CN101009973B - Resin composite copper foil, printed wiring board, and production process thereof - Google Patents
Resin composite copper foil, printed wiring board, and production process thereof Download PDFInfo
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- CN101009973B CN101009973B CN2007100082213A CN200710008221A CN101009973B CN 101009973 B CN101009973 B CN 101009973B CN 2007100082213 A CN2007100082213 A CN 2007100082213A CN 200710008221 A CN200710008221 A CN 200710008221A CN 101009973 B CN101009973 B CN 101009973B
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Abstract
A resin composite copper foil comprising a copper foil and a resin layer containing a block copolymer polyimide and a maleimide compound, the resin layer being formed on one surface of the copper foil, a production process thereof, a copper-clad laminate using the resin composite copper foil, a production process of a printed wiring board using the copper-clad laminate, and a printed wiring board obtained by the above process.
Description
Technical field
The present invention relates to be used for resin composite copper foil, the resin composite copper foil of printed substrate manufacture method, use this resin composite copper foil copper clad laminate, use the manufacture method of printed substrate and this printed substrate of this copper clad laminate.The resin composite copper foil that obtains by the present invention has excellent adhesion strength, therefore can use the surface to have the Copper Foil of minimum roughness.Use the copper clad laminate of above-mentioned resin composite copper foil to be suitable as the high density printed circuit board that contains fine circuitry.In addition, the printed substrate that obtains by method of the present invention has excellent copper coating bonding strength or thermal endurance, so this printed substrate is suitable as the high density printed circuit board that contains fine circuitry.
Background technology
In recent years, circuit conductor width in the very big reduction of the requirement printed circuit board (PCB) and the insulation spacing between the circuit are with the superelevation densification of electronic unit (semiconductor device that for example is used for electronic device) being installed and realizing semiconductor circuit.Traditionally, the electrolytic copper foil of the frosting with remarkable roughening of use Copper Foil bonding strength excellence is as the Copper Foil of the copper clad laminate of using in the printed substrate.These electrolytic copper foils have excellent adhesion strength.Yet when using this electrolytic copper foil to form fine circuitry by etching method, under the influence of the roughness of Copper Foil frosting, the bossing of Copper Foil is stayed insulation easily with on the surface of resin.When prolonging etching period when removing residual bossing fully, circuit is reduced by the positioning accuracy of over etching so that circuit or bonding strength.
In order to overcome these problems, so-called short version (low-profile) Copper Foil with controlled surface roughness has become business practice.When copper clad laminate of the high heat-resisting thermosetting resin that these Copper Foils is used for have substantially weak bonding strength etc., the bonding strength deficiency is the problem relevant with fine circuitry.This has greatly hindered the formation of superfine wire.In addition, in order to improve Copper Foil and to insulate with the bonding strength between the resin, the method that forms dielectric adhesive layer on Copper Foil has become business practice for a long time.For example, aspect paper (paper) phenol resin copper clad laminate, the technology that forms the phenol butyral resin on Copper Foil is known, and aspect the glass epoxy resin copper clad laminate, the technology that forms epobond epoxyn on Copper Foil is known.As these object lessons with the Copper Foil of adhesive, the copper clad laminate that has proposed to use the Copper Foil that has formed thin adhesive phase on it (for example, JP-A-8-216340) and the copper clad laminate of the bonding Copper Foil of use and semi-solid preparation resin molding (for example, JP-A-9-011397).Use this copper clad laminate of having the Copper Foil of adhesive after bonding strength or moisture absorption, aspect the thermal endurance problem to be arranged.Therefore, need further to improve.
Summary of the invention
An object of the present invention is to provide resin composite copper foil with excellent bonding strength---can be to its Copper Foil that uses the surface to have minimum roughness, the manufacture method of this resin composite copper foil also is provided, and provide the copper clad laminate that uses excellent heat resistance after above-mentioned resin composite copper foil and thermal endurance and the moisture absorption, use the manufacture method of printed substrate of above-mentioned copper clad laminate and the printed substrate that obtains by said method.
Another object of the present invention provides has the excellent copper coating bonding strength and the manufacture method of stable on heating printed substrate, and this method can easily form the superfine wire circuit.
According to the present invention, the resin composite copper foil that is used for printed substrate is provided, the resin bed that it comprises Copper Foil and contains block copolymer polyimide and maleimide compound, this resin bed forms on a surface of Copper Foil.
According to the present invention, resin composite copper foil as defined above further is provided, wherein block copolymer polyimide has the construction unit shown in construction unit shown in the formula (1) and the formula (2),
Wherein m and n satisfy m: n=1: 9 to 3: 1 integer.
According to the present invention, the manufacture method of the above-mentioned resin composite copper foil that is used for printed substrate further is provided again, comprise that the resin solution that will contain block copolymer polyimide and maleimide compound is coated on the surface of Copper Foil, scribble the Copper Foil of resin solution 250 to 360 ℃ of heat treatments then, thereby be formed on 200 ℃ or the low temperature resin bed that can not melt more.
According to the present invention, the copper clad laminate that is used for printed substrate further is provided, its following acquisition: will comprise Copper Foil and the resin composite copper foil and the B-b stage resin b composition layer lamination that contain the resin bed (this resin bed forms) of block copolymer polyimide and maleimide compound on a surface of Copper Foil, and then the gained sub-assembly be solidified.
According to the present invention, the manufacture method of printed substrate further is provided, this method comprises by etching removes the Copper Foil of aforesaid copper clad laminate fully to expose resin layer surface and to obtain laminated sheet, under the situation of resin layer surface of laminated sheet not being carried out roughened, form no electrolytic copper coating by electroless copper, on no electrolytic copper coating, form electrolytic copper plating layer by electrolytic copper plating then, remove no electrolytic copper coating and electrolytic copper plating layer by etching selectivity ground then, form copper circuit thus.
According to the present invention, the manufacture method of printed substrate further is provided, this method comprises that by etching the Copper Foil of removing aforesaid copper clad laminate fully is to expose resin layer surface and to obtain laminated sheet, under the situation of resin layer surface of laminated sheet not being carried out roughened, form no electrolytic copper coating by electroless copper, selectivity forms electrolytic copper plating layer on no electrolytic copper coating then, and remove no electrolytic copper coating at the position that does not form electrolytic copper plating layer at least by etching then, form copper circuit thus.
