CN104170532B

CN104170532B - Manufacturing method for laminated board and printed wiring board

Info

Publication number: CN104170532B
Application number: CN201380014295.1A
Authority: CN
Inventors: 伊藤哲平; 大东范行
Original assignee: NIPPON ELECTROLYTIC CO Ltd; Sumitomo Bakelite Co Ltd
Current assignee: NIPPON ELECTROLYTIC CO Ltd; Sumitomo Bakelite Co Ltd
Priority date: 2012-03-16
Filing date: 2013-03-07
Publication date: 2017-02-22
Anticipated expiration: 2033-03-07
Also published as: TWI590718B; CN104170532A; KR101528444B1; KR20140133910A; WO2013136729A1; JP2013219337A; JP5378620B2; TW201352085A

Abstract

Provided is a laminated board that is provided with an insulating layer and copper foil positioned on at least one surface of the insulating layer, and that is used in a device mounting substrate obtained by forming a conductor circuit by etching the copper foil. The copper foil etching rate is between 0.68[mu]m/min and 1.25[mu]m/min under conditions where the laminated board it immersed in a sulfuric acid/hydrogen peroxide etching liquid comprising 55.9g/L of sulfuric acid and 19.6cc/L of 34.5% hydrogen peroxide and at a temperature of 30 DEG C+1 DEG C.

Description

Laminate and the manufacture method of printed circuit board (PCB)

Technical field

The present invention relates to the manufacture method of laminate and printed circuit board (PCB).

Background technology

Multifunction with electronic equipment etc. requires, the high-density integrated of electronic unit, also high-density installation Advance Deng continuous, used in these printed circuit board (PCB) of corresponding high-density installation etc. compared with the past further advance little Type slimming, densification and multiple stratification.

Method as the high conductor circuit layers of pattern accuracy efficiently being formed with high density on the substrate of printed circuit board (PCB), Have started to implement semi-additive process.Manufacture method using the printed circuit board (PCB) of semi-additive process is for example civilian in patent document 1 and patent Offer on the books in 2.

In the manufacture method that patent document 1 and 2 is recorded, first, prepare to be covered with the laminate of Copper Foil in the one side of insulating barrier, Corrosion-resisting pattern is formed on this laminate.Then, fill coating in the opening portion of corrosion-resisting pattern.Then, remove corrosion-resisting pattern. Afterwards, using the pattern of coating as mask, the Copper Foil of lower floor is etched, is consequently formed the conductor being made up of coating and Copper Foil Circuit.

Prior art literature

Patent document

Patent document 1：Japanese Unexamined Patent Publication 2003-69218 publication

Patent document 2：Japanese Unexamined Patent Publication 2003-60341 publication

Content of the invention

In the manufacture process of patent document 1 and 2, the micro concavo-convex part that can be formed on the surface of insulating barrier produces copper The residue of paper tinsel.With the propulsion of miniaturization, the etch residue remaining in the Copper Foil between conductor circuit can constitute conductor circuit The reason short circuit such as defective insulation.It is therefore preferable that the etch residue of the Copper Foil on the surface of insulating barrier is removed.

Want to remove the etch residue of Copper Foil, need the surface of over etching insulating barrier.However, over etching insulating barrier When, conductor circuit also can be etched excessively, therefore it some times happens that conductor circuit form the exception, disconnection of conductor circuit, winged Go out.It is difficult to while implementing over etching maintain wiring shape to be desired shape.

As described above, in the laminate of patent document 1 and 2, reducing etch residue and the maintenance wiring shape of Copper Foil There is room for improvement in balance aspect.

According to the present invention, provide a kind of laminate,

Described laminate possesses insulating barrier and is located at the Copper Foil of at least one side of aforementioned dielectric layer, before it is used for by etching State Copper Foil and formed conductor circuit from obtained from device mounting board,

Containing sulfuric acid 55.9g/L and 34.5% aquae hydrogenii dioxidi 19.6cc/L and liquid temperature is 30 DEG C ± 1 DEG C of sulfuric acid/mistake The etch-rate impregnating the aforementioned Copper Foil under conditions of aforementioned laminate in the etching solution of oxidation hydrogen species is 0.68 μm/more than min And 1.25 μm/below min.

The present inventor etc. thinks, by improving the etch-rate of Copper Foil, is capable of reducing etch residue and the dimension of Copper Foil Hold taking into account of wiring shape.

The result studied further is distinguished, in the evaluation method of etch-rate, according to composition, the constituent concentration of etchant With the difference of the condition of liquid temperature, result can be inconsistent.

Thus found that, etchant adopts sulfuric acid, pure water and aquae hydrogenii dioxidi, determines constituent concentration, and then liquid temperature is set to 30 DEG C ± 1 DEG C, using these conditions as the premise of evaluation method, the inconsistent of result can be reduced.

And then, the present inventor etc. has carried out various experiments under precondition to the etch-rate of copper, it was found that passing through The lower limit of the etch-rate of copper is made to be not less than 0.68 μm/min, it is possible to reduce the etch residue of Copper Foil, wiring shape becomes good, Thus completing the present invention.

Additionally, according to the present invention, providing a kind of manufacture method of printed circuit board (PCB), the method includes：Prepare possess insulation Layer and the operation of the laminate of the Copper Foil of at least one side positioned at aforementioned dielectric layer, and by the aforementioned Copper Foil of selective removal Form the operation of conductor circuit, aforementioned laminate is above-mentioned laminate.

According to the present invention, the etch residue of Copper Foil is provided to reduce, wiring shape becomes good laminate.

Brief description

Fig. 1 is the sectional view of an example of the manufacture method of printed circuit board (PCB) schematically showing the 1st embodiment.

Fig. 2 is the sectional view of an example of the manufacture method of printed circuit board (PCB) schematically showing the 1st embodiment.

Fig. 3 is the sectional view of an example of the manufacture method of printed circuit board (PCB) schematically showing the 2nd embodiment.

Fig. 4 is the sectional view of an example of the manufacture method of printed circuit board (PCB) schematically showing the 2nd embodiment.

Fig. 5 is the sectional view of an example of the manufacture method of printed circuit board (PCB) schematically showing the 2nd embodiment.

Fig. 6 is the sectional view of an example of the manufacture method of printed circuit board (PCB) schematically showing the 3rd embodiment.

Fig. 7 is the sectional view of the variation of the manufacture method of printed circuit board (PCB) schematically showing the 3rd embodiment.

Specific embodiment

Hereinafter, using accompanying drawing, embodiments of the present invention are illustrated.In addition, in all of the figs, same composition Key element is marked with identical reference, suitably omits the description.

(the 1st embodiment)

Fig. 1 and Fig. 2 is the sectional view of the process of the manufacture method of printed circuit board (PCB) illustrating the 1st embodiment.

First, the summary of the printed circuit board (PCB) 101 of present embodiment is described.

The manufacture method of the printed circuit board (PCB) 101 of present embodiment includes following operations.First, prepare possess insulating barrier 102 and be located at insulating barrier 102 the Copper Foil (copper foil layer 104) of at least one side laminate (copper clad laminate 100).Then, lead to Cross selective removal Copper Foil and form conductor circuit (conductor circuit 119).Printed circuit board (PCB) 101 is used for device mounting board.

The manufacture method of the printed circuit board (PCB) 101 of present embodiment using forming conductor circuit by etching Copper Foil thus The laminate (copper clad laminate 100) obtaining.

In laminate (copper clad laminate 100), containing sulfuric acid 55.9g/L and 34.5% aquae hydrogenii dioxidi 19.6cc/L And under conditions of dipping laminate in the etching solution of sulfuric acid/hydroperoxide kind for 30 DEG C ± 1 DEG C for the liquid temperature, Copper Foil (copper foil layer 104) etch-rate is specifically for 0.68 μm/more than min and 1.25 μm/below min.

In copper clad laminate 100, the etch-rate of copper foil layer 104 is specifically for 0.68 μm/more than min.Therefore, in printing In the manufacture process of circuit board 101, copper foil layer 104 can be suppressed to remain on the insulating barrier 102 between conductor circuit 119, and And can make conductor circuit 119 wiring shape good.

Manufacturing process below for the printed circuit board (PCB) 101 of present embodiment is described in detail.

First, as shown in (a) of Fig. 1, prepare together to be fitted with Copper Foil on the two sides of insulating barrier 102 with carrier layers of foil 106 The copper clad laminate 10 with carrier foils of layer 104.Copper clad laminate 10 with carrier foils possesses insulating barrier 102, copper foil layer 104 and Carrier layers of foil 106.Together it is pasted with carrier layers of foil 106 on the two sides of insulating barrier 102 with copper foil layer 104.Present embodiment is exhausted The two sides of edge layer 102 is formed with copper foil layer 104 but it is also possible to only form copper foil layer 104 in the one side of insulating barrier 102.

As the copper clad laminate 10 with carrier foils, the such as at least one side in copper clad laminate 100 is laminated with peelable Carrier layers of foil 106.Copper clad laminate 100 (being otherwise referred to as laminate below) is not particularly limited, for example, can use (in figure eliminates fibre to be laminated with the plate of copper foil layer 104 at least one side of the insulating barrier 102 of the insulating resin layer having containing substrate Wiki material).Laminate can be individual layer, it is possible to have sandwich construction.That is, as laminate, can be only made up of sandwich layer, The plate that lamination layer is formed with sandwich layer can be used.Laminate for example can use the plate of multiple prepregs stacking Deng.Prepreg is not particularly limited, for example can be by making the resin group containing curable resin, curing agent and filler etc. Compound is impregnated into the medium method of the base materials such as glass cloth and obtains.Then, as laminate, it is possible to use in the stacking of at least one side Very thin metal forming with carrier foils simultaneously heats plate of press molding etc..Additionally, the interlayer insulating film of lamination layer can use With sandwich layer identical material, base material or resin combination can also be different.In present embodiment, insulating barrier 102 is equivalent to composition Sandwich layer or the insulating resin layer of lamination layer, can be any one in single or multiple lift structure.Possesses lamination layer with regard to using The example of laminate, illustrates in the 2nd embodiment below.

Constitute laminate used in present embodiment and the resin combination of interlayer insulating film can be used as printing The known resin (hereinafter also referred to insualtion resin composition) that the insulating materials of circuit board is used, generally mainly uses heat-resisting The good curable resin of property, chemical proofing.Above-mentioned resin combination is not particularly limited, preferably at least comprises to lead to Overheated and/or light irradiation and the resin combination of curable resin that solidifies.

As curable resin, for example, can include：Urea (urea) resin, melmac, maleimation Compound, polyurethane resin, unsaturated polyester resin, the resin with Benzoxazine ring, diallyl Na Dike acid imide chemical combination Thing, vinyl benzyl resin, vinylbenzyl ether resins, benzocyclobutane olefine resin, cyanate ester resin, epoxy resin etc..These Central, curable resin preferred glass transition temperature reaches more than 200 DEG C of combination.For example preferably use containing volution, heterocycle The more than sense epoxy resin in formula, trihydroxy methyl type, biphenyl type, naphthalene type, anthracene type, the 2 of phenolic varnish type or 3, cyanate ester resin (prepolymer containing cyanate ester resin), maleimide compound, benzocyclobutane olefine resin, there is the tree of Benzoxazine ring Fat.When using epoxy resin and/or cyanate ester resin, line expands and reduces, and heat resistance improves notable.Additionally, by epoxy resin And/or cyanate ester resin is when combining with the packing material of high filler loading capacity, have anti-flammability, heat resistance, resistance to impact, high rigidity and The excellent advantage of electrical characteristics (low-k, low-dielectric loss angle tangent).Here it is believed that the raising of heat resistance be due to：? After the curing reaction of above-mentioned curable resin, glass transition temperature reaches more than 200 DEG C, the heat of the resin combination after solidification Decomposition temperature raises, more than 250 DEG C at a temperature of the minimizing of the low molecular weight substance such as reaction residues.And then it is believed that anti-flammability Raising be due to：For the curable resin of the fragrant same clan, therefore in its structure, the ratio of phenyl ring is high, thus the easy charcoal of this phenyl ring Change (graphitization), produce charred portion.

