reactive resin.Like this, by on the one side of non-thermal plasticity Kapton 4, forming thermoplastic polyimide layer 3, on another side, form resin bed with cementability with the identical or different kind of above-mentioned thermoplastic polyimide resin, be formed in the lamination with internal substrate, owing to have the structure of suitable bond layer, therefore be applicable to the manufacturing of combination multilayer printed wiring board.In addition, adhesive linkage does not have necessity and is formed on the non-thermal plasticity Kapton, and is formed on the face that does not have metal level of thermoplastic polyimide layer passable yet.
As on the thermoplastic resin that reaches, can list polyimide resin, polyamide-imide resin, polyetherimide resin, polyamide, mylar, polycarbonate resin, polyketone resinoid, polysulfones resin, polyphenylene oxide resin, vistanex, polyphenylene sulfide, fluororesin, multi-aryl-resin and liquid crystal polymer resin etc.Also the adhesive linkage of the combination more than a kind or 2 kinds or 2 kinds in the middle of these as laminated body of the present invention can be used.Wherein, consider, preferably use thermoplastic polyimide resin from viewpoints such as the hear resistance of excellence, electric reliabilities.
As the carboxylic acid dianhydride composition of polyimide resin, can be used in combination common more than a kind or 2 kinds or 2 kinds.Melt cementability in particular for showing excellent heat, preferably use ethylenebis (trimellitic acid monoesters acid anhydrides) as carboxylic acid dianhydride, 2, two (4-hydroxy phenyl) the propane dibenzoates-3 of 2-, 3 ', 4,4 '-tetracarboxylic dianhydride, 1,2-ethylenebis (trimellitic acid monoesters acid anhydrides), 4,4 '-hexafluoroisopropyli,ene, two phthalate anhydrides, 2,3,3 ', 4 '-biphenyl tetracarboxylic dianhydride, 3,3 ', 4,4 '-biphenyl tetracarboxylic dianhydride, 4,4 '-hydroxyl, two phthalate anhydrides, 3,3 ', 4,4 '-benzophenone tetracarboxylic dianhydride, 4,4 '-(4,4 '-isopropylidene, two phenoxy groups) two (phthalic anhydrides).
In addition, as two amine components, can use known diamines, these can be separately, also can be used in combination more than 2 kinds or 2 kinds.Wherein, preferably with 1, two (3-amino-benzene oxygen) benzene, 3 of 3-, 3 '-dihydroxybiphenyl amine or two (4-(3-amino-benzene oxygen) phenyl) sulfone etc. use separately or with ratio mixing arbitrarily respectively.
As above-mentioned thermohardening type resin, can enumerate bimaleimide resin, diallyl naphthols imidodicarbonic diamide (PVC ス ア リ Le Na ジ イ ミ De) resin, phenolic resins, cyanate ester resin, epoxy resin, acrylic resin, methacrylic resin, triazine resin, hydrogenation silicyl (ヒ De ロ シ リ Le) cured resin, pi-allyl cured resin and unsaturated polyester resin etc., they can be separately, also can suitably be used in combination.In addition, except that above-mentioned heat reactive resin, also the side chain or the terminal side chain reactive group type Thermocurable macromolecule that contains epoxy radicals, pi-allyl, vinyl, alkoxysilyl, hydrogenation silicyl or hydroxyl isoreactivity group of macromolecular chain can be used as the heat cure composition.Flowability with the bonding agent of control during caking is a purpose, can be in above-mentioned thermoplastic resin the hybrid thermosetting resin.At this moment, with respect to thermoplastic resin 100 weight portions, the thermosetting resin expectation adds 1～10000 weight portion, preferred 5～2000 weight portions.If thermosetting resin is too much the time, then adhesive linkage has possibility that becomes fragile, and on the contrary, if when very few, then the flowability of bonding agent reduces, and the possibility that makes the cementability reduction is arranged.
Have again, consider, preferably use polyimide resin and epoxy resin, cyanate resin lipid or these are mixed and use from viewpoints such as cementability, processability, hear resistance, flexibility, dimensional stability, low dielectric property, prices.
Printed circuit board of the present invention is made in accordance with the following methods.
About using the wiring board manufacturing method of metal level/Kapton laminated body, in the manufacture method of first kind of printed circuit board, implement electroless plating copper at layer on surface of metal.It can be the chemical plating of using palladium catalyst that this electroless plating covers, or can be by using the direct plating of palladium or carbon etc.So, this electroless plating covers operation in order to give the operation tolerance and/or to cover the defective hole part and implement.According to circumstances different, also can save.And then, on non-electrolytic copper plating layer, form etchant resist, remove the predetermined etchant resist that will form the part of circuit by exposure and etching.Then, the part that electroless plating overlay film or metal level of the present invention are exposed forms circuit as current electrode by the pattern plating method that is formed by cathode copper.Then, remove part against corrosion, remove electroless plating that does not need part and the metal level that forms by physical method, form circuit by etching.This method is the method that is called half add.
The manufacture method of second kind of printed circuit board is following carries out.At first, the same with first kind of manufacture method, form non-electrolytic copper plating layer on the surface of metal level.The same with first kind of manufacture method, also can save electroless plating and cover operation.Then, carry out electrolytic copper plating, form etchant resist on the electrolytic copper plating layer surface.Afterwards, remove the etchant resist of the part that does not form circuit, then remove unwanted metal level and form circuit by etching by exposure process and development.This method is the method that is called subraction.
About using the wiring board manufacturing method of metal level/Kapton/layer laminate, in the manufacture method of first kind of printed circuit board, at first form the through hole that runs through laminated body.Then, implement to remove with layer on surface of metal and the inner polyimides analyte that forms of through hole and because of the carbide of thermosetting be the decontamination operation of the stain of main component.Then, at least at through hole internal implementation electroless plating copper.As mentioned above, it can be the chemical plating of using palladium catalyst that this electroless plating covers, or uses the direct plating of palladium or carbon etc.And then, behind the formation etchant resist, by exposure and the predetermined etchant resist that will form the part of circuit of the removal of developing.Then, electroless plating covered or part that metal level of the present invention exposes as current electrode, carry out the pattern plating that undertaken by cathode copper, form circuit.Then, remove part against corrosion, remove electroless plating and metal level of the present invention or the metal level of the present invention that does not need part, form circuit by etching.Sort circuit formation method is the method that is called half add.
In the manufacture method of second kind of printed circuit board, at first form the through hole that runs through laminated body.Then, pass through the decontamination operation equally, at least at the inner electroless plating copper layer that forms of through hole with first kind of manufacture method.Implement the plate plating by electrolytic copper plating then, by the metal level energising of through hole with the two sides.Then after the electrolytic copper plating layer surface forms etchant resist, remove the etchant resist that does not form circuit part by exposure and development.Then, except that removing the metal level that does not need part, form circuit by etching.
About using the wiring board manufacturing method of metal level/polyimide film layer/copper foil layer laminated body, in the manufacture method of first kind of printed circuit board, at first form run through the metal level and the polyimide film layer that form with physical method and reach/or run through the through hole of metal copper foil.Afterwards, layer on surface of metal and through hole inside are carried out decontamination.Then, at least at through hole internal implementation electroless plating copper.Then, after forming etchant resist on the non-electrolytic copper plating layer and/or on the metal level of the present invention, by exposure and the predetermined etchant resist that will form the part of circuit of the removal of developing.Then, the part that electroless plating overlay film and/or metal level of the present invention are exposed is as current electrode, carries out the pattern plating that undertaken by cathode copper, forms circuit.Then, remove part against corrosion, remove electroless plating or metal level of the present invention or the metal level of the present invention that does not need part, form circuit by etching.Also form about copper foil layer with common methods such as subractions.
In the manufacture method of second kind of printed circuit board, at first form run through the metal level and the polyimide film layer that form with physical method and reach/or run through the through hole of metal copper foil.Afterwards, with above-mentioned carry out decontamination equally after, at least at the inner electroless plating copper layer that forms of through hole.Then, implementing electrolytic copper plating on the non-electrolytic copper plating layer and/or on the metal level of the present invention, making the laminated body of two sides by the through hole conduction.Then after the electrolytic copper plating layer surface forms etchant resist, remove the predetermined etchant resist that forms circuit part by exposure and development.Then, remove the metal level that does not need part, form circuit by etching.Also form circuit about copper foil layer with common methods such as subractions.
The wiring board manufacturing method that comprises the laminated body of metal level/polyimide film layer/adhesive linkage about use, in the manufacture method of first kind of printed circuit board, at first that the adhesive linkage of above-mentioned laminated body is opposed with the circuit face of the wiring plate that forms circuit, adopt heating and/or follow the method for pressurization to carry out lamination.Then, run through metal level and polyimide film layer, form the through hole that arrives wired circuit.Afterwards, implement to remove the polyimides fusion that comes out with layer on surface of metal and through hole inside, analyte and because of the carbide of thermosetting be the decontamination operation of the stain of main component.Then, at least at through hole internal implementation electroless plating copper.Then, behind the formation etchant resist, by exposure and the predetermined etchant resist that will form the part of circuit of the removal of developing.Then, the part that electroless plating overlay film and/or metal level of the present invention are exposed is as current electrode, carries out the pattern plating that undertaken by cathode copper, forms circuit.Then, remove part against corrosion, remove electroless plating and metal level of the present invention or the metal level of the present invention that does not need part, form circuit by etching.
In the manufacture method of second kind of printed circuit board, at first that the adhesive linkage of above-mentioned laminated body is opposed with the circuit face of the wiring plate that forms circuit, adopt heating and/or follow the method for pressurization to carry out lamination.Then, run through metal level and polyimide film layer, form the through hole that arrives wired circuit.Then, carry out with above-mentioned same decontamination after, at least at through hole internal implementation electroless plating copper.Then, implementing electrolytic zinc-coated steel sheet copper facing on the non-electrolytic copper plating layer and/or on the metal level of the present invention.After the electrolytic copper plating layer surface forms etchant resist, there is not the predetermined etchant resist that will form the part of circuit then by the exposure and the removal of developing.Then, remove the metal level that does not need part, form circuit by etching.
In addition, in said method, comprise metal level/Kapton/adhesive linkage laminated body adhesive linkage and form the opposed lamination of circuit face of the wiring plate of circuit, also above-mentioned laminated body can be replaced by adhesive sheet and the wiring plate circuit face lamination that forms circuit.
In addition, use laminated body of the present invention, be manufactured on the two sides and form the printed circuit board of metal level or the multilayer printed wiring board of the further multiple stratification of laminated body is also belonged to category of the present invention.
Handle the thermoplastic polyimide layer surface in heating or ion gun, when making the two-face printing circuit layout card, the preferred use is provided with thermoplastic polyimide layer on non-thermal plasticity Kapton two sides, each surface is carried out after ion gun handles, and perhaps the limit heating edge forms the laminated body of metal level by for example sputter on the two sides.In addition, in the method for making multilayer printed wiring board, the preferred use is provided with thermoplastic polyimide layer on non-thermal plasticity Kapton two sides, and each surface is carried out after ion gun handles, and perhaps the limit heating edge forms the laminated body of metal level by for example sputter.Use this laminated body to make the two-face printing circuit layout card, realize multiple stratification by the bonding agent sheet that sandwiches the interlayer configuration.Perhaps, can use the one side that is manufactured on the non-thermal plasticity Kapton to form thermoplastic polyimide layer/metal level, at the face that does not form metal level the laminated body of bond layer (metal level/thermoplastic polyimide layer/non-thermal plasticity Kapton/bond layer), the so-called clustered operation method of overlapping layer volt circuit layer are set.