According to the present invention, the method according to above-mentioned each method further is provided, wherein after forming no electrolytic copper coating or forming electrolytic copper plating layer, heat-treat at 100 ℃ to 200 ℃.
According to the present invention, further provide printed substrate by each acquisition of said method.
Description of drawings
Fig. 1 is the key diagram of the copper clad laminate that uses among the present invention.
Fig. 2 is the key diagram that has formed the copper clad laminate of through hole.
Fig. 3 is the key diagram of following laminated sheet---by removing the resin layer surface that Copper Foil exposes this laminated sheet.
Fig. 4 is the key diagram that has formed the laminated sheet of no electrolytic copper coating on resin layer surface.
Fig. 5 is the key diagram that has formed the laminated sheet of electrolytic copper plating layer on no electrolytic copper coating.
Fig. 6 be selective removal the key diagram of printed substrate of no electrolytic copper coating and electrolytic copper plating layer.
The invention effect
The resin composite copper foil that obtains by the present invention has excellent bonding strength, therefore can use the surface to have the Copper Foil of minimum roughness. By using above-mentioned resin composite copper foil, can obtain to have stable on heating copper clad laminate after excellent heat resistance and the moisture absorption. This copper clad laminate is suitable as the high density printed circuit board that contains fine circuitry, and therefore resin composite copper foil provided by the invention and resin composite copper foil manufacture method have significantly high commercial availability.
The printed substrate that obtains by method of fabricating printed wiring board provided by the invention can form superfine wire (about 12 microns wide) copper circuit. The foregoing circuit width is significantly less than traditional fine line circuitry width. In addition, above-mentioned printed substrate has heat resistance after excellent bonding strength and the moisture absorption. Therefore, above-mentioned printed substrate is suitable as the high density printed circuit board that contains fine circuitry, and the actual utility of technology of the present invention is significantly very high.
Embodiment
The inventor has carried out diligent research for the problems referred to above that overcome traditional handicraft, and find, use comprises Copper Foil and the resin composite copper foil of the resin bed that contains specific block copolymer polyimide and specific maleimide compound that forms on surface of Copper Foil, can obtain to have excellent bonding strength and stable on heating copper clad laminate.According to above-mentioned discovery, the inventor has finished the present invention.That is to say, the invention provides the resin composite copper foil that comprises Copper Foil and contain the resin bed of block copolymer polyimide and maleimide compound, this resin bed forms on a surface of Copper Foil.Described block copolymer polyimide is preferably the block copolymer polyimide of the construction unit shown in the construction unit shown in (1) that has formula and the formula (2).The thickness of resin bed is preferably 0.1 micron to 10 microns.Contained block copolymer polyimide in the resin bed: the weight ratio of maleimide compound is preferably 10: 90 to 90: 10.
The present invention further provides the manufacture method of resin composite copper foil, this method comprises that the resin solution that will contain above-mentioned block copolymer polyimide and above-mentioned maleimide compound is coated on the surface of Copper Foil, and heat treatment scribbles the Copper Foil of resin solution in 250 to 360 ℃ temperature range then.The present invention further provides by merging above-mentioned resin composite copper foil and B-b stage resin b composition layer and solidifying gained sub-assembly copper clad laminate that gets and the printed substrate that uses above-mentioned copper clad laminate again.
The inventor further finds, use utilize the specific resin composite copper foil copper clad laminate, remove Copper Foil to expose resin layer surface, under the situation of resin layer surface not being carried out roughened, form copper coating, to remove copper coating to form copper circuit by etching selectivity then by etching, obtain to have excellent bonding strength and stable on heating printed substrate thus.
The preferred block copolymer polyimide of using in the resin bed of resin composite copper foil of the present invention is not specifically limited, as long as it is the copolymer polyimides with following structure---in this structure, the acid imide oligomer that is made of second construction unit is bonded to the end of the acid imide oligomer that is made of first construction unit.By continuous polymerization reaction synthetic segmented copolymer polyimides---in this reaction, tetracarboxylic dianhydride and diamines are reacted in polar solvent to obtain the acid imide oligomer, further add the tetracarboxylic dianhydride and the dissimilar diamines of same type then or further add dissimilar tetracarboxylic dianhydrides and the diamines of same type, thereby carry out imidization.
Used polar solvent comprises the polar solvent that dissolves polyimides, for example N-N-methyl-2-2-pyrrolidone N-, dimethylacetylamide, dimethyl formamide, methyl-sulfoxide, sulfolane and tetramethylurea.In addition, ketone solvent or ether solvents can be mixed with above-mentioned polar solvent.Available ketone solvent comprises methyl ethyl ketone, methyl propyl ketone, methyl isopropyl Ketone, methyl butyl ketone, methyl iso-butyl ketone (MIBK), methyl n hexyl ketone, metacetone, diisopropyl ketone, DIBK, cyclopentanone, cyclohexanone, methyl cyclohexanone, acetylacetone,2,4-pentanedione, diacetone alcohol and cyclohexene-n-on among the present invention.Available ether solvents comprises dipropyl ether, diisopropyl ether, butyl oxide, oxolane, oxinane, ethyl isoamyl alcohol, ETBE, ethyl benzyl ether, diethylene glycol dimethyl ether, tolyl methyl ether, methyl phenyl ethers anisole and phenetole among the present invention.In addition, in order to remove the water that in imidization, generates, require to add the solvent with the water azeotropic, for example toluene or dimethylbenzene, and from reaction solution, remove the water that generates.In addition, in order to promote reaction, the binary catalyst that preferably uses amine catalyst (for example pyridine) or constitute by alkali and cyclic ester (for example pyridine and gamma-valerolactone).Reaction temperature is 120 to 200 ℃.The independent polar solvent solution of block copolymer polyimide can obtain by solvent (for example toluene or dimethylbenzene) and the catalyst (for example pyridine) that finally distills from reaction solution with the water azeotropic.