Above-mentioned resin combination can contain fire retardant further in the range of the effect not damaging the present invention, from environment From the aspect of, preferably non-halogen based flame retardant.As fire retardant, for example, can include：Organic phosphates fire retardant, organic are nitrogenous Phosphorus compound, nitrogen compound, silicone based flame retardant, metal hydroxides etc..As organic phosphates fire retardant, can include： The phosphine compounds such as HCA, HCA-HQ, HCA-NQ that Sanko Co., Ltd. manufactures, the HFB- that Showa Highpolymer Co., Ltd manufactures The phosphorous benzoxazine compounds such as 2006M, PPQ, Clariant (Japan) K.K. that Hokko Chemical Industry Co., Ltd. manufactures The phosphate compounds such as the OP930, the PX200 of big eight KCCs manufacture that manufacture, Toto Kasei KK manufactures The phosphorous epoxy resins such as FX289, FX310, phosphorous phenoxy resin such as ERF001 that Toto Kasei KK manufactures etc..Make For the nitrogenous phosphorus compound of organic, can include：The phosphate acyls such as SP670, SP703 that Shikoku Chem manufactures Amines, the SPB100 of big KCC manufacture, SPE100, Co., Ltd.'s volt are shown in the FP- manufactured by making Phosphazene compounds such as series etc..As metal hydroxides, can include：Ube Material Industries, Ltd. system The magnesium hydroxides such as UD650, the UD653 making, the CL310 that Sumitomo Chemical Co manufactures, Showa Denko K. K manufacture Aluminium hydroxides such as HP-350 etc..

As epoxy resin used in above-mentioned resin combination, for example, can include：Bisphenol A type epoxy resin, Bisphenol F Type epoxy resin, phenol novolak type epoxy resin, cresol novolak type epoxy resin, bisphenol A novolac type epoxy Resin, biphenyl phenolic resin varnish type epoxy resin, anthracene type epoxy resin, dinitro anthracene type epoxy resin, 3 sense phenolic epoxy trees Fat, 4 sense phenol aldehyde type epoxy resins, naphthalene type epoxy resin, biphenyl type epoxy resin, aralkyl modified epoxy resin, ester ring type The double bond of epoxy resin, polyol type epoxy resin, glycidyl amine, ethylene oxidic ester, butadiene etc. carries out epoxidation and obtains Compound, by compound etc. obtained from reaction of hydroxyl organic siliconresin class and epichlorohydrin.In the middle of these, asphalt mixtures modified by epoxy resin Fat is preferably naphthalene type, aryl alkene fundamental mode epoxy resin.Aryl alkene fundamental mode epoxy resin refers to that repetitive includes fragrance Race's group combines more than one epoxy resin with the alkylidenes such as methylene, and its heat resistance, anti-flammability and mechanical strength are excellent Different.By using naphthalene type, aryl alkene fundamental mode epoxy resin, in gained laminate, moisture absorption welding heat resistance can be improved (the welding heat resistance after moisture absorption) and anti-flammability.As naphthalene type epoxy resin, can include：The HP- that Dainippon Ink Chemicals manufactures 4700th, HP-4770, HP-4032D, HP-5000, HP-6000, the NC-7300L that Nippon Kayaku K. K manufactures, Nippon Steel Learn ESN-375 that Co., Ltd. manufactures etc.；As aryl alkene fundamental mode epoxy resin, can include：Nippon Kayaku K. K NC-3000, NC-3000L, the NC-3000-FH manufacturing, the NC-7300L that Nippon Kayaku K. K manufactures, Nippon Steel's chemistry strain ESN-375 that formula commercial firm manufactures etc..

Used in above-mentioned resin combination, cyanate ester resin for example can be reacted by making halogenation cyanogen compound and phenols And obtain.As the specific example of cyanate ester resin, for example, can include：Phenol novolak type cyanate ester resin, cresols phenol The phenolic varnish type cyanate ester resins such as Novolac type cyanate ester resin, naphthols aralkyl-type cyanate ester resin, dicyclopentadiene-type Cyanate ester resin, biphenyl type cyanate ester resin, bisphenol A cyanate ester resin, bisphenol-A D type cyanate ester resin, tetramethyl Bisphenol F Bisphenol type cyanate ester resin such as type cyanate ester resin etc..

Particularly preferably contain in the middle of these phenolic varnish type cyanate ester resin, naphthols aralkyl-type cyanate ester resin, two Cyclopeutadiene type cyanate ester resin, biphenyl type cyanate ester resin.And then, resin combination preferably comprises with respect to resin combination All solids composition be more than 10 weight % this cyanate ester resin.Thereby, it is possible to improve the heat resistance (glass of prepreg Change transition temperature, heat decomposition temperature).And thermal coefficient of expansion (the thickness of particularly prepreg of prepreg can be reduced The thermal coefficient of expansion in direction).When the thermal coefficient of expansion of the thickness direction of prepreg reduces, multilayer board can be mitigated Ess-strain.And then, in the multilayer board with fine interlayer connecting portion, it can be greatly improved and connect reliability Property.

As particularly suitable material in the middle of phenolic varnish type cyanate ester resin used in above-mentioned resin combination, can lift Go out the phenolic varnish type cyanate ester resin represented by following formula (1).Preferably weight average molecular weight is more than 2000, is more preferably 2, 000～10,000, more preferably 2,200～3,500 phenolic varnish type cyanate ester resin represented by formula (1) and weight Average molecular weight is less than 1500, more preferably 200～1,300 phenolic varnish type cyanate ester resin combination represented by formula (1) Use (below, "～" in case of no particular description represent include higher limit and lower limit).In addition, in present embodiment Middle weight average molecular weight is the value being recorded with the gel permeation chromatography of polystyrene conversion.

[chemical formula 1]

In formula (1), n represents more than 0 integer.

Additionally, as cyanate ester resin, also suitably using the cyanate ester resin represented by following formulas (2).Following formulas (2) cyanate ester resin represented by is to make obtained from naphthols aralkyl resin and cyanic acid condensation, described naphthols aralkyl resin It is by the aphthols such as alpha-Naphthol or betanaphthol and terephthaldehyde's base glycol, α, α '-dimethoxy-paraxylene, 1,4- bis- Obtained from the reaction such as (2- hydroxyl -2- propyl group) benzene.The n of formula (2) is more than 1 it may be more desirable to less than 10.N is less than 10 When, resin viscosity will not increase, immersion good to base material, can suppress the reduction of the performance as laminate.Additionally, It is less likely to occur intramolecular polymerization, point fluidity during washing improves, and is prevented from the reduction of yield during synthesis.

[chemical formula 2]

In formula (2), R represents hydrogen atom or methyl, and R can be the same or different, and n represents more than 1 integer.

Additionally, as cyanate ester resin, also suitably using the dicyclopentadiene-type cyanate represented by following formulas (3) Resin.Dicyclopentadiene-type cyanate ester resin represented by following formulas (3) more preferably, the n of following formulas (3) be 0 with Upper and less than 8.When n is less than 8, resin viscosity will not increase, immersion good to base material, is prevented from as laminate The reduction of performance.Additionally, by using dicyclopentadiene-type cyanate ester resin, agent of low hygroscopicity and chemical proofing are excellent.

[chemical formula 3]

In formula (3), n represents 0～8 integer.

Additionally, resin combination can contain curing accelerator further.For example, if curable resin is asphalt mixtures modified by epoxy resin Fat, cyanate ester resin, then can use phenolic resin, epoxy resin, the curing accelerator of cyanate ester resin.Phenolic resin is not had It is particularly limited to, for example, can include：Phenol resol resins, cresol novolac resin, bisphenol A novolac resin, The novolak phenolics such as aryl alkene fundamental mode novolac resin, unmodified resol, use tung oil, flax Resol type phenol resins such as the modified oil modification resol such as seed oil, walnut oil etc..As above-mentioned phenolic resin, excellent Select phenol novolacs or cresol novolac resin.Wherein from moisture absorption weld heat resistance in terms of from the point of view of preferred biphenyl aralkyl Base modified phenol novolac resin.

Can be used alone in them a kind it is also possible to and with two or more, there is the material of different weight average molecular weight, One kind or two or more above-mentioned resin and their prepolymer can also be applied in combination.

Above-mentioned curing accelerator is not particularly limited, for example, can include：Zinc naphthenate, cobalt naphthenate, tin octoate, pungent Sour cobalt, bis-acetylacetonate close cobalt (II), praseodynium closes the organic metal salts such as cobalt (III)；Triethylamine, tri-butylamine, two The tertiary amines such as azabicyclo [2,2,2] octane；2-methylimidazole, 2- phenylimidazole, 2- phenyl -4-methylimidazole, 2- ethyl -4- Ethyl imidazol(e), 1 benzyl 2 methyl imidazole, 1- benzyl -2- phenylimidazole, 2- undecyl imidazole, 1- cyano ethyl -2- second Base -4-methylimidazole, 1- cyano ethyl -2- undecyl imidazole, 2- phenyl -4- methyl -5- hydroxy imidazole, 2- phenyl -4,5- The imidazoles such as dihydroxy imidazoles, 2,3- dihydro -1H- pyrrolo- (1,2-a) benzimidazole；The phenol such as phenol, bisphenol-A, nonyl phenol Compound；The organic acids such as acetic acid, benzoic acid, salicylic acid, p-methyl benzenesulfonic acid, salt compound etc. or its mixture.Can be independent Using Bao Kuo a kind including their derivative it is also possible to and with two or more including their derivative.

Additionally, from the point of view of in terms of the heat resistance, above-mentioned curable resin can contain maleimide compound.Horse As long as to have the compound of more than 1 dimaleoyl imino in imide compound 1 molecule, then it is not particularly limited. As its specific example, can include：N-phenylmaleimide, N- hydroxyphenyl-maleimides, double (4- maleimide Phenyl) methane, 2,2- double { 4- (4- maleimidephenoxy)-phenyl } propane, double (3,5- dimethyl -4- maleimide Phenyl) methane, double (3- ethyl -5- methyl -4- maleimide phenyl) methane, double (3,5- diethyl -4- maleimide benzene Base) methane, polyphenyl methylmethane maleimide, the prepolymer of these maleimide compounds or maleimide compound With the prepolymer of amines etc..

Additionally, from the adaptation of metal forming in terms of from the point of view of, above-mentioned curable resin can contain phenoxy group tree Fat, polyvinyl alcohol resin, polyimides, polyamide, polyamidoimide, polyethersulfone resin, polyphenylene oxide resin.

As phenoxy resin, for example, can include：The phenoxy resin with bisphenol backbone, the benzene oxygen with naphthalene skeleton Base resin, there is phenoxy resin of biphenyl backbone etc..In addition it is also possible to the benzene oxygen using the structure with these skeletons multiple Base resin.