In addition, the processing more than a kind or a kind that will select from surface treatment, flame treatment and the hydrophilicity-imparting treatment of combination plasma treatment, sided corona treatment, coupling agent processing, permanganate processing, ultraviolet treatment with irradiation, electron ray treatment with irradiation, projected at high velocity grinding agent of the use printed circuit board that carries out the surface-treated thermoplastic polyimide resin film is made in accordance with the following methods.
In the manufacture method of first kind of printed circuit board, at first form metal level with methods such as electroless plating copper on the thermoplastic polyimide resin surface.And then, after forming etchant resist on the non-electrolytic copper plating layer, remove the predetermined etchant resist that will form the part of circuit by exposure and etching.Then, the part that electroless plating film or metal level of the present invention are exposed is as current electrode, and the pattern plating method by cathode copper forms circuit.Then, remove part against corrosion, the metal level that does not need part that electroless plating is covered formation is removed by etching, forms circuit, makes printed circuit board.This method is the method that is called half add.Carrying out optionally getting through hole before electroless plating covers, after carrying out decontamination and handle with methods such as sulfuric acid, chromic acid, permanganate or plasmas, resin surface and hole wall are being carried out electroless plating cover processing, the surface and the back side that can conducting membrane.
In the manufacture method of second kind of printed circuit board,, optionally, cover the formation metal level by electroless plating getting suitable through hole and carry out the thermoplastic polyimide resin surface that decontamination handles at first with above-mentioned the same.Then implement the electrolysis plating, after metal level becomes 5 μ m or the above thickness of 5 μ m usually, form etchant resist, remove the etchant resist that does not form loop feature with developing by exposure process on the electro deposition surface.Then, remove unwanted metal level by etching and form circuit, make printed circuit board.This method is called subraction.
In the manufacture method of the third printed circuit board, at first, form metal level with the thermoplastic polyimide resin surface of carrying out the decontamination processing by any method in sputtering method, vacuum vapour deposition, ion plating method or the chemical vapor deposition method if necessary in getting suitable through hole.Afterwards, form circuit, make printed circuit board with above-mentioned half add or subraction.
In the manufacture method of the 4th kind of printed circuit board, at first, on the internal substrate that forms internal layer circuit, the lamination laminated body, making at least, skin one side of substrate is a thermoplastic polyimide resin.Optionally, after getting suitable perforation, through hole and carrying out the decontamination processing,, cover any method formation metal level in method or sputtering method, vacuum vapour deposition, ion plating method or the chemical vapor deposition method with electroless plating on the thermoplastic polyimide resin surface.Afterwards, form circuit, make multilayer printed wiring board with above-mentioned half add or subraction.
In two-face printing circuit layout card or multilayer printed wiring board, for between articulamentum, the decontamination that must form through hole and perforation, carry out for clean-out opening is handled and is covered processing for the electroless plating between articulamentum, but, the laminated body of the application of the invention, these printed circuit boards have sufficient tolerance to decontamination liquid and electroless plating copper liquid (strong basicity usually).In addition, handle or heat treated, solved when carrying out pressure boiling experiment the problem that bonding force reduces significantly by the combined ionic rifle.Can make good two sides or multilayer printed wiring board.
In addition, after having the laminated body of adhesive linkage and form the wiring plate of circuit about lamination, form the manufacture method of the printed circuit board of metal level manufacturing, in the manufacture method of first kind of printed circuit board, at first make the adhesive linkage of laminated body opposed, adopt the method lamination that heats and/or accompany by pressurization with the circuit face of the wiring plate that forms circuit.Then run through laminated body, form the through hole that arrives the wiring plate circuit.Afterwards, implement to remove the polyimides fusion that comes out with layer on surface of metal and through hole inside, analyte and because of the carbide of thermosetting be the decontamination operation of the stain of main component.Then, form conductor layer by physical vapor deposition, carry out the plate plating on the thermoplastic polyimide layer surface.At this moment, also can carry out the plate plating in through hole inside.Then, behind the formation etchant resist, by exposure and the predetermined etchant resist that will form the part of circuit of the removal of developing.Then, the part that will expose by the conductor layer that physical vapor deposition forms is as current electrode, carries out the pattern plating that undertaken by cathode copper, forms circuit.Then, remove part against corrosion, remove the conductor layer that physical vapor deposition forms that passes through that does not need part, form circuit by etching.
In this manufacture method, has the feature of carrying out the plate plating by physical vapor deposition.Usually, physical vapor deposition is the dry type operation of carrying out in a vacuum.In addition, the dry type decontamination by plasma etc. are also implemented in a vacuum, therefore, with follow-up physical vapor deposition can be in same indoor enforcement, so preferred especially.In addition, the preferred atmospheric plasma treatment of under atmospheric pressure implementing.These vacuum plasma treatment and atmospheric plasma treatment can be used as any decontamination and handle enforcement.These are handled with the decontamination of permanganic acid class and compare, and the conductor layer that forms by physical vapor deposition has than the decontamination of permanganic acid class with the adhesive strength of thermoplastic polyimide layer handles the tendency that step-down is arranged.Therefore, preferably implement vacuum plasma and atmospheric pressure plasma.It is to carry out in order to remove the stain that produces by laser boring that these decontaminations are handled, and therefore, by with the optimization of lasing condition and performance raising etc., does not have or seldom situation at stain, also can save the decontamination operation.
In the manufacture method of second kind of printed circuit board, at first make the adhesive linkage of laminated body opposed, adopt the method lamination that accompanies by heating and/or accompany by pressurization with the circuit face of the wiring plate that forms circuit.Then run through laminated body, form the through hole that arrives the wiring plate circuit.Then, after above-mentioned same decontamination, carry out carrying out the plate plating by physical vapor deposition.Then, by on the plate coating layer of physical vapor deposition, implement plate plating by electrolytic coating.Afterwards, after the metallide laminar surface forms etchant resist, by exposure and the predetermined etchant resist that does not form the part of circuit of the removal of developing.And then remove unwanted metal level by etching, form circuit.
In addition, above-mentioned such manufacture method has the feature that replaces the wet type electroless plating of original general use to cover with physical vapor deposition.Therefore, have the features such as problem of environmental pollution that can not produce the problem of electroplating as wet type.
In the manufacture method of printed circuit board of the present invention, according to the type etc. of the printed circuit board of expection, can suitably select operation and process conditions, in addition, also can make up other common technology.
That is, forming through hole can be undertaken by using boring methods such as known carbon dioxide laser, UV-YAG laser instrument or excimer laser, boring, punching.When forming little through hole, preferably use the boring method of laser instrument.Here, Zui Da problem is the decontamination operation of through hole.Usually, in this decontamination operation, implement to use the decontamination of the permanganate that presents alkalescence to handle.At this moment, for obtaining sufficient clean effect, and strengthen treatment conditions, make the very weak polyimide resin excessive damage of original alkali resistance.Therefore, particularly the thin metal conductor layer that methods such as evaporation, sputter or ion plating are formed brings fatal influence, and, under the strong oxidizing force influence of the decontamination liquid of permanganate, can produce crack and pore, or problem such as disengaging takes place at conductor layer.
But laminated body of the present invention forms the occasion of metal level on thermoplastic polyimide layer, even implement the common decontamination that permanganate carries out of passing through, crack, pore and the disengaging of metal level can not take place also.This is because thermoplastic polyimide layer has excellent alkaline-resisting medicine than non-thermal plasticity polyimides, be difficult to be corroded, and because than non-thermal plasticity polyimide layer softness, metallic is wrapped up by thermoplastic polyimide layer easily, therefore can realize the strong bond of metallic and thermoplastic polyimide layer.That is, in the decontamination operation of manufacture method of the present invention, can use wet type operations such as permanganate or organic base solution, and utilize dry type operations such as plasma.Therefore, the laminated body of the application of the invention can be carried out the decontamination of the through hole that wears at the printed circuit board that meets high density and low-k requirement really and be handled.In the manufacturing process of the printed circuit board of back, can produce the printed circuit board that defective phenomenons such as pattern disengaging do not take place.Have, the metal level among the present invention covers operation to the electroless plating that comprises interpolation catalyst operation, activation procedure and chemical plating operation after the decontamination operation and has strong durability, also can not reduce its bonding force even form non-electrolytic copper plated film on the surface again.
In addition,, be necessary in through hole, to implement at least, cover, select suitably decision according to the kind of the printed circuit board of expection but whether on metal level of the present invention and copper foil layer surface, form electroless plating carrying out electroless plating when covering.In addition, as the kind that electroless plating covers, the direct plating etc. that can use the chemical plating of utilizing precious metal catalyst effects such as palladium and use palladium, carbon, Organic Manganese conduction epithelium or electroconductive polymer.In addition, resist can use the dry film photoresist of special preferred operations excellence such as aqueous resist or dry film photoresist.In addition, when forming circuit with half add, for removing in the etching that power supply layer carries out, can use sulfuric acid/hydrogen peroxide, ammonium persulfate/sulfuric acid based etchant, perhaps optionally etching is used for the element of metal level of the present invention's various laminated body, i.e. corrosive agent such as nickel, chromium, gold and titanium.
In sum, the laminated body of the application of the invention, the electroless plating that can use the decontamination operation and optionally carry out covers manufacturing processes such as operation, can form L/S and be the following high-density circuit of 20 μ m/20 μ m or 20 μ m/20 μ m, obtain having excellent cementability and at the printed circuit board of the high bonding reliability of severe rugged environment such as hot and humid.
Embodiment
For embodiment, specifically describe effect of the present invention, but the present invention is not limited to following examples below, those skilled in the art only otherwise exceed scope of the present invention just can carry out various changes, correction and change to the present invention.In addition, the preparation of the preparation of the various Kaptons among the embodiment, metal level, various mensuration and evaluation are carried out in accordance with the following methods.
Scheme 1
(the preparation method A of non-thermal plasticity Kapton)
To by pyromellitic acid dianhydride/4,4 '-diamino-diphenyl ether/p-phenylenediamine (PPD) is with the N of 17 weight % of the synthetic polyamic acid of the ratio of mol ratio 4/3/1, among dinethylformamide (hereinafter referred to as DMF) the solution 90g, mix the transforming agent that comprises acetic anhydride 17g and isoquinolin 2g, and by stir and the centrifugation deaeration after, be coated on the aluminium foil with the thickness curtain coating of 700 μ m.From being stirred to deaeration, the limit is cooled to 0 ℃ of limit and carries out.The laminated body of this aluminium foil and polyamic acid solution was heated 4 minutes the gel film that obtains having self-supporting down at 110 ℃.The residual volatile ingredient content of this gel film is 30 weight %, and the imidization rate is 90%.This gel film is peeled off from aluminium foil, be fixed on the framework, this gel film is carried out 300 ℃, 400 ℃, 500 ℃ heated each 1 minute down, preparation thickness is 25 μ m Kaptons.