The block copolymer polyimide of using among the present invention is preferably the solvent soluble block copolymer polyimide of the construction unit of the have formula construction unit of (1) and formula (2).For above-mentioned block copolymer polyimide, use 3,4,3 ', 4 '-biphenyl tetracarboxylic dianhydride is as the tetracarboxylic dianhydride and use 1, two (3-amino-benzene oxygen) benzene and 2 of 3-, two { 4-(4-amino-benzene oxygen) phenyl } propane of 2-are as diamines.
In order to control the molecular weight of each unit condensation polymer, mol ratio in the phase I reaction between change tetracarboxylic dianhydride and the diamines is to change into end acid anhydrides or amine, then in second stage reaction between exchange tetracarboxylic dianhydride and the diamines in the phase I reaction used mol ratio, can obtain to have the block copolymer polyimide of enough molecular weight thus.The weight average molecular weight of block copolymer polyimide of the present invention (Mw) is preferably 50,000 to 300,000, and more preferably 80,000 to 200,000.When Mw less than 50,000 o'clock, therefore resin bed is frangible and be not suitable for purpose of the present invention.When Mw greater than 300,000 o'clock, it is too high that resin solution viscosity becomes, so it is difficult to use.Can in block copolymer polyimide is synthetic, change the mol ratio of tetracarboxylic dianhydride and diamines to control final molecular weight.
The unit condensation polymer of formula (1): the mol ratio between the unit condensation polymer of formula (2) is preferably 1: 9 to 3: 1, more preferably 1: 3 to 3: 1.When the percentage of the structure of formula (1) during less than 10 moles of %, problem is that bonding strength reduces.When the percentage of the structure of formula (2) during less than 25 moles of %, problem is that anti-sweating heat performance reduces.
The maleimide compound that uses in the resin bed to resin composite copper foil of the present invention is not specifically limited, as long as it is the compound that per molecule contains at least two maleimide base groups.Its preferred example comprises two (4-maleimide aminophenyl) methane, 2, two [4-(the 4-maleimide amino-benzene oxygen) phenyl] propane of 2-, polyphenylene methane maleimide, meta-phenylene bismaleimide, bisphenol-A diphenyl ether bismaleimides and 3,3 '-dimethyl-5,5 '-diethyl-4,4 '-diphenyl methane bismaleimides.These maleimide compounds can be as required separately or be used in combination.In addition, can use the prepolymer of prepolymer, maleimide compound and the amines of maleimide compound, or the like.
The contained block copolymer polyimide and the weight ratio of maleimide compound are preferably 10: 90 to 90: 10, more preferably 20: 80 to 80: 20 in the resin bed of resin composite copper foil.
Copper Foil used in the resin composite copper foil of the present invention is not specifically limited, as long as it is the known Copper Foil that can be used for printed substrate.Preferred electrolytic copper foil, rolled copper foil and their copper alloy of using.These Copper Foils can carry out surface treatment by the known treatment method, for example handle with nickel or cobalt, or handle with silane finish.Thickness to Copper Foil is not specifically limited.It is preferably 35 microns or lower.The surface roughness (Rz) of copper foil surface (will form resin bed thereon) is preferably 4 microns or lower, more preferably 2 microns or lower.In the present invention, Rz is 10 mean roughness of JIS B0601 definition.
Can regulate the resin layer thickness of resin composite copper foil of the present invention according to the surface roughness of Copper Foil.When the thickness of resin bed was too thick, the drying in the heated drying step after on being coated to Copper Foil was often not enough, therefore in some cases, uses the thermal endurance of the copper clad laminate of this resin composite copper foil to reduce.Therefore, the thickness of resin bed is preferably 0.1 to 10 micron, more preferably 1 to 7 micron.
Following manufacturing resin composite copper foil of the present invention: the resin solution that will contain block copolymer polyimide that with good grounds above-mentioned synthetic method obtains and maleimide compound is coated on the Copper Foil and to institute's applying soln and carries out heated drying.As coating method, can make in all sorts of ways, for example reverse roll, bar (rod), blade, scraper, die head, intaglio printing and rotary screen.It the heated drying method is not specifically limited, as long as can produce the temperature that is enough to remove solvent for use in the resin solution.Usually use air drier or infrared drier.In order to prevent the copper oxidation, preferably heat-treat in vacuum or in inert atmosphere (for example nitrogen).In addition, heat treated temperature preferably finally is within 250 to 360 ℃ the scope.When it is lower than above-mentioned lower limit or is higher than in limited time, use the moisture absorption of copper clad laminate of thus obtained resin composite copper foil after thermal endurance be tending towards reducing.
The example of the concrete manufacture method of resin composite copper foil is as follows.Maleimide compound is added in the polar solvent solution of block copolymer polyimide, by under room temperature or heating, stirring, maleimide compound is dissolved in polar solvent solution and mix, thus obtained resin solution is coated on the surface of Copper Foil, the Copper Foil that will scribble resin solution then in nitrogen atmosphere 120 to 180 ℃ of heated dryings 3 to 10 minutes, and then further in nitrogen atmosphere 250 ℃ to 360 ℃ heat treatments 1 to 3 minute, make resin composite copper foil thus.
Used resin combination in the B-b stage resin b composition layer that combines with resin composite copper foil of the present invention is not specifically limited, as long as it is the known compositions of thermosetting resin that can be used for printed substrate.The example of this resin comprises epoxy resin, polyimides, cyanate ester resin, maleimide resin, added the polyphenylene oxide resin of two keys and such as the resin combination of the brominated or phosphorus-containing compound of these resins.These can separately or be used in combination.Consider reliability, for example resistance to migration and thermal endurance are preferably used and are contained the resin combination of cyanate ester resin as solvent, for example contain the resin combination of the epoxy resin that combines with cyanate ester resin.Can use known catalysts, known curing agent or known curing accelerator to these thermosetting resins as required.