In the middle of these, phenoxy resin preferably uses the phenoxy resin with biphenyl backbone and bisphenol S skeleton.Thus, The rigidity being had by biphenyl backbone, it is possible to increase the glass transition temperature of phenoxy resin, and pass through bisphenol S skeleton Presence, it is possible to increase the adaptation of phenoxy resin and metal.As a result, it is possible to realize the raising of the heat resistance of insulating barrier 102, And the adaptation of wiring portion (conductor circuit 118) and insulating barrier 102 can be improved when manufacturing multilager base plate.Additionally, benzene oxygen Base resin is further preferably using the phenoxy resin with bisphenol A skeleton and Bisphenol F skeleton.Thus, when manufacturing multilager base plate, The adaptation of wiring portion and insulating barrier 102 can be improved further.

As the commercially available product of phenoxy resin, can include：FX280 and FX293 that Toto Kasei KK manufactures, Japan Epoxy Resins Co., Ltd. manufacture YX8100, YX6954, YL6974, YL7482, YL7553, YL6794, YL7213 and YL7290 etc..The molecular weight of phenoxy resin is not particularly limited, weight average molecular weight is preferably 5,000～70, 000, more preferably 10,000～60,000.

During using phenoxy resin, its content is not particularly limited, preferably 1～40 overall weight of resin combination Amount %, more preferably 5～30 weight %.

As the commercially available product of polyvinyl alcohol resin, can include：The Denka that Deuki Kagaku Kogyo Co., Ltd manufactures Butyral4000-2,5000-A, 6000-C and 6000-EP, the S-LEC BH series of Sekisui Chemical Co., Ltd's manufacture, BX series, KS series, BL series and BM series etc..Especially, particularly preferred glass transition temperature is more than 80 DEG C of resin.

As polyimides, polyamide, polyamidoimide commercially available product, can include：Toyo Boseki K.K's system " VYLOMAX HR11NN (registration mark) " made and " HR-16NN " " HR15ET ", Hitachi Chemical Co., Ltd. manufactures Polyamidoimide " KS-9300 " etc..Can include：" NEOPULIM C-1210 " that Mitsubishi Gas Chemical Co., Ltd manufactures, Soluble polyimide " RIKACOAT SN20 (registration mark) " and " RIKACOAT that New Japan Chem Co., Ltd manufactures The PEI " ULTEM (registration mark) " that PN20 (registration mark) ", GE Plastics Japan Ltd. manufactures, DIC strain " V8000 " and " V8002 " and " V8005 " that formula commercial firm manufactures, " BPAM155 " that Nippon Kayaku K. K manufactures etc..

Commercially available product as polyethersulfone resin, it is possible to use known material, for example, can include：Sumitomo Chemical strain formula meeting PES4100P, PES4800P, PES5003P and PES5200P that society manufactures etc..

As polyphenylene oxide resin, for example, can include：Poly- (2,6- dimethyl -1,4- phenylate), poly- (2,6- diethyl -1, 4- phenylate), poly- (2- methyl -6- ethyl -1,4- phenylate), poly- (2- methyl -6- propyl group -1,4- phenylate), poly- (2,6- dipropyl - 1,4- phenylate), poly- (2- ethyl -6- propyl group -1,4- phenylate) etc..As commercially available product, for example, there is GE Plastics Japan Ltd. " NORYL PX9701 (registration mark) " (number-average molecular weight Mn=14,000), " NORYL640-111 (registrar manufacturing Mark) " (number-average molecular weight Mn=25,000) and Asahi Kasei Corporation manufacture " SA202 " (number-average molecular weight Mn=20, 000) etc., with known method, their low molecule quantizations can be used.

In the middle of these, the reactivity oligomeric phenylate of preferred end functional group modification.So that and curable resin Compatibility improve, the three-dimensional crosslinking structure between polymer, therefore mechanical strength can be formed.Japan spy for example can be enumerated Open the 2,2' described in 2006-28111 publication, 3,3', 5,5'- -hexamethyl biphenyl -4,4'- glycol -2,6- xylenol Condensation polymer and the product of 1-chloro-4-methyl-benzene.

This reactive oligomeric phenylate can be manufactured by known method.In addition it is also possible to use commercially available product.For example may be used With suitably using OPE-2st2200 (Mitsubishi Gas Chemical Co., Ltd's manufacture).

The weight average molecular weight of the oligomeric phenylate of reactivity is preferably 2,000～20,000, more preferably 4,000～15,000. It becomes difficult to be dissolved in volatile solvent when the weight average molecular weight of the oligomeric phenylate of reactivity is more than 20,000.And weight average molecular weight is little When 2,000, crosslink density is too high, thus can be to the elastic modelling quantity of solidfied material, flexible generation harmful effect.

The amount of the curable resin in resin combination used in present embodiment suitably adjusts i.e. according to its purpose Can, it is not particularly limited, with respect to all solids composition of resin combination, curable resin is preferably 10～90 weight %, More preferably 20～70 weight %, still more preferably for 25～50 weight %.

Additionally, when using epoxy resin and/or cyanate ester resin as curable resin, with respect to above-mentioned resin combination The all solids composition of thing, epoxy resin is preferably 5～50 weight %, and epoxy resin is more preferably 5～25 weight %.Additionally, With respect to all solids composition of resin combination, cyanate ester resin is preferably 5～50 weight %, and cyanate ester resin is more preferably 10～25 weight %.

From the point of view of in terms of low-thermal-expansion and the mechanical strength, in preferably above-mentioned resin combination, contain inorganic filling material. Inorganic filling material is not particularly limited, for example, can include：Talcum, calcined clay, non-calcined clay, mica, glass etc. Silicate；The oxides such as titanium oxide, aluminum oxide, silica, fused silica；Calcium carbonate, magnesium carbonate, Hydrotalcite etc. Carbonate；Aluminium hydroxide, boehmite (boehmite (that is, the Al of AlO (OH), commonly referred to "false" boehmite₂O₃·xH₂O, here, X=1～2)), magnesium hydroxide, the metal hydroxides such as calcium hydroxide；The sulfate such as barium sulfate, calcium sulfate, calcium sulfite or Asia Sulfate；The borates such as Firebrake ZB, barium metaborate, aluminium borate, line borate, Boratex；Aluminium nitride, boron nitride, silicon nitride, nitridation The nitride such as carbon；Titanates such as strontium titanates, barium titanate etc..Can be used alone in them a kind it is also possible to and use two or more.

Preferred magnesium hydroxide, aluminium hydroxide, boehmite, silica, fused silica, talcum, roasting in the middle of these Burn talcum, aluminum oxide.From the point of view of in terms of low heat expansion and the insulating reliability, particularly preferred silica, further preferably Spherical fused silica.Additionally, from the point of view of in terms of the flame resistance, preferably aluminium hydroxide.Additionally, using in present embodiment Even the base material that inorganic filling material also easily impregnates, inorganic filling material in above-mentioned resin combination therefore can be made Amount is more.When inorganic filling material in resin combination is high concentration, bit wear characteristic is deteriorated, but from inorganic filling material It is preferred from the point of view of the aspect improving for bit wear characteristic during boehmite.

The particle diameter of inorganic filling material is not particularly limited, it is possible to use average grain diameter monodispersed inorganic fill material Material, it is possible to use the polydisperse inorganic filling material of average grain diameter.And then it is also possible to and use one kind or two or more average grain diameter Single dispersing and/or polydisperse inorganic filling material.The average grain diameter of inorganic filling material is not particularly limited, preferably 0.1 μm～5.0 μm, particularly preferably 0.1 μm～3.0 μm.When the particle diameter of inorganic filling material is less than aforementioned minimum value, resin group The viscosity of compound uprises, and therefore produces impact to the workability making during prepreg sometimes.In addition, exceeding aforementioned higher limit When, it some times happens that the phenomenon such as inorganic filling material precipitation in resin combination.It should be noted that average grain diameter can make Surveyed with laser diffraction/scattering formula particle size distribution device (conventional equipment such as SALD-7000 that Shimadzu Seisakusho Ltd. manufactures) Fixed.

The content of inorganic filling material is not particularly limited, with respect to all solids composition of above-mentioned resin combination, It is preferably 10～90 weight %, more preferably 30～80 weight %, still more preferably for 50～75 weight %.Above-mentioned When containing cyanate ester resin and/or its prepolymer in resin combination, with respect to all solids composition of resin combination, on The content stating inorganic filling material is preferably 50～75 weight %.When inorganic filling material content exceedes above-mentioned higher limit, then have When resin combination mobility become extreme difference, it is not preferable, during less than above-mentioned lower limit, is sometimes formed by resin combination The intensity of insulating barrier is insufficient, not preferably.

Additionally, resin combination can also be compounded rubber constituent used in present embodiment, for example, as can this Used in embodiment, the preferred example of rubber grain, can include：Core-shell-type rubber grain, crosslink propylene nitrile butadiene Rubber grain, cross-linked styrene butadiene rubber particles, acrylic rubber particle, organic silicon granule etc..

Core-shell-type rubber grain is the rubber grain with sandwich layer and shell, for example, can include：The shell of outer layer is by glass The rubber grain of 2 Rotating fields that glass shaped polymer is constituted, the sandwich layer of internal layer is made up of rubber-like polymer；Or the shell of outer layer by The rubber of the 3-tier architecture that glassy polymers is constituted, intermediate layer is made up of rubber-like polymer, sandwich layer is made up of glassy polymers Glue particle etc..Glassy polymeric nitride layer is for example made up of the polymer etc. of methyl methacrylate, and rubbery polymeric nitride layer is for example It is made up of butyl acrylate thing (butyl rubber) etc..As the specific example of core-shell-type rubber grain, can include： Stafiloid AC3832, AC3816N (trade name, Ganz Chemical Co., Ltd. manufactures), METABLEN KW-4426 (trade name, Mitsubishi Rayon Co., Ltd. manufactures).Tool as crosslink propylene nitrile butadiene rubber (NBR) particle Style, can enumerate XER-91 (0.5 μm of average grain diameter, JSR Corporation manufacture) etc..

As the specific example of cross-linked styrene butadiene rubber (SBR) particle, XSK-500 (average grain diameter 0.5 can be enumerated μm, JSR Corporation manufacture) etc..As the specific example of acrylic rubber particle, can include：METABLEN W300A (0.1 μm of average grain diameter), W450A (0.2 μm of average grain diameter) (Mitsubishi Rayon Co., Ltd. manufacture) etc..

As long as the caoutchouc elasticity particulate that organic silicon granule is formed by organopolysiloxane, it is not particularly limited, example As included：The particulate that itself formed by organic silicon rubber (organopolysiloxane cross-linked elastomer) and with three-dimensional cross-linked Core shell structure particle of core that the silicone covering of type main body is formed by the organosilicon of two dimension crosslinking main body etc..As Organic silicon rubber particulate, it is possible to use：KMP-605, KMP-600, KMP-597, KMP-594 (KCC of SHIN-ETSU HANTOTAI system Make), the commercially available product such as Trefil E-500, Trefil E-600 (Dow Corning Toray Co., Ltd. manufacture).

Coupling agent can be contained further in above-mentioned resin combination.Coupling agent is compounded for this purpose：By carrying The wetability at the interface of high solidification resin and inorganic filling material is so that resin and inorganic filling material are equably bonded to base Material, improves heat resistance, the welding heat resistance particularly after moisture absorption.

Above-mentioned coupling agent is not particularly limited, for example, can include：Epoxy silane coupling agent, cationic silane are coupled Agent, amino silicane coupling agent, titante coupling agent, silicone oil type coupling agent etc..Thereby, it is possible to improve and inorganic filling material The wetability at interface, thus, it is possible to improve heat resistance further.