(the preparation method B of non-thermal plasticity Kapton)
Remove pyromellitic acid dianhydride/4,4 '-diamino-diphenyl ether prepares Kapton with the method identical with preparation method A beyond synthesizing with the ratio of mol ratio 1/1.
(the preparation method C of non-thermal plasticity Kapton)
Use 3,3 ', 4,4 '-biphenyl tetracarboxylic dianhydride/TOPOT 2,2 (trimellitic acid monoesters acid anhydrides)/p-phenylenediamine (PPD)/4,4 '-diamino-diphenyl ether is with the N of 17 weight % of the synthetic polyamic acid of the ratio of mol ratio 4/5/7/2, N-dimethylacetylamide (DMAc) solution is not sneaked into transforming agent wherein, is coated on the aluminium foil with the thickness curtain coating of 700 μ m.The laminated body of this aluminium foil and polyamic acid solution was heated 10 minutes the gel film that obtains having self-supporting down at 110 ℃.The residual volatile ingredient content of this gel film is 30 weight %, and the imidization rate is 50%.Use this gel film, use the method same, the preparation Kapton with facture-A.
(the preparation method X of TPI precursor)
1, two [2-(4-amino-benzene oxygen) ethyoxyl] ethane of 2-(below, note is made DA3EG) and 2, two [4-(4-amino-benzene oxygen) phenyl] propane (following note is made BAPP) of 2-are dissolved among the DMF with mol ratio at 3: 7, add 3 with 5: 1 ratio of mol ratio while stirring, 3 ', 4,4 '-ethylene glycol bisthioglycolate benzoic ether tetracarboxylic dianhydride (following note is made TMEG) and 3,3 ', 4,4 '-benzophenone tetracarboxylic dianhydride (following note is made BTDA), stir about one hour obtains the polyamic acid solution that solid component concentration is 20 weight %.
(the preparation method Y of TPI precursor)
In DMF, stir on the limit with the BAPP uniform dissolution, and the limit adds 3,3 ', 4 with 4: 1 ratio of mol ratio, 4 '-biphenyl tetracarboxylic dianhydride and ethylenebis (trimellitic acid monoester acid anhydrides), and make carboxylic acid dianhydride and diamines for etc. molar ratio.Stir about one hour obtains the DMF solution of the polyamic acid of solid component concentration 20 weight %.
(preparation of lamination Kapton)
Non-thermal plasticity Kapton with above-mentioned manufacture method-A, B and C preparation uses as the core film, on its two sides or one side, with the DMF solution as the polyamic acid of the precursor of TPI of intaglio plate coating machine coating manufacture method-X and Y preparation.
After the coating, 120 ℃ of following dry solvents 4 minutes, in 390 ℃ of heating down of final heating-up temperature, carry out imidizate, preparation comprises the lamination Kapton of non-thermal plasticity Kapton and thermoplastic polyimide layer.In addition, change coating weight and can obtain the different film of thermoplasticity polyimides layer thickness.In the table, these films, for example the non-thermal plasticity Kapton is with A method preparation, and the two sides all is that the situation of the thermoplastic polyimide layer for preparing with the X method is recited as X/A/X; One side is that thermoplastic polyimide layer, another side are that the situation of Copper Foil is recited as X/A/Cu.
(forming metal level) with sputtering method
On Kapton, form metal, use (strain) clear and vacuum system sputtering equipment NSP-6, carry out with following method.With the macromolecule membrane furnace of packing into, close vacuum chamber.Lamp is carried out according to the heater heating in substrate (macromolecule membrane) limit rotation revolution limit, be evacuated to 6 * 10 -4Pa or 6 * 10 -4Below the Pa.Import argon gas afterwards, under 0.35Pa, by the DC sputter, sputter nickel and then sputter copper.DC power, any one all is decided to be 200W.Film speed is nickel 7nm/ branch, copper 11nm/ branch, adjusts film formation time and may be controlled to film thickness.
(synthesizing of adhesive linkage)
Under nitrogen environment, two { 4-(3-amino-benzene oxygen) phenyl } sulfones (following note is BAPS-M) of 1 equivalent are dissolved in N, in the dinethylformamide (following note is DMF).Stir on cooling solution limit, limit, 4,4 '-(4,4 '-isopropylidene, two phenoxy groups) two (phthalic anhydrides) (following note be BPADA) of dissolving and polymerization 1 equivalent, and obtaining the polymer/solid constituent concentration is the polyamic acid polymer solution of 30% weight %.This polyamic acid solution is heated under 200 ℃, 180 minutes, the decompression of 665Pa, obtain solid-state thermoplastic polyimide resin.Oiling Xi Er (シ エ Le) society's system) and 4 with the above-mentioned polyimide resin that obtains and phenolic resin varnish type epoxy resin (Ai Pikete (エ ピ コ one ト) 1032H60:, (following note does 4 to 4 '-DADPS, 4 '-DDS) ratio mixing with weight ratio 70/30/9, be dissolved in two oxa-s, penta ring, make that solid component concentration is 20 weight %, obtains adhesive solution.The adhesive solution that obtains is coated on the Kapton face of the laminated body after forming with above-mentioned metal level, making its dried thickness is 12.5 μ m, 170 ℃ of dry down laminated body that obtained forming adhesive linkage in 2 minutes.
(lamination procedure)
By the glass epoxide copper-coated laminated board of Copper Foil 12 μ m prepare inner layer circuit board with above-mentioned laminated body by vacuum pressed, under the condition of 200 ℃ of temperature, hot plate pressure 3MPa, 2 hours pressing times, vacuum condition 1kPa, be stacked on the inner layer circuit board, and solidify.
(mensuration of adhesive strength)
According to IPC-TM-650-method .2.4.9, under pattern width 3mm, peel angle 90 degree, peeling rate 50mm/min, measure.
(pressure boiling experiment)
Under 121 ℃, the condition of 100%RH, carry out experiment in 96 hours.
(evaluation of anti-soil release characteristics)
Use the UV laser instrument, when the two sides has the laminated body of metal level, form through hole or be to form to run through metal level and polyimide film layer when one side is Copper Foil, reach the non through hole of copper-clad surface.The person of connecing in the NaOH decontaminating solution of the potassium permanganate of 50g/L and 40g/L, under 70 ℃, is flooded the sample that worn the hole 10 minutes.Whether after the washing, remove with the stain of copper foil surface at the bottom of the hole under the stain of microscopic examination hole periphery or the non through hole situation, stain is all removed in either case fully.Here, with metal level, polyimide film layer and wall surface of the hole have or not any damage, particularly metal level to have or not to peel off with perk be that the center is observed.Under the situation that forms 100 holes, in 100 any one all fully not damage be evaluated as ◎, observe 1～3 scope small any damage be evaluated as zero, 10 or 10 with interior the average evaluation of obvious damage is arranged is △, the average evaluation more than 10 or 10 is *.
(mensuration of the swollen long coefficient of heat)
The thermal coefficient of expansion of TPI/non-thermal plasticity polyimide laminates body, with the system TMA 120C of Sai Keyinsiciermente (セ イ コ one イ Application ス Star Le メ Application ト) society, at 20 ℃/minute of programming rates, nitrogen flow 50ml/ branch, the wide 3mm of sample shape, under the condition of long 10mm, heavy burden 3g, rise to 300 ℃ from room temperature, measure 2 times.With the thermal coefficient of expansion of the 2nd time 100～200 ℃ average coefficient of linear expansion as this laminated body.
Embodiment 1～6
Make Kapton with coating on the one side of the non-thermal plasticity Kapton of the thick 25 μ m of preparation method A, B or C preparation by the method for the polyamic acid solution of manufacture method X or Y preparation.The thickness of thermoplastic polyimide layer is 3 μ m.
Then, 1 minute nickel of sputter on thermoplastic polyimide layer, forming thickness is the nickel film of 6nm.Carry out 9 minutes sputter copper continuously, forming thickness is the copper film of 100nm, obtains metal level/polyimide film layer laminated body.On the sputtered film that obtains, form the copper layer of thick 18 μ m by electrolytic plating method.Measure adhesive strength and anti-soil release characteristics after adhesive strength, the pressure boiling at normal temperatures of this laminated body tested.It the results are shown in table 2.
Table 2
Embodiment Polyimides preparation method and structure The structure of metal level Anti-soil release characteristics Peel strength (N/cm) Adhesive strength (N/cm) after the PCT experiment
1 X/A/ Ni/Cu ◎ 12 8
2 X/B/ The same ◎ 11 7
3 X/C/ The same ◎ 11 7
4 Y/A/ The same ◎ 11 7
5 Y/B/ The same ◎ 12 7
6 Y/C/ The same ◎ 12 7
Can learn that from the result laminated body of the present invention can realize excellent cementability and anti-soil release characteristics.
Embodiment 7～14
With coating is by the method for the polyamic acid solution of manufacture method Y preparation on the two sides of the non-thermal plasticity Kapton of the thick 25 μ m of preparation method C preparation, preparation forms the sample of the different thermoplastic polyimide layer of thickness.1 minute nickel of sputter on this film, forming thickness is the nickel film of 6nm.Carry out 9 minutes sputter copper continuously, forming thickness is the copper film of 100nm, obtains metal level/polyimide film layer laminated body.As power supply layer, form the copper layer of thick 18 μ m with the sputtered film that obtains by electrolytic plating method.Adhesive strength, anti-soil release characteristics and thermal coefficient of expansion after the laminated body that mensuration obtains adhesive strength, pressure boiling at normal temperatures tested.The results are shown in table 3.Here, about coefficient of thermal expansion, the coefficient of thermal expansion of non-thermal plasticity film A is 12ppm/ ℃ in this experiment, mensuration forms the coefficient of thermal expansion behind the thermoplastic layer, its value is evaluated as ◎ for time below 20ppm/ ℃ or 20ppm/ ℃, be evaluated as zero in the time of below 25ppm/ ℃ or 25ppm/ ℃, be evaluated as △ in the time of below 30ppm/ ℃ or 30ppm/ ℃, be evaluated as in the time of more than 30ppm/ ℃ *.
Table 3
Embodiment The thickness of thermoplastic polyimide layer Y (μ m) Anti-soil release characteristics Peel strength (N/cm) Adhesive strength (N/cm) after the PCT experiment Thermal coefficient of expansion (ppm/ ℃)
7 0.01 △ 7 4 ◎
8 0.05 ◎ 10 5 ◎
9 0.1 ◎ 10 6 ◎
10 1.0 ◎ 10 7 ◎
11 3.0 ◎ 12 8 ◎
12 5.0 ◎ 13 8 ○
13 10 ◎ 13 8 △
14 20 ◎ 12 7 ×
Can learn that from the result thickness of thermoplastic polyimide layer is more preferably 0.1 μ m～5 μ m preferably at 0.01 μ m～10 μ m.
Embodiment 15～22
Two sides at the non-thermal plasticity Kapton of thick 7.5 μ m, 12.5 μ m, 25 μ m and the 50 μ m of preparation method C preparation, the polyamic acid solution that coating prepares with preparation method Y, the thermoplastic polyimide layer laminated body of making the thickness that forms 1 μ m, 5 μ m and 10 μ m of the method.