In the B-b stage resin b composition layer in the used resin combination the preferred cyanate ester resin that uses be meant that per molecule contains the compound of at least two cyanato-s.The object lesson of cyanate ester resin comprises 1,3-or 1,4-two cyanato-benzene, 1,3,5-three cyanato-benzene, 1,3-, 1,4-, 1,6-, 1,8-, 2,6-or 2,7-two cyanato-naphthalenes, 1,3,6-three cyanato-naphthalenes, 4,4-two cyanato-biphenyl, two (4-cyanato-phenyl) methane, 2, two (the 4-cyanato-phenyl) propane of 2-, 2, two (3, the 5-two bromo-4-cyanato-phenyl) propane of 2-, two (4-cyanato-phenyl) ether, two (4-cyanato-phenyl) thioether, two (4-cyanato-phenyl) sulfone, three (4-cyanato-phenyl) phosphite, three (4-cyanato-phenyl) phosphate and the various cyanate ester resins that obtain by the reaction between novolac resin and the cyanogen halides.These can separately or be used in combination.
Preferably the epoxy resin that is used in combination with cyanate ester resin can be selected from known epoxy resin.The object lesson of described epoxy resin comprises bisphenol A type epoxy resin, bisphenol f type epoxy resin, novolac-type epoxy resin, cresols line style phenol aldehyde type epoxy resin, cycloaliphatic epoxy resin, biphenyl type epoxy resin, fluorenes type epoxy resin, resorcinol type epoxy resin, naphthalene type epoxy resin, phenol aralkyl-type epoxy resin, biphenyl aralkyl epoxy resin, epoxidation polyphenylene oxide resin; By the polyepoxides that butadiene, pentadiene, VCH, two double bond epoxidations that encircle amyl ethers or analog are made; The poly epihydric alcohol based compound that obtains with the reaction of silicone resin by polyalcohol, hydroxyl and chloropropylene oxide.In addition, also can use these epoxy resin known interpolation the resin and the phosphorous epoxy resin of bromine.These epoxy resin can be as required separately or be used in combination.
Manufacture method to B-b stage resin b composition layer used among the present invention is not specifically limited.For example, make B-b stage resin b composition layer by known method, for example following method: by with compositions of thermosetting resin dissolving or be dispersed in the solvent or do not use solvent, the varnish of preparation compositions of thermosetting resin also is coated to this varnish that release film (release film) is gone up and dry to obtain B-b stage resin b composition plate; Above-mentioned varnish is coated on the base material, then by dry B-rankization with the preparation prepreg; Or above-mentioned varnish is applied directly on the substrate that has formed conductor circuit, dry then to form B-b stage resin b composition layer.Thickness to B-b stage resin b composition layer is not specifically limited.Under the situation of sheet material or coating, above-mentioned thickness is preferably 4 to 150 microns.Under the situation of prepreg, thickness is preferably 10 to 200 microns.
Consider from the angle of the character of gained copper clad laminate, use base material in the preferred used in the present invention B-b stage resin b composition layer.Described base material is not specifically limited, as long as it is the known base material that can be used for printed substrate.The object lesson of base material comprises the nonwoven fabrics and the woven fabric of known glass fiber (for example E glass, NE glass, D glass, S glass and T glass).In order to improve the adhesiveness with resin combination, preferably handle base material by the known surface facture.
The method of the manufacturing copper clad laminate among the present invention is following method---wherein above-mentioned resin composite copper foil placed on the above-mentioned B-b stage resin b composition layer, so that the resin layer surface of resin composite copper foil is towards B-b stage resin b composition layer, and the gained sub-assembly is laminated into type.Particularly, resin composite copper foil placed at least one surface of B-b stage resin b composition layer or by all placing on two surfaces of laminated sheet or forming on the material that B-b stage resin b composition layer (each last B-b stage resin b composition layer in surface) obtains, so that the resin layer surface of resin composite copper foil is towards B-b stage resin b composition layer, and in heat with under pressure, preferably in a vacuum that the gained sub-assembly is laminated into type to obtain copper clad laminate.In order to make multi-layer sheet, on two surfaces of the internal layer substrate that has formed conductor circuit, all place or form B-b stage resin b composition layer (each last B-b stage resin b composition layer in surface), on two surfaces of B-b stage resin b composition layer, all place resin composite copper foil (each last resin composite copper foil in surface), so that the resin layer surface of resin composite copper foil is respectively towards B-b stage resin b composition layer, and in heat with under pressure, preferably in a vacuum that the gained sub-assembly is laminated into type to obtain the multilayer copper-clad laminated sheet.In above-mentioned copper clad laminate or multilayer copper-clad laminated sheet, form conductor circuit, carry out plating processing etc. then to obtain printed substrate by known method.
The laminated sheet that is used for above-mentioned manufacturing or the kind of circuitry substrate are not specifically limited, and can be selected from known laminate and the metal forming cladding plate that is used for the printed wire panel material, preferred copper-clad plate.Its object lesson comprises the inorfil that uses compositions of thermosetting resin and/or thermoplastic resin composition and/or organic fiber base material copper clad laminate, the copper-clad plate of heat-pesistant thin film base material, with these base materials combinations and composite substrate materials copper clad laminate, these multilayer copper-clad plate and the multilayer copper-clad plate of making by addition process or similar approach.Conductor thickness to circuitry substrate is not specifically limited.It is preferably 3 to 35 microns.Preferably improve the fusible known treatment with the resin of B-b stage resin b composition layer on above-mentioned conductor circuit, for example the block cupric oxide is handled or with chemical treatments (for example CZ of MECK processing)
The lamination that is used to make copper clad laminate is not specifically limited.Laminated into type preferably 100 to 250 ℃ temperature and 5 to 40kgf/cm
2Pressure, under 30mmHg or lower vacuum degree, carried out 30 minutes to 5 hours.Lamination can carry out from start to finish under these conditions.Can also carry out laminated into typely, take out the gained material then and in heating furnace, will solidify thereafter until gelling.
As the Copper Foil of the copper clad laminate that is used for printed substrate, usually use treat to have formed on the bonding copper foil surface coarse to guarantee the Copper Foil bonding strength and to contain the Copper Foil of antirust coat.Yet when forming the fine lines circuit by etching, the width limit of the fine lines that can be shaped circuit is about 50 microns, because the copper of the boss at the coarse place of Copper Foil is residual and because the etching speed of antirust coat is slow, the cross section of copper circuit often is trapezoidal.In addition, as forming the more method of fine-line, there is following graphic plating method, wherein on the laminated sheet of extra thin copper foil, form the copper fine rule of about 25 micron thickness by the plating selectivity with about 3 micron thickness, with about 5 microns of whole lip-deep copper etching, form the copper fine rule thus then.Even according to the graphic plating method, the boss at coarse place is also residual, and the etching speed of antirust coat is slow, therefore is difficult to form thickness less than about 30 microns copper circuit.