The addition of above-mentioned coupling agent is not particularly limited, with respect to inorganic filling material 100 weight portion, preferably 0.05～3 weight portion, particularly preferably 0.1～2 weight portion.When content is less than aforementioned minimum value, sometimes due to cannot be abundant Coating inorganic filling material and lead to improve heat resistance effect reduce, when exceeding aforementioned higher limit, then on reaction produce impact, Sometimes bending strength etc. can reduce.

Defoamer, levelling agent, ultraviolet can be added as desired in resin combination used in present embodiment Beyond the mentioned components such as the flame retardants such as absorbent, foaming agent, antioxidant, fire retardant, organosilicon powder, ion capturing agent Additive.

From the point of view of in terms of low linear expansion, high rigidity and the high resistance to thermalization easily realizing prepreg, above-mentioned resin Composition preferably at least contains epoxy resin, cyanate ester resin and inorganic filling material.Central, consolidating with respect to resin combination Body composition, preferably comprises epoxy resin, the cyanate ester resin of 5～50 weight % and 10～90 weight % of 5～50 weight % Inorganic filling material, the epoxy resin of further preferably 5～25 weight %, the cyanate ester resin of 10～25 weight % and 30 The inorganic filling material of～80 weight %.

Used in present embodiment, prepreg is the varnish of dipping or coating resin combination in the substrate, As base material, it is possible to use for the well-known material of various insulating material laminates.Material as base material Example, can include：The inorganic matter fibers such as E glass, D glass, NE glass, T glass, S glass or Q glass；Polyimides, poly- The organic fiber such as ester or tetrafluoroethene and their mixture etc..These base materials have for example weave cotton cloth, non-woven fabrics, rove, be chopped The shapes such as felt, surface felt, material and shape select according to purposes, the performance of target molding, can individually make as desired With or use material of more than two kinds and shape.The thickness of base material is not particularly limited, 0.01～0.5mm is usually used Material, from heat resistance, moisture-proof, processability in terms of from the point of view of, be suitably and carried out surface treatment with silane coupler etc. Material, implement mechanization fibrillation process and flattening material.Additionally, prepreg generally can obtain as follows：To base material Dipping or coated with resins make its resin containing ratio reach 20～90 weight % after the drying, add at a temperature of 120～220 DEG C Heated drying 1～20 minute, makes semi-cured state (B scalariform state), thus obtains.And then, generally it is laminated 1～20 this semi-solid preparation Piece, is laminated so that the composition being configured with the ultrathin copper foil with carrier foils on its two sides carries out heating pressurization further, thus permissible Obtain laminate.The thickness of multi-disc layer of prepreg is different according to purposes, is generally suitably the thickness of 0.03～2mm.As Laminating method, can apply the gimmick of common laminate, for example can be using multistage compacting, multi-stage vacuum compacting, continuous one-tenth Shape, autoclave forming machine etc. are generally in 100～250 DEG C of temperature, pressure 0.2～10MPa, the condition of 0.1～5 hour heat time Under be laminated, or vacuum lamination apparatus etc. can be used in 50～150 DEG C of lamination, 0.1～5MPa, vacuum pressure It is laminated under conditions of 1.0～760mmHg.

Additionally, the roughening face of the ultrathin copper foil of the ultrathin copper foil with carrier foils (copper foil layer 104) can be through based on formation The electro-deposition nitride layer of convex (is referred to as plating spot.For example, see Japanese Unexamined Patent Publication 9-195096), oxidation processes, reduction treatment, The roughening face of etching etc. is processed.Thus, the one side in the main part of copper foil layer 104 forms band bossing (hereinafter also referred to Roughening foot divides (roughened part)).

Additionally, in the present embodiment, as copper foil layer 104, the Copper Foil except being formed by copper (can not be kept away in manufacturing process Except the tramp material being mixed into exempting from) beyond, can also be and add the Copper Foil of metal ingredient (in the case of being somebody's turn to do, to copper containing nickel, aluminium etc. Content be not particularly limited, with respect to constitute copper foil layer 104 whole metal ingredients weight total value, preferably 90 weights Amount more than %, more than more preferably 95 weight %, more than more preferably 99 weight %.Additionally, as interpolation metal ingredient, Can be used alone one kind it is also possible to and with multiple).In addition it is also possible to replace copper foil layer using the metal forming such as nickel foil, aluminium foil 104.

Here, illustrating to the detailed forming method of release Copper Foil peelable used in copper foil layer 104.

As the manufacture method of Copper Foil used in present embodiment, it is not particularly limited, for example, manufacture and there is carrier During peelable release Copper Foil, the carrier foils of 10～50 μm of thickness are formed metal as peel ply etc. inorganic compound or Person's organic compound layer, forms Copper Foil by plating on this peel ply.As plating liquid, for example, can use sulfuric acid Copper or cupric pyrophosphate etc. are carried out.In addition, it is contemplated that the physical property of Copper Foil, flatness, various interpolations can be added in above-mentioned bath Agent.In addition, peelable release metal forming refers to carrier and the strippable metal forming of carrier.

In the present embodiment, the formation of the Copper Foil on peel ply for example can be bright by using containing as additive The copper sulfate bath of glue and chloride ion carries out catholyte and processes to carry out, thus carrying out.Copper sulfate bath for example contains 15～35ppm mean molecule quantity is less than 5000 gelatin.Additionally, for copper sulfate bath, for example dense as chloride ion Degree is containing 0.1～100ppm, preferably 0.5～50ppm, particularly preferably 1～25ppm.

In the case of being somebody's turn to do, being formed of Copper Foil as negative electrode and uses above-mentioned copper sulphate by the carrier foils being formed with peel ply Plating bath carries out electrolysis and processes copper facing on peel ply and carry out.According to the forming method of this Copper Foil, even if can be formed in height The Copper Foil that temperature also has appropriate mechanical strength after heating, etching is excellent and treatability is also excellent.This effect is by passing through Adding gelatin can make the crystal miniaturization of composition Copper Foil be brought.

When the mean molecule quantity of gelatin is less than 5000, the recrystallization of thin copper layer being led to by heating can be suppressed.Thus Realize the miniaturization of the crystal after heating.Not yet fully understand fully with regard to its reason it is believed that by make gelatin molecular weight be one Below definite value, gelatin easily enters crystal grain boundary in plating, and result can suppress recrystallization to carry out.The mean molecule quantity of gelatin It is preferably 500～5000, more preferably 1000～5000.By make gelatin mean molecule quantity be more than 500, can suppress to add The gelatin being added in copper sulfate bath is decomposed in an acidic solution and is decomposed into the organic compounds such as the amino acid of low-molecular-weight. Thereby, it is possible to suppress to prevent the effect recrystallizing from reducing by making gelatin enter crystal grain boundary in plating.

The concentration of the gelatin in copper sulfate bath is preferably 15～35ppm.When the concentration of gelatin is more than 15ppm, can Fully obtain the inhibition to the recrystallization being led to by heating.Therefore, it can maintain micro crystal state after the heating.Gelatin Concentration be below 35ppm when, the internal stress of the Copper Foil being formed by plating can be suppressed to increase.Thereby, it is possible to suppress to carry The ultrathin copper foil of carrier foils crimps and in conveyance, rough sledding occurs.

As copper sulfate bath, for example, suitably use the sulfuric acid containing copper sulfate pentahydrate, sulfuric acid, gelatin and chlorine Copper sulfate bath.The concentration of the copper sulfate pentahydrate in copper sulfate bath is preferably 50g/L～300g/L, more preferably 100g/L～200g/L.The concentration of sulfuric acid is preferably 40g/L～160g/L, more preferably 80g/L～120g/L.The concentration of gelatin As mentioned above.Chloride ion concentration is preferably 1～20ppm, more preferably 3～10ppm.The solvent of plating bath is usually water.Plating The temperature of bath is preferably 20～60 DEG C, more preferably 30～50 DEG C.Current density when electrolysis is processed is preferably 1～15A/dm², More preferably 2～10A/dm².

When forming Copper Foil, carrying out being electrolysed before processing using above-mentioned copper sulfate bath, in order to prevent the generation of pin hole, permissible Using the so-called strike plating (strike plating) employing the good plating bath of covering power.Used as strike plating Plating bath, for example, can include：Cupric pyrophosphate plating bath, copper citrate plating bath, copper citrate nickel plating bath etc..

As cupric pyrophosphate plating bath, for example, it is suitably the plating bath containing cupric pyrophosphate and potassium pyrophosphate.Cupric pyrophosphate plating bath In cupric pyrophosphate concentration be preferably 60g/L～110g/L, more preferably 70g/L～90g/L.The concentration of potassium pyrophosphate is preferred For 240g/L～470g/L, more preferably 300g/L～400g/L.The solvent of plating bath is usually water.The pH of plating bath is preferably 8.0 ～9.0, more preferably 8.2～8.8.Ammoniacal liquor etc. (similarly hereinafter) can be added to adjust pH value.The temperature of plating bath is preferably 20 ～60 DEG C, more preferably 30～50 DEG C.Current density when electrolysis is processed is preferably 0.5～10A/dm², more preferably 1～7A/ dm².Electrolytic processing time preferably 5～40 seconds, more preferably 10～30 seconds.

As copper citrate plating bath, for example, it is suitably the plating containing copper sulfate pentahydrate and citrate trisodium dihydrate Bath.The concentration of the copper sulfate pentahydrate in copper citrate plating bath is preferably 10g/L～50g/L, more preferably 20g/L～40g/ L.The concentration of citrate trisodium dihydrate is preferably 20g/L～60g/L, more preferably 30g/L～50g/L.The solvent of plating bath It is usually water.The pH of plating bath is preferably 5.5～7.5, more preferably 6.0～7.0.The temperature of plating bath is preferably 20～60 DEG C, more It is preferably 30～50 DEG C.Current density when electrolysis is processed is preferably 0.5～8A/dm², more preferably 1～4A/dm².At electrolysis Preferably 5～40 seconds reason time, more preferably 10～30 seconds.

As copper citrate nickel plating bath, for example, it is suitably containing copper sulfate pentahydrate, nickel sulfate hexahydrate compound and lemon The plating bath of sour trisodium dihydrate.The concentration of the copper sulfate pentahydrate in copper citrate nickel plating bath is preferably 10g/L～50g/ L, more preferably 20g/L～40g/L.The concentration of nickel sulfate hexahydrate compound preferably 1g/L～10g/L, more preferably 3g/L～ 8g/L.The concentration of citrate trisodium dihydrate is preferably 20g/L～60g/L, more preferably 30g/L～50g/L.Plating bath molten Agent is usually water.The pH of plating bath is preferably 5.5～7.5, more preferably 6.0～7.0.The temperature of plating bath is preferably 20～60 DEG C, More preferably 30～50 DEG C.Current density when electrolysis is processed is preferably 0.5～8A/dm², more preferably 1～4A/dm².Electrolysis Process time preferably 5～40 seconds, more preferably 10～30 seconds.

Above-mentioned peel ply is inorganic compound or the organic compound layers such as metal oxide, as long as standing when being laminated Heat treatment between 100～300 DEG C can also be peeled off and then can be used known material.As metal oxide, for example, can make Mixture with zinc, chromium, nickel, copper, molybdenum, alloy system, metal and metallic compound.As organic compound, preferably use by selecting The material of the one kind or two or more formation from organic compounds containing nitrogen, organic compounds containing sulfur and carboxylic acid.