1 minute nickel of sputter on this film, forming thickness is the nickel film of 6nm.Carry out 9 minutes sputter copper continuously, forming thickness is the copper film of 100nm, obtains metal level/polyimide film layer laminated body.As power supply layer, form the copper layer of thick 5nm with the sputtered film that obtains by electrolytic plating method.Adhesive strength, anti-soil release characteristics and thermal coefficient of expansion after the laminated body that mensuration obtains adhesive strength, pressure boiling at normal temperatures tested.The results are shown in table 4.Here, about coefficient of thermal expansion, the coefficient of thermal expansion of non-thermal plasticity film A is 12ppm/ ℃ in this experiment, mensuration forms the thermal coefficient of expansion behind the thermoplastic layer, its value is evaluated as ◎ for time below 20ppm/ ℃ or 20ppm/ ℃, be evaluated as zero in the time of below 25ppm/ ℃ or 25ppm/ ℃, be evaluated as △ in the time of below 30ppm/ ℃ or 30ppm/ ℃, be evaluated as in the time of more than 30ppm/ ℃ *.
Table 4
Embodiment The thickness of non-thermal plasticity polyimide layer C (μ m) The thickness of thermoplastic polyimide layer Y (μ m) Anti-soil release characteristics Peel strength (N/cm) Adhesive strength (N/cm) after the PCT experiment Thermal coefficient of expansion (ppm/ ℃)
15 7.5 1 ◎ 11 6 ◎
16 7.5 5 ◎ 12 7 ×
17 7.5 10 ◎ 12 7 ×
18 12.5 5 ◎ 12 8 △
19 12.5 10 ◎ 12 8 ×
20 25 5 ◎ 13 8 ○
21 25 10 ◎ 13 8 △
22 50 10 ◎ 13 8 ○
Can learn from the result, as printed circuit board, the rerum natura (for example thermal coefficient of expansion etc.) that has the non-thermal plasticity Kapton of excellent specific property for generation, the thickness of thermoplastic polyimide layer must be than the thin thickness of non-thermal plasticity Kapton, the thickness of each face of preferred thermoplastic polyimide layer is below 1/2 or 1/2 of non-thermal plasticity polyimide layer, is more preferably below 1/5 or 1/5.
Comparative example 1
Non-thermal plasticity Kapton (that is, not having the film of thermoplastic polyimide layer) surface with manufacture method-A makes with method similarly to Example 1, makes metal film, uses the same method and measures cementability and anti-soil release characteristics.Its result, adhesive strength are 7N/cm, and it is 2N/cm that the adhesive strength after the pressure boiling experiment lowers.In addition, anti-soil release characteristics be *.This result is by comparing with table 2, learn under the situation that does not have thermoplastic polyimide layer, and the characteristic that can not obtain stipulating has been confirmed the effect of thermoplastic polyimide layer.
Embodiment 23～32
With the method identical with embodiment 1, form the nickel bottom (the 1st metal level) of all thickness and the metal level (the 2nd metal level) of cupric, measure its adhesive strength, the results are shown in table 5.
Table 5
Embodiment The thickness of nickel bottom (nm) The thickness (nm) of copper layer (the 2nd metal level) Anti-soil release characteristics Peel strength (N/cm) Adhesive strength (N/cm) after the PCT experiment
23 0 100 × 7 3
24 2 100 △ 11 5
25 5 100 ◎ 11 7
26 10 5 × 9 2
27 10 10 △ 10 5
28 10 100 ◎ 12 7
29 10 200 ◎ 12 7
30 20 500 ◎ 12 7
31 50 100 ◎ 10 6
32 100 100 ◎ 8 4
Learn the preferred 2nm of bottom nickel dam or more than the 2nm, the preferred 10nm of copper layer or more than the 10nm from this result.
Embodiment 33
Preparation prepares the laminated body of the thick copper metal layer (the 2nd metal level) of the thick nickel bottom (the 1st metal level) of the 5nm that forms with sputtering method and 100nm on the two sides of the Kapton of the laminated body with Y/B/Y (Y is 1 μ m, and B is 25 μ m) structure.Use this laminated body to form circuit in order to following method.
At first, after forming the internal diameter run through laminated body and be the through hole of 30 μ m with the UV-YAG laser instrument, in the decontaminating solution of the NaOH of the potassium permanganate of 50g/L and 40g/L, under 70 ℃, flood 10 minutes, carry out the decontamination processing.Then, cover method at layer on surface of metal and the inner copper coating that forms of through hole with electroless plating.The formation method of electroless plating is as follows.At first, laminated body is cleaned in alkaline cleaner, then, in acid, carried out short time pre-preg.Then, carry out in aqueous slkali that palladium adds and reduce by alkali.Afterwards, carry out non-cathode copper plating in alkali.The temperature of plating is that the time of room temperature, plating is 10 minutes, and this method can form the thick non-electrolytic copper plating layer of 300nm.
Afterwards, coating liquid light sensitivity plating resist (Japanese synthetic rubber (strain) society system, THB320P) carries out mask exposure with high-pressure mercury-vapor lamp then, and forming L/S is the corrosion-resisting pattern of 10 μ m/10 μ m.Then, carry out electrolytic copper plating, form copper circuit on the surface of non-electrolytic copper plating layer epithelium exposed portions serve.Electrolytic copper plating, at first in 10% sulfuric acid, wash 30 seconds in advance after, carry out 40 minutes plating then at room temperature.Current density is 2A/dm 2The thickness of electrolysis copper film is 10 μ m.Then, peel off the plating etchant resist with alkali type stripper, the sputter nickel dam is removed with the selective etching liquid (plum gram (メ Star Network) (strain) system etching solution NH-1862) of nickel, obtains printed circuit board.
The printed circuit board that obtains has the L/S that conforms to design load, and does not have undercut.The Auger (オ one シ エ) that further carries out the power supply layer glass part is analyzed and the kish that undertaken by EPMA has or not mensuration, but does not think and have kish.In addition, circuit pattern is bonding securely with the intensity of 11N/cm.
Embodiment 34
At first, prepare the laminated body of X/A/Cu (X is that 1 μ m, A are that 25 μ m, Copper Foil are 15 μ m) structure, preparation forms the laminated body of the thick copper metal layer (the 2nd metal level) of the thick nickel bottom (the 1st metal level) of 5nm and 100nm with sputtering method at the X laminar surface.Use this laminated body to form circuit in order to following method.
At first, at the macromolecule membrane of the layer on surface of metal attaching that forms with sputtering method as diaphragm.Then, the dry film photoresist of fitting on Copper Foil (the dry film photoresist AQ of Asahi Chemical Industry) exposes and develops, and forms the circuit of L/S=30 μ m/30 μ m with common subraction.The etchant that uses is ferric chloride in aqueous solution.Then, remove diaphragm, use the fine circuits that forms L/S=10 μ m/10 μ m with the same method of embodiment 33 at the splash-proofing sputtering metal laminar surface.With through hole in embodiment 33 is that through hole is relative, for running through splash-proofing sputtering metal layer and polyimide film layer, reaches the hole of the circuit the inside that forms with Copper Foil in the present embodiment, and this point is different.
The printed circuit board that obtains has the L/S that conforms to design load, and does not have undercut.The Auger (オ one シ エ) that further carries out the power supply layer glass part is analyzed and the kish that undertaken by EPMA has or not mensuration, but does not think and have kish.In addition, circuit pattern is bonding securely with the intensity of 11N/cm.
Embodiment 35
On the two sides of Kapton, form the laminated body of the thick copper metal layer (the 2nd metal level) of the thick nickel bottom (the 1st metal level) of 5nm and 100nm with sputtering method with X/A/X (X is that 1 μ m, A are 25 μ m) structure.Use this laminated body to form circuit in order to following method.
At first, forming the internal diameter that runs through laminated body with the UV-YAG laser instrument is the through hole of 30 μ m.Then carry out after the decontamination processing, cover method at layer on surface of metal and the inner copper coating that forms of through hole with electroless plating.The formation method of electroless plating is as follows.At first, laminated body is washed in alkaline cleaner, then, in acid, carry out short time pre-preg.Then, in aqueous slkali, add palladium and reduce by alkali.Afterwards, carry out chemical plating in alkali.The temperature of plating is that the time of room temperature, plating is 10 minutes, and this method can form the thick non-electrolytic copper plating layer of 300nm.Then carry out electrolytic copper plating, form the thick copper coating of 10 μ m.Electrolytic copper plating washed in 10% sulfuric acid 30 seconds in advance, at room temperature carried out 40 minutes plating then.Current density is 2A/dm 2The thickness of electrolysis copper film is 10 μ m.
Afterwards, coating liquid light sensitivity plating resist (Japanese synthetic rubber (strain) society system, THB320P) carries out mask exposure with high-pressure mercury-vapor lamp then, and forming L/S is the corrosion-resisting pattern of 10 μ m/10 μ m.Pattern with such making is by common subraction (medicine name: iron chloride) form circuit.Then, the sputter nickel dam is removed with the selective etching liquid (plum gram (メ Star Network) (strain) system etching solution NH-1862) of nickel, has again, peels off the plating etchant resist with alkali type stripper,, make printed circuit board.
The printed circuit board that obtains has the L/S that conforms to design load, and does not have undercut.The Auger (オ one シ エ) that further carries out the power supply layer glass part is analyzed and the kish that undertaken by EPMA has or not mensuration, but does not think and have kish.In addition, circuit pattern is bonding securely with the intensity of 11N/cm.
Embodiment 36
Make Kapton with coating on the one side of the non-thermal plasticity Kapton of the thick 25 μ m of preparation method A preparation by the method for the polyamic acid solution of manufacture method X preparation.The thickness of thermoplastic polyimide layer is 3 μ m.1 minute nickel of sputter on this film, forming thickness is the nickel film of 6nm.Carry out 9 minutes sputter copper continuously, forming thickness is the copper film of 100nm, obtains metal level/polyimide film layer laminated body.
Then, be coated with adhesive linkage, obtain comprising the laminated body of metal level/polyimide film layer/adhesive linkage.And then, with this laminated body lamination and be solidificated on the inner layer circuit board of making by above-mentioned glass epoxide copper-coated laminated board, obtain assembled substrate.The thickness formation method and the laminating method of adhesive linkage were introduced.
At first, form the through hole of arrival internal layer circuit that internal diameter is 30 μ m with the UV-YAG laser instrument after, in the decontaminating solution of the NaOH of the potassium permanganate of 50g/L and 40g/L, under 70 ℃, flood 10 minutes, carry out the decontamination processing.Then, cover method at layer on surface of metal and the inner copper coating that forms of through hole with electroless plating.The formation method of electroless plating is as follows.At first, laminated body is washed in alkaline cleaner then, in acid, carry out short time pre-preg.Then, palladium adds and reduces by alkali in aqueous slkali.Afterwards, the electroless plating that carries out in alkali covers.The temperature of plating is that the time of room temperature, plating is 10 minutes, can form the thick non-electrolytic copper plating layer of 300nm with this method.