Subsequently, be explained with reference to the drawings the present invention.The present invention relates to the manufacture method of printed substrate, it has overcome that circuit to the copper clad laminate fine rule in forming forms and copper circuit hangs down the restricted problem of bonding strength.The present invention relates to the manufacture method of printed substrate, be included in form on the surface of Copper Foil (1 among Fig. 1) contain block copolymer polyimide and maleimide compound resin bed (2 among Fig. 1) with the preparation resin composite copper foil, on the surface of the resin bed of resin composite copper foil, pile up B-b stage resin b composition layer (3 among Fig. 1), then that the gained sub-assembly is laminated into type to form copper clad laminate, the Copper Foil of removing copper clad laminate by etching fully is to expose resin layer surface (2 among Fig. 3) and cambium layer pressing plate, under the situation of resin layer surface of laminated sheet not being carried out roughened, form no electrolytic copper coating (5 among Fig. 4) by electroless copper, on no electrolytic copper coating, form electrolytic copper plating layer (6 among Fig. 5) by electrolytic copper plating then, remove no electrolytic copper coating and electrolytic copper plating layer by etching selectivity then, form copper circuit (7 among Fig. 6) thus.Can form through hole or blind hole (4 among Fig. 2) as required.
There are two kinds by the universal method of etching selectivity removal copper plate with the formation copper circuit.One of said method is with the position that will form copper circuit on the resist covering copper coating, and to pass through known etching method formation circuit.Other method is, on the whole surface of laminated sheet, form thin no electrolytic copper coating, in the position beyond the position that will form copper circuit, cover no electrolytic copper coating with resist plating, form electrolytic copper plating layer by graphic plating, divest resist plating then, and etching does not form the no electrolytic copper coating of electrolytic copper plating layer on it at least, forms circuit thus.
No electrolytic copper coating in the printed substrate of the present invention is owing to the resin bed that forms in resin composite copper foil in advance has high bonding strength (because the bonding strength of B-b stage resin b composition obtains the adhesiveness between above-mentioned resin bed and the compositions of thermosetting resin).By after electroless copper or electrolytic copper plating, heat-treating, can further improve the bonding strength of copper coating at 100 ℃ to 200 ℃.Printed substrate of the present invention is also in the thermal endurance that has remarkable excellence aspect the parts installation capability (for example solder reflow after the moisture absorption).
In the manufacture method of printed substrate provided by the invention, at first, in above-mentioned copper clad laminate, use awl, laser or analog manufacturing hole, for example through hole or blind hole (blind bia), carrying out desmearing with permanganate as required handles, with the copper clad laminate of preparation processing via hole, remove Copper Foil fully by etching then.Aspect the kind of etching solution, the method for removing Copper Foil by etching is not specifically limited.Can use known method.
Then, under the situation of the roughened of the exposure resin layer surface that does not carry out laminated sheet, carry out electroless copper.For the method for fabricating printed wiring board that forms conductor layer by copper-plating method, usually,, require by coming on resin surface, to form coarse with permanganate or analog etching resin in order to ensure the bonding strength between copper coating and the curable resin.Yet, the invention is characterized in, do not require any roughened.The electroless copper method can be selected from known method.Usually, on the surface of above-mentioned resin bed, form palladium catalyst, then the gained laminated sheet is immersed in the electroless copper plating liquid, form thickness thus and be 0.5 to 2 micron copper layer.Then, by the whole surface of electrolytic copper plating plating, and be etched with the strong bonded copper circuit of formation.In addition, by selectivity adhere to electrolytic copper plating then etching and remove gained copper surface at least with the corresponding thickness of the thickness of no electrolytic copper coating, form strong bonded copper circuit thus.Select the thickness of electrolytic copper plating as required.In this case, in order further to improve the bonding strength of copper coating, preferably after forming no electrolytic copper coating or forming electrolytic copper plating layer, heat-treat at 100 ℃ to 200 ℃.Heat treatment period is not specifically limited.It is preferably 30 minutes to 5 hours.In order to prevent the Copper Foil oxidation, preferably heat in a vacuum or in inert gas.
Carry out subsequently copper electroforming according to known elimination approach (subtractive process) or graphic plating method, prepare printed substrate thus.Particularly, when forming figure,, and pass through known etching method selective removal copper coating, make printed substrate thus to form circuitous pattern with the position that will form copper circuit on the resist covering copper coating by elimination approach.When forming figure by the graphic plating method, by forming about 0.5 to the 1 micron no electrolytic copper coating of thickness, cover the position in addition, position that will form copper circuit with the resist plating selectivity then, form about 10 to the 30 microns electrolytic copper plating layer of thickness by graphic plating, divest resist plating then, then at least etching do not form electrolytic copper plating layer on it no electrolytic copper coating to form circuit, make printed substrate thus.
Embodiment
Below with reference to synthesis example, contrast synthesis example, embodiment and the present invention of Comparative Examples specific explanations.
(synthesis example)
Have the anchor type stirring rod made by stainless steel, be furnished with the trap that draws nitrogen pipe and plug and be installed in 2 liters of three-neck flasks of reflux condenser of the cooling water pipe on the trap with dribbling, add 117.68 gram (400 mMs) 3,4,3 ', 4 '-biphenyl tetracarboxylic dianhydride, 87.7 gram (300 mMs) 1, two (3-amino-benzene oxygen) benzene of 3-, 4.0 gram (40 mM) gamma-valerolactones, 4.8 gram (60 mM) pyridines, 300 gram N-N-methyl-2-2-pyrrolidone N-s (hereinafter being known as " NMP ") and 20 gram toluene.This mixture 180 ℃ of heating 1 hour, is cooled to about room temperature then.Add 29.42 gram (100 mMs) 3,4,3 ', 4 '-biphenyl tetracarboxylic dianhydride, 82.12 gram (200 mMs) 2, two { 4-(4-amino-benzene oxygen) phenyl } propane of 2-, 200 gram NMP and 40 gram toluene, and with these components mixed at room temperature 1 hour, be 38% block copolymer polyimide 180 ℃ of heating 3 hours to obtain solids content then.Block copolymer polyimide has 3: 2 formula (1): formula (2) ratio, 70,000 number-average molecular weight and 150,000 weight average molecular weight.