Above-mentioned organic compounds containing nitrogen preferably has the organic compounds containing nitrogen of substituent.Specifically, preferably use L, 2,3 triazole (hereinafter referred to as " BTA ") as the triazole compounds with substituent, carboxyl benzotriazole are (hereinafter referred to as For " CBTA "), N', N'- double (BTA ylmethyl) urea (hereinafter referred to as " BTD-U "), 1H-1,2,4- triazole are (hereinafter referred to as " TA ") and 3- amino -1H-1,2,4- triazole (hereinafter referred to as " ATA ") etc..

As organic compounds containing sulfur, preferably use mercaptobenzothiazoler (hereinafter referred to as " MBT "), thiocyanuric acid (below It is referred to as " TCA ") and 2- benzimidazole mercaptan (hereinafter referred to as " BIT ") etc..

As carboxylic acid, particularly preferably using monocarboxylic acid, central preferably use oleic acid, linoleic acid and linoleic acid etc..

Suitably control manufacture method by as above improving electrolysis density or thinning thickness etc., can be in present embodiment Desired orientation is realized in the upper surface of copper foil layer 104.

Additionally, at least lower surface 22 of copper foil layer 104 (is contacted with the one side of insulating barrier 102 used in present embodiment Face) can be in order that the adaptation of copper foil layer 104 and insulating barrier 102 reaches realistic scale or higher above and implement at surface Reason.As the surface treatment for metal forming used in copper foil layer 104, for example can include antirust treatment, chromic acid salt treatment, Silane coupled process in any one or combinations thereof etc..The resin material constituting insulating barrier 102 can be coordinated suitably to select Select arbitrary surfaces processing means.

Above-mentioned antirust treatment for example can pass through any one in the metals such as nickel, tin, zinc, chromium, molybdenum, cobalt or their alloy Form film on metal foil and implement using sputtering, plating, chemical plating.Preferably electroplate from the point of view of in terms of the cost.In order that Metal ion easily separates out it is also possible to add the complexing agents such as the desired amount of citrate, tartrate, sulfamic acid.Plating liquid Generally use in acidic region, carry out at a temperature of room temperature (such as 25 DEG C)～80 DEG C.Plating conditions from current density 0.1～ 10A/dm², 1～60 second conduction time, be preferably in the scope of 1～30 second and suitably select.The amount of antirust treatment metal is according to gold Belong to species and different, be suitably 10～2000 μ g/dm by summation meter².When antirust treatment is blocked up, etching suppression and electricity can be caused Characteristic reduces, and when excessively thin, can constitute the main cause reducing with the peel strength of resin.

Additionally, in the resin combination constituting insulating barrier 102 containing cyanate ester resin when, preferably antirust treatment is using containing The metal having nickel is carried out.Under this combination, the peel strength in resistance to heat deterioration test, moisture-proof deterioration test reduces less, is useful 's.

As above-mentioned chromic acid salt treatment, preferably use the aqueous solution containing hexavalent chromium.Chromic acid salt treatment also can be passed through Simple impregnation process, to carry out, is preferably carried out by cathode treatment.Preferably in sodium dichromate 0.1～50g/L, pH1～13, bath Warm 0～60 DEG C, current density 0.1～5A/dm², electrolysis time carries out under conditions of 0.1～100 second.Weight chromium can also be replaced Sour sodium is carried out using chromic acid or potassium bichromate.Additionally, above-mentioned chromic acid salt treatment is superimposed in fact preferably on above-mentioned antirust treatment Apply.Thus, it is possible to improve the adaptation of insualtion resin composition layer (insulating barrier 102) and metal forming (copper foil layer 104) further.

As silane coupler used in above-mentioned silane coupled process, for example, can use 3- glycidoxypropyl group front three The Silanes such as TMOS, 2- (3,4- epoxycyclohexyl) ethyl trimethoxy silane, 3- aminopropyl trimethoxy Base silane, N-2- (amino-ethyl) 3- TSL 8330, N-2- (amino-ethyl) 3- amino propyl methyl diformazan The amino-functional silane such as TMOS, vinyltrimethoxy silane, ethenylphenyl trimethoxy silane, vinyl three The alkene functional silanes such as (2- methoxy ethoxy) silane, the acrylic compounds official such as 3- acryloxypropyl trimethoxy silane Energy property silane, the methacrylic functional silanes such as 3- methacryloxypropyl trimethoxy silane, 3- mercaptopropyi Mercaptofunctional silane such as trimethoxy silane etc..These can be used alone it is also possible to mix multiple uses.These coupling agents It is dissolved in water equal solvent with the concentration of 0.1～15g/L and uses, by being coated with resulting solution at a temperature of room temperature～50 DEG C Or electro-deposition makes silane coupler adsorb on metal foil in metal forming.These silane couplers by with metal foil surface The hydroxyl of antirust treatment metal carries out condensation bonding and forms overlay film on metal foil.By heating, purple after silane coupled process Outside line irradiate etc. and make described bonding stabilisation.In heating, for example preferably the temperature at 100～200 DEG C carries out 2～60 The drying of second.Ultraviolet irradiates preferably in such as wavelength 200～400nm, 200～2500mJ/cm²Scope carry out.Additionally, silicon The outermost layer of alkane coupling processing preferred pair metal forming is carried out.Contain cyanic acid in the insualtion resin composition constituting insulating barrier 102 During ester resin, preferably processed with the coupling agent of amino silicone alkanes.This group is combined in heat-resisting deterioration test, in moisture-proof deterioration test Peel strength reduce few, be useful.

Additionally, as silane coupled process used in silane coupler, preferably by preferably 60～200 DEG C, more excellent Select 80～150 DEG C of heating that the material of chemical reaction occurs with the insualtion resin composition constituting insulating barrier 102.Thus, on There is chemical reaction with the functional group of silane coupler in the functional group stating in insualtion resin composition, it is possible to obtain more excellent is close Conjunction property.For example, for the insualtion resin composition containing epoxy radicals, preferably use silane coupled containing amino-functional silane Agent.This is because, epoxy radicals and amino easily form firm chemical bond because of heat, this key is extremely steady with respect to heat, moisture Fixed.As the combination being thusly-formed chemical bond, can exemplify：Epoxy radicals-amino, epoxy radicals-epoxy radicals, epoxy radicals-sulfydryl, Epoxy radicals-hydroxyl, epoxy radicals-carboxyl, epoxy radicals-cyanate radical, amino-hydroxy, amino-carboxyl, amino-cyanate radical etc..

Additionally, as the insulating resin of insualtion resin composition used in present embodiment, preferably using at normal temperatures For the epoxy resin of liquid, in the case of being somebody's turn to do, because viscosity during melting is greatly reduced, therefore the wetability at bonding interface carries Height, becomes to be susceptible to the chemical reaction of epoxy resin and silane coupler, result can obtain firm peel strength.Concrete and Speech, the preferably bisphenol A type epoxy resin of epoxide equivalent 200 about, bisphenol f type epoxy resin, phenol novolak-type epoxy tree Fat.

Additionally, when insualtion resin composition contains curing agent, as curing agent, particularly preferably using heat-curing type potential Property curing agent.That is, when the functional group of the functional group in insualtion resin composition and silane coupler occurs chemical reaction, preferably select Selecting curing agent makes the functional group in insualtion resin composition be less than insulation tree with the reaction temperature of the functional group of silane coupler Oil/fat composition proceeds by the temperature of curing reaction.Thus, preferentially and optionally carry out the sense in insualtion resin composition Roll into a ball the reaction with the functional group of silane coupler, metal forming (copper foil layer 104) and insualtion resin composition layer (insulating barrier 102) Adaptation improves further.As the thermohardening type potentiality curing agent for the insualtion resin composition containing epoxy resin, For example can include：Solid dispersion-the heating for dissolving such as dicyandiamide, dihydrazide compound, imidazolium compounds, amine-epoxy adduct Type curing agent, urea compounds, salt, boron chloride amine salt, block carboxylic acid compound isoreactivity group block type Curing agent.

More than, make the prepreg containing insualtion resin composition and the very thin copper with carrier foils by using preceding method Layers of foil folds integration, can obtain the copper clad laminate 10 with carrier foils as shown in (a) of Fig. 1.Then, as (b) institute of Fig. 1 Show, by peeling off carrier layers of foil 106, can get the copper clad laminate 100 on the two sides of insulating barrier 102 with copper foil layer 104.Need It is noted that being not limited to which, copper foil layer 104 is formed at least one side of insulating barrier 102, furthermore, it is possible to shape Become in the whole face of insulating barrier 102 or a part.Additionally, the copper foil layer 104 of present embodiment preferably has main part and roughening Foot divides.

Here, being described in detail to laminate (copper clad laminate 100).

Copper foil layer 104 (thin layer Copper Foil) etch-rate subject to the foregoing is 0.68 μm/more than min and 1.25 μm/min Hereinafter, more preferably 0.68 μm/more than min and 1.24 μm/below min, more preferably 0.69 μm/more than min and 1.23 μ Below m/min.The etch-rate of copper foil layer 104 recited herein only refers in particular to the etch-rate of main part.

In the present embodiment, it is not less than lower limit by making the etch-rate of copper foil layer 104, copper foil layer can be reduced 104 etch residue, and it is good to enable to wiring shape.Additionally, being not higher than higher limit by making the etch-rate of Copper Foil, The side wall in copper foil layer 104 can be suppressed to form breach and connect up the adaptation reduction with insulating barrier.That is, it is being etched to copper The roughening foot timesharing of layers of foil 104, can suppress the main part in copper foil layer 104 to produce abnormal contraction.

In the present embodiment, the etch-rate of the main part of Copper Foil can be measured by the following method.

1. substrate (the copper clad laminate of the ultrathin copper foil eliminating carrier foils (carrier layers of foil 106) will be laminated with two sides 100) it is cut into 40mm × 80mm and obtain sample strip.For sample strip, read to decimal point 2 with slide measure, calculate sample The piece area of product piece.

2. 80 DEG C of dried process of 1 minute × 3 times are carried out to sample strip on horizontal drying line.

3. initial stage weight W0 (including substrate weight) of determination sample piece.

4. prepare etching solution.

4-1：Weigh 60g95% sulfuric acid (and the manufacture of Guang Chun medicine Co., Ltd., superfine), put into the beaker of 1L.

4-2：Pure water is put into beaker used in 4-1 so that total amount is 1000cc.

4-3：Stirred 3 minutes at 30 DEG C ± 1 DEG C with magnetic stirrer.

4-4：Weigh 20cc34.5% aquae hydrogenii dioxidi (Kanto Kagaku K. K.'s manufacture, deer one-level), putting in 4-1 makes Beaker is so that after total amount is 1020cc, stir 3 minutes at 30 DEG C ± 1 DEG C.Thus can get sulfuric acid 55.9g/L and The etching solution of 34.5% aquae hydrogenii dioxidi 19.6cc/L.

5. in above-mentioned etching solution (liquid temperature：30 DEG C ± 1 DEG C, stirring condition：Magnetic stirrer, 250rmp) in impregnated sample piece.

6. weight W1 of a sample strip till the main part of ultrathin copper foil is possible to determine when the sample has been completely etched, was measured every 30 seconds (including substrate weight).

7. calculate etching weight (W0-W1)/(two sides area=m being impregnated²), with X-axis as etching period (second), with Y Axle is etching quality (g/m²) mapping.Between 0～150 second, calculate slope K using least square method.

Provide the conversion formula of the etch-rate of present embodiment.