Afterwards, coating liquid light sensitivity plating resist (Japanese synthetic rubber (strain) society system, THB320P) carries out mask exposure with high-pressure mercury-vapor lamp then, and forming L/S is the corrosion-resisting pattern of 10 μ m/10 μ m.Then, carry out electrolytic copper plating, form copper circuit on the surface of non-electrolytic copper plating layer epithelium exposed portions serve.Electrolytic copper plating washed in 10% sulfuric acid 30 seconds in advance, carried out 40 minutes plating then at room temperature.Current density is 2A/dm 2The thickness of electrolysis copper film is 10 μ m.Then, peel off the plating etchant resist with alkali type stripper, the sputter nickel dam is removed with the selective etching liquid (plum gram (メ Star Network) (strain) system etching solution NH-1862) of nickel, obtains printed circuit board.
The printed circuit board that obtains has the L/S that conforms to design load, and does not have undercut.The Auger (オ one シ エ) that further carries out the power supply layer glass part is analyzed and the kish that undertaken by EPMA has or not mensuration, but does not think and have kish.In addition, circuit pattern is bonding securely with the intensity of 13N/cm.Anti-decontamination operation is also good.
Embodiment 37
With the method identical with embodiment 36, form the laminated body that comprises splash-proofing sputtering metal layer/Y/C/ adhesive linkage, with this laminated body lamination and be solidificated on the inner layer circuit board of making by above-mentioned glass epoxide copper-coated laminated board, obtain assembled substrate.
Then, form the through hole of arrival internal layer circuit that internal diameter is 30 μ m with the UV-YAG laser instrument after, in the decontaminating solution of the NaOH of the potassium permanganate of 50g/L and 40g/L, under 70 ℃, flood 10 minutes, carry out the decontamination processing.Then, cover method at layer on surface of metal and the inner copper coating that forms of through hole with electroless plating.The formation method of electroless plating is as follows.At first, laminated body is washed in alkaline cleaner, then, in acid, carry out short time pre-preg.Then, in aqueous slkali, add palladium and the reduction by alkali.Afterwards, the electroless plating that carries out in alkali covers.The temperature of plating is that the time of room temperature, plating is 10 minutes, can form the thick non-electrolytic copper plating layer of 300nm with this method.
Afterwards, coating liquid light sensitivity plating resist (Japanese synthetic rubber (strain) society system, THB320P) carries out mask exposure with high-pressure mercury-vapor lamp then, and forming L/S is the corrosion-resisting pattern of 10 μ m/10 μ m.Then, carry out electrolytic copper plating, form copper circuit on the surface of non-electrolytic copper plating layer epithelium exposed portions serve.Electrolytic copper plating washed in 10% sulfuric acid 30 seconds in advance, carried out 40 minutes plating then at room temperature.Current density is 2A/dm 2The thickness of electrolysis copper film is 10 μ m.Then, peel off the plating etchant resist with alkali type stripper, the sputter nickel dam is removed with the selective etching liquid (plum gram (メ Star Network) (strain) system etching solution NH-1862) of nickel, obtains printed circuit board.
The printed circuit board that obtains has the L/S that conforms to design load, and does not have undercut.The Auger (オ one シ エ) that further carries out the power supply layer glass part is analyzed and the kish that undertaken by EPMA has or not mensuration, but does not think and have kish.In addition, circuit pattern is bonding securely with the intensity of 13N/cm.Anti-decontamination operation is also good.
Scheme 2 (surface treatment)
Embodiment 38
(preparation of non-thermal plasticity Kapton)
To by pyromellitic acid dianhydride/TOPOT 2,2 (trimellitic acid monoesters acid anhydrides)/p-phenylenediamine (PPD)/4,4 '-diamino-diphenyl ether is with the N of 17 weight % of the synthetic polyamic acid of the ratio of mol ratio 1/1/1/1, among the dinethylformamide solution 90g, mix the transforming agent that comprises acetic anhydride 17g and isoquinolin 2g.Then by stirring, after the centrifugation deaeration, being coated on the aluminium foil with the thickness curtain coating of 300 μ m.From being stirred to deaeration, the limit is cooled to 0 ℃ of limit and carries out.The laminated body of this aluminium foil and polyamic acid solution was heated 4 minutes the gel film that obtains having self-supporting down at 110 ℃.The residual volatile ingredient content of this gel film is 30 weight %, and the imidization rate is 90%.This gel film is peeled off from aluminium foil, be fixed on the framework, this gel film is carried out 300 ℃, 400 ℃, 500 ℃ heated each 1 minute down, preparation thickness is the non-Kaptons of 25 μ m.
(manufacture method of TPI precursor)
Will be as 2,2 ' of diamines-two [4-(4-amino-benzene oxygen) phenyl] propane uniform dissolution in N, in the dinethylformamide.Stir on the limit, and add as 3,3 ', 4 of carboxylic acid dianhydride with 4: 1 ratio of mol ratio on the limit, 4 '-biphenyl ketone tetracarboxylic dianhydride and ethylenebis (trimellitic acid monoester acid anhydrides), and carboxylic acid dianhydride and diamines are become etc. mole.Stir about one hour obtains the N that solid component concentration is the polyamic acid of 20 weight %, dinethylformamide solution.
(manufacturing of lamination Kapton)
Use as the core film with above-mentioned non-thermal plasticity Kapton, on its two sides, with the N of intaglio plate coating machine coating as the polyamic acid of the precursor of TPI, dinethylformamide solution.After the coating, by the heat treated dry solvent, and the imidizate that carries out polyamic acid, prepare the lamination Kapton that comprises non-thermal plasticity polyimides layer film and TPI down for 390 ℃ in final heating-up temperature.With system NweView5030 system of optical interference formula surface roughometer ZYGO society, 10 mean roughness measuring the thermoplastic polyimide layer surface of the lamination Kapton that obtains are 0.1 μ m.
(formation of metal level)
One side at above-mentioned lamination Kapton, use (strain) clear and vacuum system sputtering equipment NSP-6, at first by Yi Enteke (イ オ Application テ Star Network) society system filament cathode ion gun (model name: 3-1500-100FC) with ion gun power supply (MPS3000), under the condition of argon gas, electron-beam voltage 400V, accelerating potential 500V and electron beam current 20mA, carry out 20 minutes ion guns and handle.Thereafter, sputter nickel 6nm (0.2Pa, DC power output 200W, sputtering time 1 minute are pressed in sputter), copper 200nm (0.2Pa, DC power output 200W, sputtering time 18 minutes are pressed in sputter) make laminated body.Here above-mentioned sputtering equipment NSP-6 has, and above-mentioned ion gun treatment facility is installed in the vacuum chamber, can carry out the structure of ion gun processing and sputter process continuously.In addition, this equipment can rotation revolution in limit, 11 substrate limits carry out ion gun processing and sputter process in vacuum chamber.That is, each substrate carries out that ion gun is handled and the time of sputter process is 5～7% of whole processing times.Protective film (Japan's seal strange (イ Application キ) manufacturing (strain) system: Leo En Ermu (リ オ エ Le system) LE952-T1) that hear resistance and releasable are then arranged at metal level upper strata pressing element.
(synthesizing of adhesive linkage)
To be coated on the adhesive solution that scheme 1 obtains equally on the face of the metal level that does not form above-mentioned laminated body; and thickness is 12.5 μ m after making it dry; form adhesive linkage in dry 2 minutes down at 170 ℃ then, obtain comprising the laminated body of heat-resistance protection film/metal level/thermoplastic polyimide resin layer/non-thermal plasticity Kapton/adhesive linkage.
(lamination procedure)
The same with scheme 1, in inner layer circuit board superimposed layer and curing, obtain comprising the laminated body of heat-resistance protection film/metal level/polyimide film layer/bond layer/glass epoxide copper-coated laminated board.
(punching, decontamination, electroless copper operation)
After peeling off the heat-resistance protection film on laminated body surface, be to estimate anti-decontamination fluidity of laminated body and the copper of anti-electroless plating fluidity, laminated body carry out table 6 in each operation of condition.
Table 6
Operation Prescription for the treatment of liquid Treatment conditions
1 Do special P (ス ウ エ リ Application グ セ キ ユ リ ガ Application ト) NaOH in the Si Weilingesaike 500ml/l 3g/l 60 ℃ 5 minutes
(washing)
2 Kern Sai Enteleite Kern Parker spy (コ Application セ Application ト レ one ト コ Application パ Network ト) CP (※) NaOH 550ml/l 40g/l 80 ℃ 5 minutes
(washing)
3 The Li Dakexiao ENSO stays to cut does special (リ ダ Network シ ヨ Application ソ リ ユ シ ヨ Application セ キ ユ リ ガ Application ト) P500 (※) sulfuric acid in the Encke 70ml/l 50ml/l 40 ℃ 5 minutes
(washing)
4 Do special (Network リ one Na one セ キ ユ リ ガ Application ト) 902 (※) Ke Linayadetebo (Network リ one Na one ア デ イ テ イ) 902 (※) NaOH in the Ke Linake 40ml/l 3ml/l 20g/l 60 ℃ 5 minutes
(washing)
5 Pu Lidepuneiao does special (プ リ デ イ プ ネ オ ガ Application ト) B (※) sulfuric acid 20ml/l 1ml/l Room temperature 1 minute
6 (※) the NaOH boric acid of special (ア Network チ ベ one one ネ オ ガ Application ト) 834 elder brothers grams (コ Application Network) of doing difficult to understand in the Ya Keqi beta 40ml/l 4g/l 5g/l 40 ℃ 5 minutes
(washing)
7 In excellent Sha Neiao does special (リ デ ユ one サ one ネ オ ガ Application ト) (※) NaOH 1g/l 5g/l Room temperature minute
(washing)
8 The excellent effect of Bei Xikesuoli An Pulinte does dried special (the カ Star パ one ソ リ ユ one シ ヨ Application プ リ Application ト ガ Application ト) MSK (※) of spy (ベ one シ Star Network ソ リ ユ one シ ヨ Application プ リ Application ト ガ Application ト) the excellent effect of MSK-DK (※) Ka Pasuoli An Pulinte, and this reaches inner excellent Sha (リ デ ユ one サ one) copper (※) that gets than dried special (the ス PVC ラ イ ザ one プ リ Application ト ガ Application ト) MSK-DK (※) of Rye Zha Pulinte 80ml/l 40ml/1 3ml/l 4ml/l 35 ℃ 15 minutes
(washing)
(※) (Ya Tedekejiapaen (ア ト テ Star Network ジ ヤ パ Application) (strain) system)
(electro-coppering operation)
Using copper sulphate plating bath (Ha イ ス ロ one bathes), is 2A/dm in current density 2Down, carry out 40 minutes electroplating, the thickness of copper film is 18 μ m.In addition, use the wild pharmacy system Mortopl Er Qinameikeyapu of society difficult to understand (ト Star プ Le チ Na メ one Network ア Star プ) (10ml/l) and pul very receive (プ Le チ Na) (2.5ml/l) 81-HL as the additive of plating bath.
In addition, determining bonding strength under the normality and pressure boiling experiment and state 1 carry out equally.