(contrast synthesis example)
Have the anchor type stirring rod made by stainless steel, be furnished with the trap that draws nitrogen pipe and plug and be installed in 2 liters of three-neck flasks of reflux condenser of the cooling water pipe on the trap with dribbling, add 164 gram (400 mM) ethylene glycol bis trimellitate dianhydrides, 124 gram (400 mMs) 4,4 '-diaminourea-3,3 ', 5,5 '-tetraethyl diphenyl methane, 4.0 gram (40 mM) gamma-valerolactones, 4.8 gram (60 mM) pyridines, 300 gram NMP and 20 gram toluene.Is 48% polyimides 180 ℃ of heating 3 hours to obtain solid content with this mixture.Polyimides has 31,000 number-average molecular weight and 78,000 weight average molecular weight.
(embodiment 1-4)
Further with the preparation solid content 10% block copolymer polyimide solution with the block copolymer polyimide solution that obtains in the NMP dilution synthesis example.According to the solid content ratio shown in the table 1, this block copolymer polyimide solution and two (4-maleimide aminophenyl) methane (BMI-H is provided by K I KASEI KK) are melted and mixed 20 minutes at 60 ℃, prepare resin solution thus respectively.It is (F0-WS paper tinsel on 12 microns the frosting of electrolytic copper foil that the resin solution that will make thus with reverse roll coater is coated to thickness respectively, the Rz=1.5 micron, by Furukawa circuit foil Co., Ltd. provide), then under nitrogen atmosphere 120 ℃ of dryings 3 minutes, and,, prepare resin composite copper foil thus respectively at last 300 ℃ of heat treatments 2 minutes 160 ℃ of dryings 3 minutes.On the other hand, with 400 grams 2, two (the 4-cyanato-phenyl) propane of 2-are 150 ℃ of fusings and it was under agitation reacted 4 hours, the gained product is dissolved in methyl ethyl ketone, and add 600 gram brominated bisphenol a type epoxy resin (EPICLON 1123P, by Dainippon Ink and Chemicals, Incorporated provides) and 0.1 part of zinc octoate with preparation varnish.Making varnish immerse thickness is 100 microns glass woven fabric base material, and 150 ℃ of dryings 6 minutes, preparing amount of resin thus was 45%, and 105 microns of thickness and gelling time (at 170 ℃) are 120 seconds B-b stage resin b composition layer (prepreg).Pile up four prepreg.The resin composite copper foil of the same type that as above obtains is placed upper surface and the lower surface that piles up prepreg, each resin composite copper foil in surface, thereby the resin layer surface that makes resin composite copper foil is towards the upper and lower surface of piling up prepreg, and with the gained sub-assembly at 220 ℃ and 40kgf/cm
2Pressure and 30mmHg or lower vacuum degree laminated moulding 1 hour, make the copper clad laminate of 0.4 millimeter of thickness thus respectively.Table 1 has shown evaluation result.
(embodiment 5)
Except using 2, two [4-(the 4-maleimide amino-benzene oxygen) phenyl] propane (BMI-80 of 2-, provide by K I KASEI KK) replace outside two (4-maleimide aminophenyl) methane used among the embodiment 3, according to embodiment 3 in identical mode make resin composite copper foil and copper clad laminate.Table 1 has shown evaluation result.
(table 1) evaluation result
Example=embodiment
(Comparative Examples 1)
Respectively do for oneself 12 microns the electrolytic copper foil (F0-WS paper tinsel) except resin composite copper foil used among the embodiment 1 being changed into thickness, according to embodiment 1 in identical mode make the copper clad laminate of 0.4 millimeter of thickness.Table 2 has shown evaluation result.
(Comparative Examples 2)
Except the preparation solid content is that 15% block copolymer polyimide solution replaces that used solid content is 10% block copolymer polyimide solution and does not use two (4-maleimide aminophenyl) methane among the embodiment 1, according to embodiment 1 in identical mode prepare resin composite copper foil.Except using above-mentioned resin composite copper foil to replace the resin composite copper foil used among the embodiment 1, according to embodiment 1 in identical mode make the copper clad laminate of 0.4 millimeter of thickness.
Table 2 has shown evaluation result.
(Comparative Examples 3)
Except block copolymer polyimide used among the embodiment 3 being changed into the polyimides that contrast obtains in the synthesis example, according to embodiment 3 in identical mode prepare resin composite copper foil.Except using above-mentioned resin composite copper foil to replace the resin composite copper foil used among the embodiment 3, according to embodiment 3 in identical mode make the copper clad laminate of 0.4 millimeter of thickness.Table 2 has shown evaluation result.
(table 2) evaluation result
(method of measurement)
1) gross thickness:
Use micrometer in 500 * 500 millimeters sample thickness of five point measurements according to JIS C6481, and obtain mean value.
2) Copper Foil bonding strength:
Carry out three times according to JIS C6481 and measure, and obtain mean value.
3) airborne thermal endurance:
According to JIS C6481, in air drier, heat-treated 30 minutes, and carried out 30 minutes at 280 ℃ at 240 ℃.Then, the range estimation whether exist cosmetic variation defect condition (zero: the zero defect situation, *: expand or peel off).
4) thermal endurance after the moisture absorption:
Remove the whole copper foil of half lip-deep Copper Foil of sample, 50 millimeters * 50 millimeters square samples in addition by etching.With sample pressure cooker test machine (PC-3 type, provide by HirayamaManufacturing Corporation) 121 ℃ and the 2 atmospheric pressure treatment scheduled times, make sample then in 260 ℃ scolder is bathed floating 60 seconds, and the range estimation whether exist cosmetic variation defect condition (zero: the zero defect situation, *: expand or peel off).