Etch-rate (μm/min)=K (g/sec m²) ÷ 8.92 (copper proportion g/cm³)×60(sec/min)

The difference of before and after 230 DEG C, the heating of the condition of 1 hour, copper foil layer 104 Vickers hardness is preferably 0Hv Above and below 50Hv, more preferably more than 0Hv below 30Hv.It is not higher than by the difference making the Vickers hardness of copper foil layer 104 Limit value, can suppress the recrystallization making copper foil layer 104 because of heating to carry out, that grain size increases the etch-rate that leads to is slack-off, or The strain accumulation of the thin circuit after can suppressing to etch.Here, the Copper Foil before and after 230 DEG C, the heating of the condition of 1 hour The absolute value of the difference of Vickers hardness of layer 104 preferably employs more than 0Hv and below 50Hv, more preferably adopts more than 0Hv and 30Hv Below.

Additionally, the Vickers hardness after copper foil layer 104 heats at 230 DEG C, 1 hour is preferably more than 180Hv and 240Hv Hereinafter, more preferably more than 185Hv and below 235Hv.Vickers hardness after making heating is more than 180Hv, can suppress So that grain size is increased, the circuit line after etching can be suppressed Property reduce.And the Vickers hardness after making heating is below 240Hv, can suppress that fragility is led because thin copper layer becomes really up to the mark Crack during the process causing, and the cold-resistant thermal impact of the fine wiring being formed can be improved.

In the present embodiment, Vickers hardness for example can be measured by the following method.

That is, the mensure of Vickers hardness, according to JIS Z2244, according to the following steps, is manufactured using Akashi Corporation Micro-hardness tester (model MVK-2H) carry out at 23 DEG C.(1) formation is existed to the ultrathin copper foil with carrier foils for the copper foil layer It is heated in 230 DEG C of baking oven (nitrogen atmosphere) placing 1 hour afterwards, cut into 10 × 10mm square.(2) cutting sample is existed Loading speed 3 μm/second, test load 5gf, formation impression under conditions of 15 seconds retention times, the measurement result according to impression is calculated Go out Vickers hardness.(3) using the mean value of any 5 points recorded of Vickers hardness as the Vickers hardness of present embodiment value.

In addition, as sample, it is possible to use the newly formed pole with carrier foils heated to copper foil layer Thin copper foil.

Additionally, in copper foil layer 104,230 DEG C, 1 hour heat after section grain size be preferably 2.0 μm with Under, more preferably less than 0.5 μm, more preferably more than 0.25 μm and less than 0.5 μm.By making the crystal grain of copper foil layer 104 Degree is not higher than higher limit, and the circuit linearity after can suppressing to etch reduces.Lower limit is not less than by the grain size making copper foil layer 104 Value, the internal stress (tensile stress) before heating after can suppressing thin copper layer plating becomes too high, and suppression is very thin with supporter Copper Foil integrally crimps and in conveyance, rough sledding occurs.

In the present embodiment, the grain size of copper foil layer 104 can be measured by the following method.

That is, the grain size of copper foil layer 104 is measured according to JIS H 0501.Specific step is as follows.First, use FIB (focused ion beam, focused ion bundle) processing unit (plant) is processed to laminate (copper clad laminate 100), shoots SIM (Scanning Ion Microscope) observes photo.According to specified in JIS H0501, the standard photographs of comparison method calculate institute The grain size of the section of photo shooting.

Present embodiment is passed through to reduce the grain size of copper foil layer 104, reduces the change of the Vickers hardness after heating, and carries Etch-rate that high roughening foot divides etc., it is possible to increase the etch-rate of copper foil layer 104 (particularly main part).Additionally, it is thick The etch-rate that change foot divides is generally slow than the etch-rate of main part, for example, can be improved by reducing electrolysis density.

The thickness of copper foil layer 104 arbitrarily can set according to purposes.For example, the thickness of copper foil layer 104 is preferably 0.1 μm Above and less than 5 μm, more preferably more than 1 μm and less than 4 μm.By the thickness that makes copper foil layer 104 within the above range, energy Enough form good fine circuits.

Then, as shown in (c) of Fig. 1, the interlayer that surface from it is through to lower surface is formed on copper clad laminate 100 The through hole 108 connecting.The method forming through hole 108 can use various known means, for example, forming aperture 100 During through hole 108 more than μm, from the perspective of productivity ratio, it is suitably the means using drill bit etc., forming less than 100 μm Through hole 108 when, be suitably the means using Solid State Lasers such as the gas lasers such as carbonic acid gas, excimers, YAG.

Although can also be at least to catalysis core be given on copper foil layer 104, present embodiment is on the whole face of copper foil layer 104 It is catalyzed core with giving on the internal face of through hole 108.As this catalysis core, it is not particularly limited, for example, can use noble metal Ion, palladium colloid.Then, chemical deposit is formed as core using this catalysis core, and in this chemical plating before processing it is also possible to copper Carry out for example utilizing desmear of liquid etc. in layers of foil 104, the surface of through hole 108.At desmear Reason, is not particularly limited, it is possible to use following known methods：Using the oxidizing agent solution with organic matter decomposition etc. Damp process, and the active material (plasma, free radical etc.) strong to the object direct irradiation oxidation as object To remove dry processes such as the plasma method of debris etc..Desmear as damp process is processed, specifically, After the swelling process of enforcement resin surface can be included, it is etched using alkali process, is then neutralized method of process etc..

Then, as shown in (d) of Fig. 1, on the copper foil layer 104 imparting catalysis core and logical on the inwall of through hole 108 Cross the chemical deposit 110 that chemical plating forms thin layer.This chemical deposit 110 is by the copper foil layer on the upper surface of insulating barrier 102 104 are electrically connected with the copper foil layer 104 on its lower surface.Chemical plating can use and for example contain copper sulphate, formalin, complexing The material of agent, NaOH etc..In addition, after chemical plating, the heating being preferable to carry out 100～250 DEG C makes plating film stable Change.From can be formed can suppress aoxidize overlay film in terms of from the point of view of, particularly preferred 120～180 DEG C of heating.Additionally, changing The average thickness learning coating 110 is the thickness that can carry out follow-up plating, and for example, 0.1～1 μm about be enough to.This Outward, conductive paste or insulation paste can be filled in the inside of through hole 108, can be filled with by pattern plating.

Then, as shown in (e) of Fig. 1, the chemical deposit 110 on being arranged on copper foil layer 104 is formed there is regulation The resist layer 112 of patterns of openings.This patterns of openings is equivalent to conductor circuit pattern described later.Therefore, resist layer 112 is to cover copper The mode of the inverter circuit forming region in layers of foil 104 is arranged.In other words, resist layer 112 is not formed on through hole 108 and Copper Foil Conductor circuit forming region on layer 104.As resist layer 112, it is not particularly limited, it is possible to use known material, permissible Using liquid and dry film.When forming fine wiring, as resist layer 112, preferably use photosensitive dry film etc..Want to be formed and resist Erosion layer 112, for example, is laminated photosensitive dry film on chemical deposit 110, inverter circuit forming region is exposed make its light solid Change, with developing solution dissolution, remove unexposed portion.In addition, the cured photosensitive dry film of residual becomes resist layer 112.Against corrosion The suitable thickness adopting with the thickness equal extent or thicker of the conductor (coating 114) of plating afterwards of the thickness of layer 112.

Then, as shown in (a) of Fig. 2, pass through at least in the patterns of openings inside of resist layer 112 and on chemical deposit 110 Electroplating processes form coating 114.Now copper foil layer 104 plays the effect of power supply layer.Present embodiment can be upper in insulating barrier 102 Surface, the inwall of through hole 108 and its lower surface continuously arrange coating 114.As such plating, it is not particularly limited, can With the known method being used using common printed circuit board (PCB), for example, can use in impregnated in the plating liquids such as copper sulphate In the state of to methods such as this plating liquid galvanizations.The thickness of coating 114 is not particularly limited, can make as circuit conductor With, such as preferably 1～100 μm of scope, more preferably 5～50 μm of scope.Coating 114 both can be individual layer, Can have sandwich construction.As the material of coating 114, be not particularly limited, for example can using copper, copper alloy, 42 alloys, Nickel, iron, chromium, tungsten, gold, scolding tin etc..

Then, as shown in (b) of Fig. 2, removed against corrosion using alkaline stripper, sulfuric acid or commercially available anticorrosive additive stripping liquid controlling etc. Layer 112.

Then, as shown in (c) of Fig. 2, remove chemical deposit 110 and the copper foil layer being formed with beyond the region of coating 114 104.The gimmick removing this copper foil layer 104 is for example using soft etching (fast-etching, flash etching) etc..Thus can be with shape Become the pattern of the conductor circuit 118 of copper foil layer 104 and metal level 116 (chemical deposit 110 and coating 114) stacking composition.

Here, etching solution illustrates used in the following soft etching to present embodiment.As etching solution, there is no spy Do not limit, during using the existing etching solution spreading speed limit type, the fluid exchange of the fine fraction of wiring all can become anyway , therefore there is the tendency of circuit formative variation in difference.Therefore, etching solution is preferably reacted using the reaction of copper and etching solution Speed limit and type that non-diffusing speed limit is carried out.If copper is reaction speed limit with the reaction of etching solution, even if strengthening further expanding Dissipate, etch-rate also will not change.That is, the etch-rate at the good position of fluid exchange and the position of difference will not produce difference Different.As this reaction speed limit etching solution, for example, can include with hydrogen peroxide and not contain the acid of halogens as main component Liquid.Due to using hydrogen peroxide as oxidant, therefore pass through to manage its concentration, tight etch-rate control can be carried out System.In addition, if being mixed into halogens in etching solution, then dissolving reaction easily becomes diffusion speed limit.As not halogen-containing acid, Nitric acid, sulfuric acid, organic acid etc. can be used, due to inexpensively and preferably sulfuric acid.And then in sulfuric acid and hydrogen peroxide for mainly becoming Timesharing, in terms of etch-rate, the liquid stability from the point of view of, preferably respective concentration is 5～300g/L, 5～200g/L.For example may be used Include ammonium persulfate, sodium peroxydisulfate, sodium peroxydisulfate class etc..

As engraving method, can adopt in various manners.For example both copper clad laminate 100 can be impregnated in and be contained in beaker Deng in the etching solution in liquid storage container it is also possible to etching solution be coated copper foil layer 104 with spray pattern.

So, by the etch-rate of suitably selected copper foil layer 104, can get the conductor circuit of desired shape 118.Can get the printed circuit board (PCB) 200 being formed with conductor circuit 118 on the two sides of insulating barrier 102 from above.

In addition, as shown in (d-1) of Fig. 2, can be to cover the side with a part for conductor circuit 118 on insulating barrier 102 Formula forms solder mask 120.As solder mask 120, for example can be containing the excellent packing material of insulating properties or base material, using photosensitive The heat-resistant resin compositions such as property resin, curable resin and thermoplastic resin.Then, solder mask 120 can be provided with Form the 1st coating 122 and the 2nd coating 124 further on the conductor circuit 118 of opening portion.Thus metal level 116 can be made More than 2 layers of sandwich construction.As these the 1st coating 122 and the 2nd coating 124, Gold plated Layer can be adopted.As gold-plated side Method, is existing known method, is not particularly limited, for example there are as below methods：0.1～10 μ is carried out on coating 114 M about chemical nickel plating and carry out 0.01～0.5 μm about immersion gold plating after carry out 0.1～2 μm about of chemical gilding. Can get the printed circuit board (PCB) 202 shown in (d-1) of Fig. 2 from above.