(formation of fine circuits)
Use comprises the laminated body of metal level/thermoplastic polyimide layer/non-thermal plasticity Kapton/adhesive linkage/glass epoxide copper-coated laminated board, and by half add, forming L/S is the circuit of 15 μ m/15 μ m.Can to form metal level/thermoplastic polyimide layer interface be level and smooth (Rz=0.1 μ m), do not produce the good circuit of etch residue.
Comparative example 2
Except that not forming on the non-thermal plasticity Kapton the thermoplastic polyimide layer, when making laminated body with the same method of embodiment 38, in the decontamination operation, metal level the crack occurs and peels off, and can not make laminated body.
Comparative example 3
On the coarse epoxy resin base plate that turns to Rz=3 μ m, form metal level on the substrate through the processing 4～8 of table 6.Use it to form the circuit of L/S=15 μ m/15 μ m, but etch residue is arranged on the resin surface, can not form good circuit with half add.
Embodiment 39
(making of thermoplastic polyimide film)
The TPI precursor that embodiment 38 is obtained is coated on the intaglio plate coating machine on the PET film of thick 125 μ m, 120 ℃ of following heat dryings 4 minutes, the semi-solid preparation film that obtains having self-supporting.This TPI precursor is peeled off from the PET film, anchor portion, in 390 ℃ of heating down of final heating-up temperature, imidizate obtains the monolayer thermoplastic Kapton of thick 25 μ m.
(lamination of the metal level that forms by sputter)
In the one side of the thermoplastic polyimide film that obtains, the same with embodiment 38, sputter nickel and copper obtain metal/thermo polyimide laminates body.
(lamination procedure)
BT resin substrate with Copper Foil 12 μ m is made internal layer circuit.The face and the opposite face and the internal layer circuit of metal level that forms above-mentioned laminated body is opposed, by vacuum pressed, under the condition of 260 ℃ of temperature, hot plate pressure 3MPa, 10 minutes pressing times, vacuum condition 1kPa, be stacked on the internal layer circuit.
With the method identical, estimate the adhesive strength after normality and the pressure boiling experiment with embodiment 1.
The measurement result of the adhesive strength of embodiment 38,39 and comparative example 2 is shown in table 7.
Table 7
The formation of laminated body The sputter pre-treatment Adhesive strength (N/cm)
Normality Behind the PCT
Embodiment 38 Metal level/thermoplasticity polyimide layer/non-thermoplasticity Kapton Ion gun 13 5
Embodiment 39 Metal level/thermoplasticity polyimide layer Ion gun 14 6
Comparative example 2 Metal level/non-thermoplasticity Kapton Ion gun Metal level breaks away from, and can not measure
Scheme 3 (heat treated)
Embodiment 40
With the non-thermal plasticity Kapton and the TPI precursor that obtain by scheme 2 same preparation methods, make the lamination Kapton same with scheme 2.
(formation of metal level)
One side at above-mentioned lamination Kapton, use (strain) clear and vacuum system sputtering equipment NSP-6, the limit is heated to 270 ℃ with the infrared lamp heater, (0.2Pa is pressed in sputter to limit sputter nickel 6nm, DC power output 200W, sputtering time 1 minute), (0.2Pa, DC power output 200W are pressed in sputter to copper 200nm, sputtering time 18 minutes), make laminated body.
Here above-mentioned sputtering equipment NSP-6 has, and above-mentioned infrared radiation equipment is installed in the vacuum chamber, can heat the structure with sputter process simultaneously.That is, this equipment can heat and sputter process on the infrared lamp heater on 11 substrate limits of vacuum chamber inner edge rotation revolution.The time that each substrate carries out sputter process is 5～7% of whole processing times.The temperature of lamp heater is measured and is controlled by thermocouple is set between lamp heater and substrate.Protective film (Japan's seal strange (イ Application キ) manufacturing (strain) system: Leo En Ermu (リ オ エ Le system) LE952-T1) that hear resistance and releasable are arranged at metal level upper strata pressing element in addition.
(synthesizing of adhesive linkage)
The bonding solution coat that will obtain equally with scheme 1 is on the face of the metal level that does not form above-mentioned laminated body; and thickness is 12.5 μ m after making it dry; 170 ℃ formed adhesive linkage in dry 2 minutes down, obtain comprising the laminated body of heat-resistance protection film/metal level/thermoplastic polyimide layer/non-thermal plasticity Kapton/bond layer.
(lamination procedure)
Under the condition the same with scheme 1, be stacked in inner layer circuit board after, solidify, obtain comprising the laminated body of heat-resistance protection film/metal level/polyimide film layer/bond layer/glass epoxide copper-coated laminated board.
(punching, decontamination, electroless copper operation)
After peeling off the heat-resistance protection film on laminated body surface, be to estimate anti-decontamination fluidity of laminated body and the copper of anti-electroless plating fluidity, laminated body carry out table 6 in each operation of condition.
(electro-coppering operation)
Carry out the electrolytic copper plating identical with scheme 2.
In addition, determining bonding strength under the normality and pressure boiling experiment and scheme 1 are carried out equally.
(formation of fine circuits)
Use comprises the laminated body of metal level/thermoplastic polyimide layer/non-thermal plasticity Kapton/bond layer/glass epoxide copper-coated laminated board, and by half add, forming L/S is the circuit of 15 μ m/15 μ m.Can to form metal level/thermoplastic polyimide layer interface be level and smooth (Rz=0.1 μ m), do not produce the good circuit of etch residue.
Embodiment 41
Except that the heating-up temperature with the lamp heater is decided to be 150 ℃, uses with the same method of embodiment 40 and make laminated body, and measure the adhesive strength after normality and the pressure boiling.The laminated body that comprises metal level/thermoplastic polyimide layer/non-thermal plasticity Kapton/adhesive linkage/glass epoxide copper-coated laminated board that use obtains, by half add, forming L/S is the circuit of 15 μ m/15 μ m.Can to form metal level/thermoplastic polyimide layer interface be level and smooth (Rz=0.1 μ m), do not produce the good circuit of etch residue.
Comparative example 4
Except that on the non-thermal plasticity Kapton, not forming the thermoplastic polyimide layer, use when making laminated body with the same method of embodiment 40, the crack in the decontamination operation, occurs and break away from, can not make laminated body.
Comparative example 5
On the coarse epoxy resin base plate that turns to Rz=3 μ m, carry out the processing 4～8 of table 6, on substrate, form metal level.Use it to form the circuit of L/S=15 μ m/15 μ m, but etch residue is arranged on the resin surface, can not form good circuit with half add.
Embodiment 40,41 and comparative example 4 the results are shown in table 8.
Table 8
The formation of laminated body Heating-up temperature Adhesive strength (N/cm)
Normality Behind the PCT
Embodiment 40 Metal level/thermoplasticity polyimide layer/non-thermoplasticity Kapton 270℃ 15 9
Embodiment 41 Metal level/thermoplasticity polyimide layer/non-thermoplasticity Kapton 150℃ 13 8
Comparative example 4 Metal level/non-thermoplasticity Kapton 270℃ Metal level breaks away from, and can not measure
Scheme 4
Embodiment 42
Non-thermal plasticity Kapton and the TPI precursor of use by obtaining with the same manufacture method of scheme 2 made the lamination Kapton equally with scheme.
(surface treatment of thermoplastic polyimide resin layer)
In the one side of the lamination Kapton that obtains, with the gas composition be that argon/helium/nitrogen, intrinsic standoff ratio are 8/2/0.2, pressure 13300Pa, handle density 1000[W branch/m 2] carry out plasma treatment.
(formation of metal level)
In one side through above-mentioned surface-treated thermoplastic polyimide resin, carry out decontamination and electroless plating copper with the method for above-mentioned table 6, form electroless plating copper film (thickness 0.3 μ m) on the thermoplastic polyimide resin surface.Then, using copper sulphate plating bath (Ha イ ス ロ one bathes), is 2A/dm in current density 2Down, carry out 40 minutes plating, the thickness of copper film is 18 μ m.In addition, use the wild pharmacy system Mortopl Er Qinameikeyapu of society difficult to understand (ト Star プ Le チ Na メ one Network ア Star プ) (10ml/l) and pul very receive the additive of (プ Le チ Na) 81-HL (2.5ml/l) as plating bath.
In addition, the mensuration of the adhesive strength under the normality and pressure boiling experiment and scheme 1 are carried out equally.
(formation of fine circuits)
On the laminated body of surface-treated thermoplastic polyimide resin/non-thermal plasticity Kapton, use electroless plating copper, by half add, forming L/S is the circuit of 15 μ m/15 μ m.Can to form metal level/thermoplastic polyimide layer interface be level and smooth (Rz=0.1 μ m), do not produce the good circuit of etch residue.
Embodiment 43
Remove plasma treatment is replaced with processing density 1000[W branch/m 2] sided corona treatment outside, use with the same method of embodiment 42 and make laminated body, and measure the adhesive strength after normality and the pressure boiling.In addition, use the laminated body that comprises thermoplastic polyimide layer/non-thermal plasticity Kapton that obtains, by half add, forming L/S is the circuit of 15 μ m/15 μ m.Can to form metal level/thermoplastic polyimide layer interface be level and smooth (Rz=0.1 μ m), do not produce the good circuit of etch residue.
Embodiment 44
Except that Y-aminopropyl triethyl silicane (the silane etchant KBE903 that plasma treatment is replaced with as coupling agent solution; SHIN-ETSU HANTOTAI's chemical industry (strain) system) beyond the 0.1 weight % methanol solution, uses with the same method of embodiment 42 and make laminated body, and measure the adhesive strength after normality and the pressure boiling.In addition, use the laminated body that comprises thermoplastic polyimide layer/non-thermal plasticity Kapton that obtains, by half add, forming L/S is the circuit of 15 μ m/15 μ m.Can to form metal level/thermoplastic polyimide layer interface be level and smooth (Rz=0.1 μ m), do not produce the good circuit of etch residue.
Embodiment 45
Remove plasma treatment is replaced with Ya Tedekejiapaen (ア ト テ Star Network ジ ヤ パ Application) system Kern Sai Enteleite Kern Parker spy (コ Application セ Application ト レ one ト コ パ Network ト) CP 550ml and NaOH 40g dissolving, impregnated in water at 80 ℃, to adjust volume be in 1 liter the aqueous sodium permanganate solution outside 5 minutes, with making laminated body, and measure the adhesive strength after normality and the pressure boiling with the same method of embodiment 42.In addition, use the laminated body that comprises thermoplastic polyimide layer/non-thermal plasticity Kapton that obtains, by half add, forming L/S is the circuit of 15 μ m/15 μ m.Can to form metal level/thermoplastic polyimide layer interface be level and smooth (Rz=0.1 μ m), do not produce the good circuit of etch residue.
Embodiment 46
Remove plasma treatment is replaced with illumination 20mW/cm 2, outside 5 minutes the ultraviolet treatment with irradiation of irradiation time, use with the same method of embodiment 42 and make laminated body, and measure the adhesive strength after normality and the pressure boiling.In addition, use the laminated body that comprises thermoplastic polyimide layer/non-thermal plasticity Kapton that obtains, by half add, forming L/S is the circuit of 15 μ m/15 μ m.Can to form metal level/thermoplastic polyimide layer interface be level and smooth (Rz=0.1 μ m), do not produce the good circuit of etch residue.