Embodiment 6-9
Further with the preparation solid content 10% block copolymer polyimide solution with the block copolymer polyimide solution that obtains in the NMP dilution synthesis example.According to the solid content ratio shown in the table 3, this block copolymer polyimide solution and two (4-maleimide aminophenyl) methane (BMI-H is provided by K I KASEI KK) are melted and mixed 20 minutes at 60 ℃, prepare resin solution thus respectively.It is (F0-WS paper tinsel on 12 microns the frosting of electrolytic copper foil that the resin solution that will make thus with reverse roll coater is coated to thickness respectively, the Rz=1.5 micron, by Furukawa circuit foil Co., Ltd. provide), then under nitrogen atmosphere 120 ℃ of dryings 3 minutes, and,, prepare resin composite copper foil thus respectively at last 300 ℃ of heat treatments 2 minutes 160 ℃ of dryings 3 minutes.
On the other hand, with 400 grams 2, two (the 4-cyanato-phenyl) propane of 2-are 150 ℃ of fusings and it was under agitation reacted 4 hours, product is dissolved in methyl ethyl ketone, and add 600 gram brominated bisphenol a type epoxy resin (EPICLON 1123P, by Dainippon Ink andChemicals, Incorporated provides) and 0.1 part of zinc octoate with preparation varnish.Make varnish immerse the glass woven fabric base material of 100 microns of thickness, and 150 ℃ of dryings 6 minutes, preparing amount of resin thus was 45%, 105 microns of thickness and gelling time (at 170 ℃) are 120 seconds B-b stage resin b composition layer (prepreg).Pile up four prepreg.The resin composite copper foil of the same type that as above obtains is placed upper surface and the lower surface that piles up prepreg, each resin composite copper foil in surface, thereby the resin layer surface that makes resin composite copper foil is respectively towards the upper and lower surface of piling up prepreg, and with the gained sub-assembly at 220 ℃ and 40kgf/cm
2Pressure and 30mmHg or lower vacuum degree laminated moulding 1 hour, make the copper clad laminate of 0.4 millimeter of thickness thus respectively.In these copper clad laminates, make the hole that has 0.2 mm dia separately with awl.Then, remove the Copper Foil of copper clad laminate fully with hydrogen peroxide sulfuric acid etchant liquid.In addition, forming thickness separately with electroless plating liquid (ATS ADCOPPER CT, by OkunoChemical Industries Co., Ltd. provides) on the gained copper clad laminate is 1 micron copper layer.In heating furnace, heated 2 hours at 130 ℃.Then, use the sulfuric acid copper plating bath with 1.5A/dm
2Electroplated 70 minutes, and on copper clad laminate, formed thickness separately thus respectively and be 20 microns copper layer.With thickness is that 10 microns etchant resist adheres on each laminated sheet that has formed above-mentioned copper layer on it, exposes then and develops, from only cover the position (width is 34 microns a circuit) that will form copper circuit with resist.Then, carry out etching, and divest resist, make respectively thus that to contain mean breadth respectively be the printed substrate of 25 microns copper circuit with the copper chloride etching solution.Table 3 has shown the result.
(table 3) evaluation result
Example=embodiment
Embodiment 10-13
Using electroless plating liquid to form the program of thickness before respectively being 1 micron the step of copper layer according to what the mode identical with embodiment 6-9 carried out carrying out in embodiment 6-9.Then, the anti-plate film of 15 micron thickness is adhered to respectively on the gained laminated sheet, and expose and develop to cover the position beyond the position that will form copper circuit with resist plating.Remove resist plating.With the sulfuric acid copper plating bath with 1.5A/dm
2Carry out electrolytic copper plating 50 minutes, thereby form the copper circuit of 17 micron thickness respectively.Then, use hydrogen peroxide sulfuric acid etchant liquid (by Mitsubishi Gas ChemicalCo., Inc. provides, trade name CPE800) to be etched with and form circuit with about 12/12 micron live width/line-spacing.Then, in stove, heated 2 hours, make printed substrate thus respectively at 130 ℃.Table 4 has shown the result.
(table 4) evaluation result
Example=embodiment
Comparative Examples 4 and 5
In not using embodiment 6 and 10 the used bismaleimides, respectively according to embodiment 6 and 10 in identical mode make printed substrate.Table 5 has shown evaluation result.
(table 5) evaluation result
(method of measurement)
1) gross thickness:
According to the thickness of JIS C6481, obtain mean value thus in five point measurement resin composite copper foils (500 * 500 millimeters of sizes).
2) copper facing bonding strength
The thickness that obtains by electroless plating and the electrolytic copper plating plating whole surface by the Copper Foil of etching copper clad laminate under the situation that does not form circuit is 0.4 millimeter laminated sheet, thereby preparation has the laminated sheet of copper coating on whole surface.Measure the copper facing bonding strength three times of laminated sheet according to JIS C6481, and obtain mean value.
3) thermal endurance after the moisture absorption:
The cutting printed substrate is to obtain 50 millimeters * 50 millimeters square samples.With sample pressure cooker test machine (PC-3 type, provide by Hirayama Manufacturing Corporation) 121 ℃ and the 2 atmospheric pressure treatment scheduled times, make sample then in 260 ℃ scolder is bathed floating 60 seconds, and the range estimation whether exist cosmetic variation defect condition (zero: the zero defect situation, *: expand or peel off).
Claims (12)
1. resin composite copper foil that is used for printed substrate, the resin bed that it comprises Copper Foil and contains block copolymer polyimide and maleimide compound, this resin bed forms on a surface of Copper Foil.
2. resin composite copper foil according to claim 1, wherein said block copolymer polyimide have the construction unit shown in construction unit shown in the formula (1) and the formula (2),
Wherein m and n satisfy m: n=1: 9 to 3: 1 integer.
3. resin composite copper foil according to claim 1, wherein said resin bed has 0.1 micron to 10 microns thickness.
4. resin composite copper foil according to claim 1, the weight ratio of contained block copolymer polyimide and maleimide compound is 10: 90 to 90: 10 in the wherein said resin bed.