Additionally, formation the 1st coating the 122 and the 2nd plating as shown in (d-2) of Fig. 2 it is also possible to around conductor circuit 118 Layer 124 and do not form solder mask 120.As these the 1st coating 122 and the 2nd coating 124, for example, can adopt nickel coating and plating The duplexer of layer gold.Can get the printed circuit board (PCB) 204 shown in (d-2) of Fig. 2 from above.

Furthermore, it is possible to install semiconductor chip (not shown) on these printed circuit board (PCB)s 200,202 and 204 partly be led Body device.

(the 2nd embodiment)

Then, the manufacture method of the printed circuit board (PCB) of the 2nd embodiment is illustrated.

Fig. 3～Fig. 5 is the section view of the step of the manufacturing process of the manufacture method of printed circuit board (PCB) illustrating the 2nd embodiment Figure.The manufacture method of the printed circuit board (PCB) of the 2nd embodiment is, for example,：Using the printed circuit board (PCB) obtaining in the 1st embodiment 200th, 202 and 204 as internal layer circuit substrate, forms lamination layer further on this internal layer circuit substrate.

First, as internal layer circuit substrate, using the printed circuit board (PCB) 200 obtaining in (c) of Fig. 2.To this printed circuit The internal layer circuit (conductor circuit 118) of plate 200 implements roughening treatment.Here, roughening treatment refers to conductor circuit surface is implemented Liquid process and corona treatment etc..As roughening treatment, for example, can use using redox Darkening process, or Processed using the liquid of the known coarsening solution of Sulfuric-acid-hydrogen-peroxide class etc..Thereby, it is possible to improve the layer constituting insulating barrier 130 Between insulating materials and printed circuit board (PCB) 200 conductor circuit 118 adaptation.Additionally, internal layer circuit substrate can also replace the 1st The printed circuit board (PCB) 200 obtaining in embodiment uses and is laminated with prepreg by plated-through-hole method, lamination method etc. or does not contain The common multilayer board of the resin composition layer of base material etc., is not particularly limited.Conductor electricity as internal layer circuit Road floor can be formed by existing known circuit forming method.Additionally, it is also possible to pass through to work in multilayer board Duplexer (being laminated duplexer obtained by multiple prepregs) for its sandwich layer and metal-coated laminated board carry out drill bit processing, laser Processing etc. and form through hole, then, by plating etc., the internal layer circuit on two sides is electrically connected.

Then, as shown in (a) of Fig. 3, it is respectively configured in the both sides of the printed circuit board (PCB) 200 on conductor circuit surface roughening Insulating barrier 130 (prepreg) and the copper foil layer with carrier layers of foil 107 105 (with the ultrathin copper foil of carrier foils).Then, as Fig. 3 (b) shown in, by the duplexer being overlapped into them is carried out heat pressurized treatments and form multilayer laminate.Then, such as Shown in (c) of Fig. 3, peel off and remove carrier layers of foil 107.

Then, as shown in (d) of Fig. 3, remove insulating barrier 130 and a part for copper foil layer 105 forms hole 109.In hole 109 Bottom surface, the part on the surface of conductor circuit 118 exposes.As the gimmick forming this hole 109, it is not particularly limited, for example Following gimmicks etc. can be used：Form aperture 100 using Solid State Lasers such as the gas lasers such as carbonic acid gas, excimers, YAG Blind via hole (blind via hole) below μm.In addition, though hole 109 is expressed as non-through hole in (d) of Fig. 3, but It can be through hole.Additionally, when being through hole, it is possible to use laser irradiates and is formed, it is possible to use drill bit processing machine is formed.

Then, as Fig. 4 (a) shown in, aforementioned impart catalysis core conductor circuit 118 on, on the inwall in hole 109 and The lamellar chemical deposit of shape 111 on copper foil layer 105.Chemical deposit 111 and afore mentioned chemical coating 110 equally operate formation.? Before this chemical plating, as it was previously stated, the desmears such as the desmear using liquid can be carried out processing.Additionally, changing The thickness learning coating 110 is the thickness that can carry out follow-up plating, is 0.1～1 μm about and be enough to.Additionally, hole 109 Conductive paste or insulation paste can be filled in the inside of (blind via hole), can be filled with by pattern plating.

Then, the resist layer 113 with the patterns of openings being equivalent to conductor circuit pattern is formed on chemical deposit 110. In other words, shelter inverter circuit forming portion by forming resist layer 113.As this resist layer 113, it is possible to use with aforementioned resist layer 112 same layers.The suitable thickness equal extent or thicker adopting with the conductor circuit of plating afterwards of the thickness of resist layer 113 Thickness.

Then, as shown in (c) of Fig. 4, it is internally formed coating 132 in the patterns of openings of resist layer 113.This coating 132 was both Can be formed on the conductor circuit 118 within hole 109 it is also possible to be formed at the chemical deposit 111 within above-mentioned patterns of openings On.The plating forming coating 132 can use the gimmick same with aforementioned coating 114.The thickness of this coating 132 can be used as electricity Road conductor uses, such as preferably 1～100 μm of scope, more preferably 5～50 μm of scope.

Then, as shown in (a) of Fig. 5, equally operate, with aforementioned resist layer 112, the stripping carrying out resist layer 113.Then, As shown in (b) of Fig. 5, remove copper foil layer 105 and chemical deposit with aforementioned copper foil layer 104 again by soft etching (fast-etching) 111.The conductor circuit pattern being made up of copper foil layer 105, chemical deposit 111 and coating 132 thus can be formed.Additionally, leading The path being connected electrically and pad can be formed by coating 132 on body circuit 118.Can get printed circuit board (PCB) 201 from above.

In addition, as shown in (c-1) of Fig. 5, can be on insulating barrier 130, on the coating 132 of conductor circuit pattern and pad A part for coating 132 on formed solder mask 121.As solder mask 121, it is possible to use same with aforementioned solder mask 120 Layer.Then, can be formed further on the coating 132 of the opening portion being provided with solder mask 121 for example by nickel coating and gold-plated The 1st coating 123 and the 2nd coating 125 that layer is constituted.Can get the printed circuit board (PCB) 203 shown in (c-1) of Fig. 5 from above.

Additionally, as shown in (c-2) of Fig. 5, surrounding's formation the aforementioned 1st that can be around conductor circuit pattern with pad Coating 123 and the 2nd coating 125 and do not form solder mask 121.Can get the printed circuit board (PCB) 205 shown in (c-2) of Fig. 5 from above. Also effect in a same manner as in the first embodiment can be obtained in the 2nd embodiment.

(the 3rd embodiment)

Then, the manufacturing process of the printed circuit board (PCB) 101 of the 3rd embodiment is described in detail.

As shown in (a) of Fig. 6, prepare the copper clad laminate 10 with carrier foils.Then, as shown in (b) of Fig. 6, shelled From etc., carrier foils layer 106 is removed from the copper clad laminate 10 with carrier foils.Then, as shown in (c) of Fig. 6, in the copper staying The resist layer 112 of the patterns of openings with regulation is formed on layers of foil 104.With copper foil layer 104 in the patterns of openings of resist layer 112 Above coating (metal level 115) ((d) of Fig. 6) is formed by plating.Then, as shown in (e) of Fig. 6, remove resist layer 112.Thus can on copper foil layer 104 metal level 115 of selectively formed regulation pattern.Then, as (f) institute of Fig. 6 Show, remove the copper foil layer 104 in the region not being covered, typically with metal layers 115 coverings by for example soft etching.The removal work of this copper foil layer 104 The pattern of conductor circuit 119 after sequence, can be formed by the copper foil layer 104 staying and metal level 115.Can be obtained by above operation Printed circuit board (PCB) 101 to the 3rd embodiment.Also effect in a same manner as in the first embodiment can be obtained in the 3rd embodiment.

(the 4th embodiment)

Then, the manufacturing process of the printed circuit board (PCB) 101 of the 4th embodiment is described in detail.

First, as shown in (a) of Fig. 7, prepare the copper clad laminate 10 with carrier foils.In the copper clad laminate with carrier foils In 10, all it is pasted with carrier layers of foil 106 together with copper foil layer 104 on the two sides of insulating barrier 102.Then, as shown in (b) of Fig. 7, Peel off carrier layers of foil 106 from the copper clad laminate 10 with carrier foils.Then, as shown in (c) of Fig. 7, in the whole face of copper foil layer 104 Above metal level 115 (coating) is formed by plating.Then, as shown in (d) of Fig. 7, shape on plane metal level 115 Become to have the resist layer 112 of the patterns of openings of regulation.Then, as shown in (e) of Fig. 7, remove this resist layer by for example etching Metal level 115 in 112 patterns of openings and copper foil layer 104.Then, as shown in (f) of Fig. 7, remove resist layer 112.Thus The pattern of the conductor circuit 119 being made up of copper foil layer 104 and metal level 115 can be formed.Can get the 4th by above operation real Apply the printed circuit board (PCB) 101 of mode.Also effect in a same manner as in the first embodiment is can get in the 4th embodiment.

As above, according to present embodiment it is provided that the ultrathin copper foil with carrier foils fine circuits processing, fine circuits Shape and the excellent manufacture method of printed circuit board (PCB) of insulating reliability and this printed circuit board (PCB).

The manufacture method of the printed circuit board (PCB) of present embodiment can be applied not only to the two of use in printed circuit board substrate Face forms the situation of conductor circuit layers, can also be applied to only form conductor circuit layers in the one side of use in printed circuit board substrate Situation.Further, it is also possible to be applied to as shown in (c) of Fig. 2 using two-face printing circuit board as the 3rd embodiment party of inner layer circuit board The situation of the multilayer board of formula.Therefore, by the manufacture method of the printed circuit board (PCB) of present embodiment, list can be manufactured Any one in face printed circuit board (PCB), two-face printing circuit board and multilayer board.

Embodiment

Hereinafter manufacture the ultrathin copper foil with carrier foils and the copper clad laminate using this Copper Foil of the present invention, to the present invention's The embodiment of the manufacture method of printed circuit board (PCB) illustrates.Here by carrier foils using the situation of electrolytic copper foil centered on enter Row explanation.Based on embodiment and comparative example, the present invention is described in detail, but the present invention is not limited to this.

In the case of especially recording, " part " expression " weight portion " of below recording, " % " expression " weight % ".

1. the manufacture of the ultrathin copper foil with carrier foils

Manufacture to the ultrathin copper foil with carrier foils illustrates below.

(Production Example 1)

As carrier foils (support metal forming), peel ply and pole are sequentially formed on the glassy surface of the electrolytic copper foil of 18 μ m-thick Thin copper foil layer.Manufacturing condition is as follows.