Embodiment 47
Except that the electron ray treatment with irradiation that plasma treatment is replaced with useful to irradiation of rays dosage 500kGy, use with the same method of embodiment 42 and make laminated body, and measure the adhesive strength after normality and the pressure boiling.In addition, use the laminated body that comprises thermoplastic polyimide layer/non-thermal plasticity Kapton that obtains, by half add, forming L/S is the circuit of 15 μ m/15 μ m.Can to form metal level/thermoplastic polyimide layer interface be level and smooth (Rz=0.1 μ m), do not produce the good circuit of etch residue.
Embodiment 48
Remove plasma treatment is replaced with the silica sand that uses particle diameter 0.1～1mm, blow out the angle between nozzle and Kapton and be respectively 45 degree, 100mm at interval, the amount of blowing is beyond the blasting treatment of 6kg/ branch, with making laminated body, and measure the adhesive strength after normality and the pressure boiling with the same method of embodiment 42.In addition, use the laminated body that comprises thermoplastic polyimide layer/non-thermal plasticity Kapton that obtains, by half add, forming L/S is the circuit of 15 μ m/15 μ m.Can to form metal level/thermoplastic polyimide layer interface be level and smooth (Rz=0.1 μ m), do not produce the good circuit of etch residue.
Embodiment 49
Remove the flame that plasma treatment is replaced with 1600 ℃ of uses, chill-roll temperature is 50 ℃, be beyond the flame treatment of 1/3 position traveling film of the length of flame apart from flame front, use with the same method of embodiment 42 and make laminated body, and measure the adhesive strength after normality and the pressure boiling.In addition, use the laminated body that comprises thermoplastic polyimide layer/non-thermal plasticity Kapton that obtains, by half add, forming L/S is the circuit of 15 μ m/15 μ m.Can to form metal level/thermoplastic polyimide layer interface be level and smooth (Rz=0.1 μ m), do not produce the good circuit of etch residue.
Embodiment 50
Except that replacing with plasma treatment containing 5mol/L hydrazine hydrate and 1mol/L NaOH is in the aqueous solution of ratio, beyond 2 minutes hydrophilic treated of dipping under 30 ℃, with making laminated body, and measure the adhesive strength after normality and the pressure boiling with the same method of embodiment 42.In addition, use the laminated body that comprises thermoplastic polyimide layer/non-thermal plasticity Kapton that obtains, by half add, forming L/S is the circuit of 15 μ m/15 μ m.Can to form metal level/thermoplastic polyimide layer interface be level and smooth (Rz=0.1 μ m), do not produce the good circuit of etch residue.
Comparative example 6
On the non-thermal plasticity Kapton that makes in method, do not form the thermoplastic polyimide resin layer, use with the same method of embodiment 42 and make laminated body, and measure the adhesive strength after normality and the pressure boiling with embodiment 42 record.In addition, use the laminated body that comprises thermoplastic polyimide layer/non-thermal plasticity Kapton that obtains, by half add, forming L/S is the circuit of 15 μ m/15 μ m.A little less than metal level/thermoplastic polyimide layer interface bonding, so pattern peels off, and can not make printed circuit board.
Comparative example 7
Except that the electron ray treatment with irradiation that plasma treatment is replaced with useful to irradiation of rays dosage 500kGy, use with the same method of comparative example 6 and make laminated body, and measure the adhesive strength after normality and the pressure boiling.In addition, use the laminated body that comprises thermoplastic polyimide layer/non-thermal plasticity Kapton that obtains, by half add, forming L/S is the circuit of 15 μ m/15 μ m.A little less than metal level/thermoplastic polyimide layer interface bonding, so pattern peels off, and can not make printed circuit board.
Comparative example 8
Remove plasma treatment is replaced with Ya Tedekejiapaen (ア ト テ Star Network ジ ヤ パ) system Kern Sai Enteleite Kern Parker spy (コ Application セ Application ト レ one ト コ パ Network ト) CP 550ml and NaOH 40g dissolving, impregnated in water at 80 ℃, to adjust volume be in 1 liter the aqueous sodium permanganate solution beyond 5 minutes, with making laminated body, and measure the adhesive strength after normality and the pressure boiling with the same method of comparative example 6.In addition, use the laminated body that comprises thermoplastic polyimide layer/non-thermal plasticity Kapton that obtains, by half add, forming L/S is the circuit of 15 μ m/15 μ m.A little less than metal level/thermoplastic polyimide layer interface bonding, so pattern peels off, and can not make printed circuit board.
Comparative example 9
On the coarse epoxy resin base plate that turns to Rz=3 μ m, form metal level on the substrate surface through the processing 4～8 of table 6.Use it to form the circuit of L/S=15 μ m/15 μ m, but etch residue is arranged on the resin surface, can not form good circuit with half add.
The measurement result of the adhesive strength of embodiment 42～50 and comparative example 6～8 is shown in table 9.
Table 9
Polyimide resin Surface treatment The bonding force of non-electrolytic copper plating layer (N/cm)
(normality) (behind the PCT)
Embodiment 42 TPI/non-thermal plasticity polyimides Plasma 7 4
Embodiment 43 Corona 8 5
Embodiment 44 Coupling agent 7 4
Embodiment 45 Permanganate 7 4
Embodiment 46 The ultraviolet ray irradiation 8 5
Embodiment 47 The electron ray irradiation 7 4
Embodiment 48 Sandblast 7 4
Embodiment 49 Flame 6 3
Embodiment 50 Hydrophiling 7 4
Comparative example 6 The non-thermal plasticity polyimides Plasma 1 0.1
Comparative example 7 Electron ray 2 0.2
Comparative example 8 Permanganate 1 0.1
Scheme 5 (with the laggard andante plating of inner layer circuit board lamination)
(manufacturing of laminated body)
The TPI precursor that the non-thermal plasticity Kapton that manufacture method-A, the B of record and C make in the operational version 1, TPI precursor manufacture method-X and Y make, and adhesive solution.
Non-thermal plasticity Kapton with above-mentioned manufacture method-A, B and C preparation uses as the core film, on its one side, with the DMF solution as the polyamic acid of the precursor of TPI of intaglio plate coating machine coating autofrettage-X and Y preparation.
After the coating, carry out the imidizate by heat treated dry solvent and polyamic acid, in 390 ℃ of heating down of final heating-up temperature, preparation comprises the lamination Kapton of non-thermal plasticity polyimide layer and thermoplastic polyimide layer.Change coating weight, can obtain the different film of thermoplasticity polyimides layer thickness.
Above-mentioned adhesive solution is coated on the above-mentioned non-thermal plasticity Kapton face, and making its dried thickness is 12.5 μ m, then 170 ℃ of down dry laminated body that obtained forming adhesive linkage in 2 minutes.In the table, the laminated body that obtains, for example the non-thermal plasticity Kapton prepares with the A method, and it simultaneously is when using the thermoplastic polyimide layer of X method making, to be recited as the X/A/ adhesive linkage.
(lamination procedure)
Glass epoxide copper-coated laminated board by Copper Foil 12 μ m prepares inner layer circuit board, then, above-mentioned laminated body by vacuum pressed, is stacked in back curing on the inner layer circuit board under the condition of 200 ℃ of temperature, hot plate pressure 3MPa, 2 hours pressing times, vacuum condition 1KPa.
(by the plate plating of sputtering method)
To forming plate coating on the thermoplastic polyimide layer resin bed behind the lamination, use (strain) clear and vacuum system sputtering equipment NSP-6, carry out with following method.
To be stacked on substrate on the inner layer circuit board furnace of packing into to laminated body, close vacuum chamber.Aforesaid substrate limit rotation revolution limit with the heating of lamp heater, is vacuumized 6 * 10 -4Pa or 6 * 10 -4Below the Pa.Pass through afterwards to import argon gas, under 035Pa, by the DC sputter, sputter nickel and then sputter copper.DC power, any one all is decided to be 200W.Film speed is nickel 7nm/ branch, copper 11nm/ branch, adjusts film formation time and may be controlled to film thickness.
In addition, determining bonding strength under the normality and pressure boiling experiment is carried out equally according to scheme 1.According to mensuration, on the copper layer that sputter forms, formed the copper layer of 18 μ m by metallide.
Embodiment 51～56
Use the polyamic acid solution by manufacture method X or Y preparation on the one side with the non-thermal plasticity Kapton of the thick 25 μ m of preparation method A, B or C preparation, another side uses adhesive solution, obtains laminated body.The thickness of thermoplastic polyimide layer is 3 μ m.Above-mentioned laminated body is stacked on the glass epoxy substrate that forms circuit.Then forming the internal diameter that reaches the internal diameter circuit with the UV-YAG laser instrument is the through hole of 30 μ m.Then, the oxygen plasma of correcting one's mistakes carries out decontamination.Then on thermoplastic polyimide layer, form the nickel film of thick 10nm by sputter nickel, by continuous sputter copper, obtaining the copper film of thick 250nm.Form the copper layer of thick 18 μ m on the sputtered film that obtains by electrolytic plating method.Estimate the state that adhesive strength, the adhesive strength after the pressure boiling experiment and the decontamination at normal temperatures of this laminated body handled, it the results are shown in table 10.
Table 10
Embodiment Polyimides preparation method and structure The structure of metal level Peel strength (N/cm) Adhesive strength (N/cm) after the PCT experiment Carry out the state of decontamination by oxygen plasma
51 The X/A/ adhesive linkage Ni/Cu 14 8 Well
52 The X/B/ adhesive linkage The same 12 9 Well
53 The X/C/ adhesive linkage The same 11 9 Well
54 The Y/A/ adhesive linkage The same 14 9 Well
55 The Y/B/ adhesive linkage The same 13 7 Well
56 The Y/C/ adhesive linkage The same 12 8 Well
Can learn that from the result laminated body of the present invention can realize excellent cementability.In addition, can carry out decontamination well, form conductor layer well in through hole inside.
Comparative example 10
Remove and use non-thermal plasticity Kapton A (promptly, the film that does not have thermoplastic polyimide layer), do not form in its surface beyond the thermoplastic polyimide layer, use the method perparation of specimen identical, use the same method and estimate the state that cementability and decontamination are handled with embodiment 51.Its result, adhesive strength are 7N/cm, and the adhesive strength after the pressure boiling is reduced to 2N/cm.In addition, can not carry out decontamination well.This result is by comparing with table 10, and learning is not having under the situation of thermoplastic polyimide layer, and the characteristic that can not obtain stipulating has been confirmed the effect of thermoplastic polyimide layer.
Embodiment 57～71
Except that the metal level of nickel bottom that forms all thickness and copper layer or form the nickel individual layer, carry out the operation same with embodiment 51, estimate the state that cementability and decontamination are handled after the same method, it the results are shown in table 11.In addition, the non-thermal plasticity Kapton uses C, and TPI uses Y.