5. one kind is used to make the method that is used for the resin composite copper foil of printed substrate as claimed in claim 1, comprise that the resin solution that will contain block copolymer polyimide and maleimide compound is coated on the surface of Copper Foil, scribble the Copper Foil of resin solution 250 to 360 ℃ of heat treatments then, thereby be formed on 200 ℃ or the low temperature resin bed that can not melt more.
6. copper clad laminate that is used for printed substrate, it is made up of resin composite copper foil that is used for printed substrate and B-b stage resin b composition layer, the described resin composite copper foil that is used for printed substrate comprises Copper Foil and contains the resin bed of block copolymer polyimide and maleimide compound, and this resin bed forms on a surface of Copper Foil.
7. the manufacture method of a printed substrate, this method comprises by etching removes the Copper Foil of copper clad laminate as claimed in claim 6 fully to expose resin layer surface and to obtain laminated sheet, under the situation of resin layer surface of laminated sheet not being carried out roughened, form no electrolytic copper coating by electroless copper, on no electrolytic copper coating, form electrolytic copper plating layer by electrolytic copper plating, remove no electrolytic copper coating and electrolytic copper plating layer by etching selectivity then, form copper circuit thus.
8. method according to claim 7 is wherein heat-treated at 100 ℃ to 200 ℃ after forming no electrolytic copper coating or forming electrolytic copper plating layer.
9. method of making printed substrate, this method comprises by etching removes the Copper Foil of copper clad laminate as claimed in claim 6 fully to expose resin layer surface and to obtain laminated sheet, under the situation of resin layer surface of laminated sheet not being carried out roughened, form no electrolytic copper coating by electroless copper, selectivity forms electrolytic copper plating layer on no electrolytic copper coating then, at least remove no electrolytic copper coating at the position that does not form electrolytic copper plating layer by etching then, form copper circuit thus.
10. method according to claim 9 is wherein heat-treated at 100 ℃ to 200 ℃ after forming no electrolytic copper coating or forming electrolytic copper plating layer.
11. printed substrate by method acquisition as claimed in claim 7.
12. printed substrate by method acquisition as claimed in claim 9.
Applications Claiming Priority (6)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2006016081A JP4896533B2 (en) | 2006-01-25 | 2006-01-25 | Resin composite copper foil and method for producing the same |
| JP2006016081 | 2006-01-25 | ||
| JP2006-016081 | 2006-01-25 | ||
| JP2006065010A JP4829647B2 (en) | 2006-03-10 | 2006-03-10 | Printed wiring board and manufacturing method thereof |
| JP2006-065010 | 2006-03-10 | ||
| JP2006065010 | 2006-03-10 |
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| CN101009973A CN101009973A (en) | 2007-08-01 |
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| JP4829647B2 (en) * | 2006-03-10 | 2011-12-07 | 三菱瓦斯化学株式会社 | Printed wiring board and manufacturing method thereof |
| TWI342323B (en) * | 2007-01-22 | 2011-05-21 | Chang Chun Plastics Co Ltd | Thermoset resin modified polyimide resin composition |
| JP4752910B2 (en) * | 2007-12-26 | 2011-08-17 | 三菱瓦斯化学株式会社 | Entry sheet for drilling |
| EP2428535A4 (en) * | 2009-05-08 | 2014-05-07 | Mitsubishi Gas Chemical Co | Thermosetting polyimide resin composition, cured product, and adhesive |
| JP5494341B2 (en) * | 2010-08-12 | 2014-05-14 | Ｄｉｃ株式会社 | Thermosetting resin composition, cured product thereof and interlayer adhesive film for printed wiring board |
| TW201235411A (en) * | 2011-02-01 | 2012-09-01 | Dainippon Ink & Chemicals | Hot curable polyimide resin composition, cured article thereof and interlayer adhesive film for printed wiring board |
| CN104735929B (en) * | 2013-12-24 | 2017-12-29 | 深南电路有限公司 | Circuit board processing method and equipment |
| CN111201277B (en) * | 2017-10-10 | 2021-12-03 | 三井金属矿业株式会社 | Resin composition for printed wiring board, copper foil with resin, copper-clad laminate, and printed wiring board |
| CN110381676B (en) * | 2018-04-13 | 2021-10-12 | 台郡科技股份有限公司 | Method for manufacturing thin embedded circuit roll type by exposure and hole forming |
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| US5298331A (en) * | 1990-08-27 | 1994-03-29 | E. I. Du Pont De Nemours And Company | Flexible multi-layer polyimide film laminates and preparation thereof |
| CN1402959A (en) * | 1999-12-06 | 2003-03-12 | 出光石油化学株式会社 | Multilayered printed circuit board |
| CN1410262A (en) * | 2001-10-10 | 2003-04-16 | 台虹科技股份有限公司 | High efficiency production method of double layer circuit soft board |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| JP3897576B2 (en) * | 2001-10-12 | 2007-03-28 | 株式会社ピーアイ技術研究所 | Block copolymerized polyimide composition soluble in ketone and / or ether solvent and process for producing the same |
| JP2003147171A (en) * | 2001-11-15 | 2003-05-21 | Hitachi Chem Co Ltd | Method for producing insulating resin composition, insulating resin composition, and copper-foil laminated insulating material and copper-clad laminate |
| JP4303623B2 (en) * | 2003-04-07 | 2009-07-29 | 三井化学株式会社 | Method for producing polyimide metal laminate and adhesive composition |
| JP4767517B2 (en) * | 2004-09-14 | 2011-09-07 | 三菱瓦斯化学株式会社 | Resin composite copper foil, copper-clad laminate and printed wiring board using the same |
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| US5298331A (en) * | 1990-08-27 | 1994-03-29 | E. I. Du Pont De Nemours And Company | Flexible multi-layer polyimide film laminates and preparation thereof |
| US5411765A (en) * | 1990-08-27 | 1995-05-02 | E. I. Du Pont De Nemours And Company | Flexible multi-layer polyimide film laminates and preparation thereof |
| CN1402959A (en) * | 1999-12-06 | 2003-03-12 | 出光石油化学株式会社 | Multilayered printed circuit board |
| CN1410262A (en) * | 2001-10-10 | 2003-04-16 | 台虹科技股份有限公司 | High efficiency production method of double layer circuit soft board |
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| JP4896533B2 (en) | 2012-03-14 |
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