Table 11
Embodiment The thickness of nickel bottom (nm) The thickness (nm) of copper layer (the 2nd metal level) Adhesive strength (N/cm) Adhesive strength (N/cm) after the PCT experiment Carry out the state of decontamination by oxygen plasma
57 2 250 11 5 Well
58 5 250 11 8 Well
59 10 50 10 5 Well
60 10 100 12 5 Well
61 10 250 12 8 Well
62 10 500 12 8 Well
63 10 1000 12 9 Well
64 10 2500 12 8 Well
65 20 250 14 8 Well
66 50 250 10 7 Well
67 250 0 10 6 Well
68 500 0 10 6 Well
69 1000 0 9 5 Well
70 1500 0 9 4 Well
71 3000 0 8 4 Well
From the result, cementability is good.In addition, decontamination can be carried out well, has formed conductor layer well in through hole inside.
Embodiment 72
Use the polyamic acid solution by manufacture method-Y preparation on the one side with the non-thermal plasticity Kapton of the thick 25 μ m of preparation method-C preparation, another side uses adhesive solution, obtains laminated body.The thickness of thermoplastic polyimide layer is 3 μ m.Above-mentioned laminated body is stacked on the glass epoxy substrate that forms circuit.Then forming the internal diameter that reaches the internal diameter circuit with the UV-YAG laser instrument is the through hole of 30 μ m.Then, carry out the decontamination of oxygen plasma.Then on thermoplastic polyimide layer, form the nickel film of thick 6nm by sputter nickel, by continuous sputter copper, obtain the copper film of thick 100nm.Afterwards, coating liquid light sensitivity plating resist (Japanese synthetic rubber (strain) society system, THB320P) carries out mask exposure with high-pressure mercury-vapor lamp then, and forming L/S is the corrosion-resisting pattern of 10 μ m/10 μ m.Then, carry out electrolytic copper plating, form copper circuit on the surface of non-electrolytic copper plating layer epithelium exposed portions serve.Electrolytic copper plating, at first in 10% sulfuric acid, wash 30 seconds in advance after, carry out 40 minutes plating then at room temperature.Current density is 2A/dm 2The thickness of electrolysis copper film is 10 μ m.Then, peel off the plating etchant resist with alkali type stripper, the sputter nickel dam is removed with the selective etching liquid (plum gram (メ Star Network) (strain) system etching solution NH-1862) of nickel, obtains printed circuit board.
The printed circuit board that obtains has the L/S that conforms to design load, and does not have undercut.The Auger (オ one シ エ) that further carries out the power supply layer released part is analyzed and the kish that undertaken by EPMA has or not mensuration, but does not think and have kish.In addition, circuit pattern is bonding securely with the intensity of 13N/cm.Decontamination can be carried out well, has formed conductor layer well in through hole inside.
Industrial practicality
Use has the printed circuit board of the laminated body manufacturing of the present invention of thermoplastic polyimide layer and metal level or thermoplastic polyimide layer, non-thermal plasticity polyimide layer and metal level, can high-density wiring, bonding excellent in stability, compression resistance boiling experiment had excellently bonding reliability, in addition, the operations such as decontamination also there is tolerance.
In addition, when making laminated body of the present invention, because heating above-mentioned thermoplastic polyimide layer Surface Edge, the limit forms metal level, laminated body and the printed circuit board that therefore can be had simultaneously the compression resistance cooking of anti-decontamination fluidity and adhesive strength.
In addition, when making laminated body of the present invention, because above-mentioned thermoplastic polyimide layer is carried out selecting in surface treatment, flame treatment and the hydrophilicity-imparting treatment of the processing of combined ionic rifle, plasma treatment, sided corona treatment, coupling agent processings, permanganate processings, ultraviolet treatment with irradiation, electron ray treatment with irradiation, projected at high velocity grinding agent the surface treatment of processing more than a kind or a kind, thus can obtain strong bond on level and smooth thermoplastic polyimide layer surface, laminated body and the printed circuit board of environmental resistance excellence.
In addition, when making printed circuit board, do not use original wet type electroless plating, and form metal level by physical vapor deposition, reduced the load to environment.
Therefore, the printed circuit board of the present invention flexible rigid circuit wiring plate, combinational circuit wiring plate, TAB of multilayer printed wiring board, lamination flexible printed circuit board and rigid printed circuit wiring plate that can be used as flexible printed circuit board, the lamination flexible printed circuit board of anti-environmental stability excellence under high density uses with band, the e-machine printed circuit board of the COF substrate of semiconductor element and MCM substrate etc. directly being installed at printed circuit board.

Claims (25)

1. laminated body, this laminated body comprises the metal level on thermoplastic polyimide layer and thermoplastic polyimide layer surface.
2. the laminated body of putting down in writing according to claim 1, it is characterized in that above-mentioned thermoplastic polyimide layer is the processing more than a kind or a kind selected of combination and carry out the surface-treated layer from surface treatment, flame treatment and the hydrophilicity-imparting treatment of plasma treatment, sided corona treatment, coupling agent processing, permanganate processing, ultraviolet treatment with irradiation, electron ray treatment with irradiation, projected at high velocity grinding agent.
3. the laminated body of putting down in writing according to claim 1 is characterized in that, above-mentioned thermoplastic polyimide layer is to carry out the surface-treated layer by ion gun.
4. the laminated body of putting down in writing according to claim 3 is characterized in that, it is the processing of being undertaken by argon ion that above-mentioned ion gun is handled.
5. the laminated body of putting down in writing according to claim 1 is characterized in that, above-mentioned metal level is that heat thermoplastic polyimide layer on the limit, limit deposit element and the layer that forms.
6. the laminated body of putting down in writing according to claim 5 is characterized in that, heating-up temperature is more than 100 ℃ or 100 ℃.
7. according to claim 1,2,3 or 4 laminated body of being put down in writing, it is characterized in that above-mentioned metal level is an electroless plating.
8, according to claim 1,2,3,4,5 or 6 laminated body of being put down in writing, it is characterized in that above-mentioned metal level is the layer that forms by the method for selecting more than a kind or a kind from sputtering method, vacuum vapour deposition, ion plating method, electron beam evaporation plating method and chemical vapor deposition method.
9. according to claim 1,2,3,4,5,6,7 or 8 laminated body of being put down in writing, it is characterized in that above-mentioned metal level comprises the 1st metal level and the 2nd metal level.
10. the laminated body of putting down in writing according to claim 9 is characterized in that, above-mentioned the 1st metal level comprises nickel, cobalt, chromium, titanium, molybdenum, tungsten, zinc, tin, indium, gold or their alloy.
11., it is characterized in that above-mentioned the 2nd metal level comprises copper or its alloy according to claim 9 or 10 laminated body of being put down in writing.
12. a laminated body is characterized in that, the metal level that comprises the non-thermal plasticity polyimide layer that has thermoplastic polyimide layer on the face of at least one side and form on the face of at least one side on above-mentioned thermoplastic polyimide layer surface.
13. a laminated body is characterized in that, has the metal level in thermoplastic polyimide layer and the formation of above-mentioned thermoplastic polyimide layer surface on the one side, another side has adhesive linkage.
14. a laminated body is characterized in that, has the metal level in thermoplastic polyimide layer and the formation of above-mentioned thermoplastic polyimide layer surface on the one side, another side has Copper Foil.
15. according to claim 12,13 or 14 laminated body of being put down in writing, it is characterized in that above-mentioned thermoplastic polyimide layer is the processing more than a kind or a kind selected of combination and carry out the surface-treated layer from surface treatment, flame treatment and the hydrophilicity-imparting treatment of plasma treatment, sided corona treatment, coupling agent processing, permanganate processing, ultraviolet treatment with irradiation, electron ray treatment with irradiation, projected at high velocity grinding agent.
16., it is characterized in that above-mentioned thermoplastic polyimide layer is to handle by ion gun to carry out the surface-treated layer according to claim 12,13 or 14 laminated body of being put down in writing.
17. the laminated body according to claim 16 is put down in writing is characterized in that, it is the processing of being undertaken by argon ion that above-mentioned ion gun is handled.
18., it is characterized in that above-mentioned metal level is heating thermoplastic polyimide layer limit, limit deposit element and the layer that forms according to claim 12,13 or 14 laminated body of being put down in writing.
19. the laminated body according to claim 18 is put down in writing is characterized in that, heating-up temperature is more than 100 ℃ or 100 ℃.
20. laminated body, this laminated body is the laminated body that comprises Kapton and metal level, above-mentioned Kapton comprises the non-thermal plasticity polyimide layer and at least 2 layers of structure of the thermoplastic polyimide layer that forms on the one side at least of non-thermal plasticity polyimide layer, and above-mentioned metal level comprises the 1st metal level of the nickel, cobalt, chromium, titanium, molybdenum, tungsten, zinc, tin, indium, gold or their alloy that contain the thermoplastic polyimide layer surface and the 2nd metal level that contains copper or its alloy on the 1st metal level.
21., it is characterized in that above-mentioned thermoplastic polyimide layer contains following general formula (1) according to claim 1,2,3,4,5,6,7,8,9,10,11,12,13,14,15,16,17,18,19 or 20 laminated body of being put down in writing
General formula (1)
(in the formula, A selects 4 valency organic groups from following formula group (2), can be the same or different, and X is the divalent organic group of selecting from following formula group (3), can be the same or different.B is 4 valency organic groups outside enumerating in the following formula group (2), can be the same or different, and Y is the divalent organic group outside enumerating in the following formula group (3), and can be the same or different m: n is 100: 0～50: 50),
Group (2)
Group 3
Figure A2003801051890004C2
The TPI that the polyamic acid dehydration ring closure of expression obtains.
22., it is characterized in that the thickness of above-mentioned thermoplastic polyimide layer is 0.01～10 μ m, and thinner than non-thermal plasticity polyimide layer according to claim 12,13,14,15,16,17,18,19 or 20 laminated body of being put down in writing.
23. thermoplastic polyimide film, it is characterized in that, carried out surface treatment from surface treatment, flame treatment and the hydrophilicity-imparting treatment of plasma treatment, sided corona treatment, coupling agent processing, permanganate processing, ultraviolet treatment with irradiation, electron ray treatment with irradiation, projected at high velocity grinding agent by the processing more than a kind or a kind that combination is selected.
24. the manufacture method of a printed circuit board, this manufacture method comprises following operation: form the operation of adhesive linkage on the operation that forms the thermoplastic polyimide resin layer on the face of non-thermal plasticity Kapton one side, face at the opposite side of this non-thermal plasticity Kapton, so that this adhesive linkage is relative with the circuit face of the wiring plate of formation circuit, the method that adopts heating and/or accompany by pressurization is carried out the operation of lamination, and the operation of plate plating is carried out on the thermoplastic polyimide layer surface behind lamination by the vapour deposition method of physics.
25. the manufacture method of a printed circuit board, this manufacture method comprises following operation: on non-thermal plasticity Kapton one side, form the thermoplastic polyimide resin layer operation, the another side of this non-thermal plasticity Kapton is passed through adhesive sheet, adopt heating and/or accompany by the method for pressurization, be laminated to the plate plating is carried out on operation on the wiring plate that forms circuit and the thermoplastic polyimide layer surface behind lamination by the vapour deposition method of physics operation.
CN 200380105189 2002-12-05 2003-12-05 Laminate, printed wiring board and method for manufacturing them Pending CN1720136A (en)

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JP354424/2002 2002-12-05
JP23399/2003 2003-01-31
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