First, by carrier foils in acid elution groove (sulfuric acid：In 30g/L), dipping removes the oil on surface, oxidation overlay film for 5 seconds Deng.Then, using formation groove (the nickel sulfate hexahydrate compound of peel ply：30g/L, sodium molybdate dihydrate：3g/L, citric acid three Sodium dihydrate：30 DEG C of 30g/L, liquid temperature) with current density 20A/dm²Electrolysis is processed 5 seconds, is formed on the glassy surface of carrier foils Peel ply.Then, main part (hereinafter referred to as main body layers of copper) is formed on peel ply.Main body layers of copper is formed as follows.First, make With plating bath (cupric pyrophosphate：80g/L, potassium pyrophosphate：320g/L, ammoniacal liquor：40 DEG C of 2ml/L, liquid temperature) with current density 2.0A/dm² Electrolysis is processed 15 seconds, forms the 1st main body layers of copper on peel ply.Then, using plating bath (copper sulfate pentahydrate：160g/L, sulphur Acid：100g/L, gelatin (Nippi, Inc. manufacture, trade name PBH, weight average molecular weight (MW) 5000)：15ppm, chloride ion： 40 DEG C of 5ppm, liquid temperature) with current density 3.5A/dm²Electrolysis is processed 150 seconds, forms the 2nd main body layers of copper in the 1st main body layers of copper. It is consequently formed main body layers of copper.Then, using plating bath (copper sulfate pentahydrate：150g/L, sulfuric acid：30 DEG C of 100g/L, liquid temperature) with Current density 30A/dm²Electrolysis processes 3 seconds afterwards with current density 5A/dm²Electrolysis is processed 70 seconds, is formed thick in main body layers of copper Change foot and divide (being hereinafter referred to as roughened layers of copper).Then, using antirust treatment groove (sodium dichromate dihydrate：3.5g/L, liquid temperature 28 DEG C) with current density 0.5A/dm²Electrolysis processes and carries out antirust treatment in 2.5 seconds.Then, it is immersed in N- phenyl amino propyl three It is surface-treated in the aqueous solution of methoxy silane 1wt%.Then, it is dried 10 minutes at 80 DEG C.It is consequently formed Production Example 1 The ultrathin copper foil with carrier foils.

(Production Example 2)

It is similarly formed the ultrathin copper foil with carrier foils with Production Example 1 in addition to the manufacturing condition of main body layers of copper.

In this Production Example, main body layers of copper is formed as follows.First, using plating bath (copper sulfate pentahydrate：30g/L, lemon Sour trisodium dihydrate：40 DEG C of 40g/L, liquid temperature) with current density 2.0A/dm²Electrolysis is processed 15 seconds, forms the on peel ply 1 main body layers of copper.Then, using plating bath (copper sulfate pentahydrate：160g/L, sulfuric acid：100g/L, gelatin (Nippi, Inc. system Make, trade name PBF, weight average molecular weight (MW) 3000)：20ppm, chloride ion：40 DEG C of 5ppm, liquid temperature) with current density 3.5A/dm²Electrolysis is processed 150 seconds, forms the 2nd main body layers of copper in the 1st main body layers of copper.It is consequently formed main body layers of copper.

(Production Example 3)

In this Production Example, main body layers of copper is formed as follows.First, using plating bath (copper sulfate pentahydrate：30g/L, lemon Sour trisodium dihydrate：40 DEG C of 40g/L, liquid temperature) with current density 2.0A/dm²Electrolysis is processed 15 seconds, forms the on peel ply 1 main body layers of copper.Then, using plating bath (copper sulfate pentahydrate：160g/L, sulfuric acid：100g/L, gelatin (Nippi, Inc. system Make, trade name PA-10, weight average molecular weight (MW) 1000)：25ppm, chloride ion：40 DEG C of 5ppm, liquid temperature) with current density 3.5A/dm²Electrolysis is processed 150 seconds, forms the 2nd main body layers of copper in the 1st main body layers of copper.It is consequently formed main body layers of copper.

(Production Example 4)

In this Production Example, main body layers of copper is formed as follows.First, using plating bath (copper sulfate pentahydrate：30g/L, sulfuric acid Nickel hexahydrate：5g/L, citrate trisodium dihydrate：40 DEG C of 40g/L, liquid temperature) with current density 2.0A/dm²Electrolysis is processed 15 seconds, the 1st main body layers of copper is formed on peel ply.Then, using plating bath (copper sulfate pentahydrate：160g/L, sulfuric acid：100g/ L, gelatin (Nippi, Inc. manufacture, trade name PA-10, weight average molecular weight (MW) 1000)：35ppm, chloride ion：5ppm、 40 DEG C of liquid temperature) with current density 3.5A/dm²Electrolysis is processed 150 seconds, forms the 2nd main body layers of copper in the 1st main body layers of copper.Thus Form main body layers of copper.

(Production Example 5)

In this Production Example, main body layers of copper is formed as follows.First, using plating bath (copper sulfate pentahydrate：30g/L, sulfuric acid Nickel hexahydrate：5g/L, citrate trisodium dihydrate：40 DEG C of 40g/L, liquid temperature) with current density 2.0A/dm²Electrolysis is processed 15 seconds, the 1st main body layers of copper is formed on peel ply.Then, using plating bath (copper sulfate pentahydrate：160g/L, sulfuric acid：100g/ L, gelatin (Nippi, Inc. manufacture, trade name PBH, weight average molecular weight (MW) 5000)：30ppm, chloride ion：5ppm, liquid 40 DEG C of temperature) with current density 3.5A/dm²Electrolysis is processed 150 seconds, forms the 2nd main body layers of copper in the 1st main body layers of copper.By this shape Become main body layers of copper.

(Production Example 6)

First, by carrier foils in acid elution groove (sulfuric acid：In 50g/L), dipping removes the oil on surface, oxidation overlay film for 15 seconds Deng.Then, in formation groove (the carboxyl benzotriazole solution of peel ply：40 DEG C of reagent, liquid temperature) in dipping 15 seconds, in carrier foils Peel ply is formed on glossy surface.Then, using plating bath (copper sulfate pentahydrate：150g/L, sulfuric acid：150g/L, gelatin (Nippi, Inc. manufacture, trade name PBH, weight average molecular weight (MW) 5000)：15ppm, chloride ion：5ppm, liquid temperature 40 DEG C) with current density 10A/dm²Electrolysis is processed 180 seconds, forms main body layers of copper on peel ply.Then, using plating bath (copper sulphate Pentahydrate：150g/L, sulfuric acid：30 DEG C of 100g/L, liquid temperature) with current density 30A/dm²Electrolysis process 3 seconds close with electric current afterwards Degree 5A/dm²Electrolysis is processed 70 seconds, forms roughening layers of copper in main body layers of copper.Then, using antirust treatment groove (sodium dichromate two Hydrate：28 DEG C of 3.5g/L, liquid temperature) with current density 0.5A/dm²Electrolysis processes and carries out antirust treatment in 2.5 seconds.Then, impregnate It is surface-treated in the aqueous solution of N- phenyl amino propyl trimethoxy silane 1wt%.Then, it is dried 10 points at 80 DEG C Clock.It is consequently formed the ultrathin copper foil with carrier foils of Production Example 6.

(Production Example 7)

In this Production Example, main body layers of copper is formed as follows.First, using plating bath (copper sulfate pentahydrate：30g/L, lemon Sour trisodium dihydrate：40 DEG C of 40g/L, liquid temperature) with current density 2.0A/dm²Electrolysis is processed 15 seconds, forms the on peel ply 1 main body layers of copper.Then, using plating bath (copper sulfate pentahydrate：160g/L, sulfuric acid：100g/L, chloride ion：5ppm, liquid 40 DEG C of temperature) with current density 3.5A/dm²Electrolysis is processed 150 seconds, forms the 2nd main body layers of copper in the 1st main body layers of copper.By this shape Become main body layers of copper.

(Production Example 8)

In this Production Example, main body layers of copper is formed as follows.First, using plating bath (copper sulfate pentahydrate：30g/L, lemon Sour trisodium dihydrate：40 DEG C of 40g/L, liquid temperature) with current density 2.0A/dm²Electrolysis is processed 15 seconds, forms the on peel ply 1 main body layers of copper.Then, using plating bath (copper sulfate pentahydrate：160g/L, sulfuric acid：100g/L, gelatin (Nippi, Inc. system Make, trade name PBF, weight average molecular weight (MW) 3000)：40 DEG C of 20ppm, liquid temperature) with current density 3.5A/dm²Electrolysis process 150 Second, the 2nd main body layers of copper is formed on the 1st main body layers of copper.It is consequently formed main body layers of copper.

(Production Example 9)

In this Production Example, main body layers of copper is formed as follows.First, using plating bath (copper sulfate pentahydrate：30g/L, lemon Sour trisodium dihydrate：40 DEG C of 40g/L, liquid temperature) with current density 2.0A/dm²Electrolysis is processed 15 seconds, forms the on peel ply 1 main body layers of copper.Then, using plating bath (copper sulfate pentahydrate：160g/L, sulfuric acid：100g/L, gelatin (Nippi, Inc. system Make, trade name AP, weight average molecular weight (MW) 8000)：30ppm, chloride ion：40 DEG C of 5ppm, liquid temperature) with current density 3.5A/dm²Electrolysis is processed 150 seconds, forms the 2nd main body layers of copper in the 1st main body layers of copper.It is consequently formed main body layers of copper.

(Production Example 10)

In this Production Example, main body layers of copper is formed as follows.First, using plating bath (copper sulfate pentahydrate：30g/L, lemon Sour trisodium dihydrate：40 DEG C of 40g/L, liquid temperature) with current density 2.0A/dm²Electrolysis is processed 15 seconds, forms the on peel ply 1 main body layers of copper.Then, using plating bath (copper sulfate pentahydrate：160g/L, sulfuric acid：100g/L, gelatin (Nippi, Inc. system Make, trade name PBF, weight average molecular weight (MW) 3000)：5ppm, chloride ion：40 DEG C of 5ppm, liquid temperature) with current density 3.5A/dm²Electrolysis is processed 150 seconds, forms the 2nd main body layers of copper in the 1st main body layers of copper.It is consequently formed main body layers of copper.

2. the manufacture of resin varnish

Dissolve in MEK and mix naphthalene ether type epoxy (Dainippon Ink Chemicals's manufacture, HP-6000) 20 weight portions, naphthalene Type epoxy resin (Dainippon Ink Chemicals manufacture, HP4032D) 5 weight portions, cyanate ester resin (Lonza Japan Ltd. manufactures, PT-30) 17 weight portions, bimaleimide resin (K.I Kasei Co., Ltd. manufacture, BMI-70) 7.5 weight %, dioxy Silicon carbide particle (Tokuyama Corp manufactures NSS-5N, average grain diameter 70nm) 7 weight portions, spherical silicon dioxide (Admatechs Co., Ltd. manufacture SO-25R, 0.5 μm of average grain diameter) 35.5 weight portions, organic silicon granule (Shin-Etsu Chemial Co., Ltd's system Make, KMP600,5 μm of average grain diameter) 7.5 weight portions, zinc octoate 0.01 weight portion, epoxy silane (SHIN-ETSU HANTOTAI's chemical industry strain formula meeting Society's manufacture, KBM-403E) 0.5 weight portion.Then, being adjusted to nonvolatile component using high-speed stirring apparatus stirring is 70 weights Amount %, prepared resin varnish.

3. the manufacture of prepreg

Use glass woven fabric (Nitto Boseki Co. Ltd's manufacture, T glass woven fabric, WTX-1078, basic weight as fiber base material 48g/m², 45 μm of thickness), the aforementioned prepared resin varnish of dip coated, in 180 DEG C of heating furnace be dried 2 minutes, obtain thickness The prepreg of degree 0.05mm.

4. the manufacture of copper clad laminate

4 aforementioned prepregs obtaining of stacking, in the ultrathin copper foil (2 μm) of its two sides laminated belt carrier foils, by Carry out 60 minutes (heating 60 minutes after reaching 200 DEG C) heating press moldings at pressure 3MPa, 200 DEG C of temperature, obtain on two sides There is the copper clad laminate of Copper Foil.In addition, such as table 1 and the table of the ultrathin copper foil with carrier foils used in each embodiment and comparative example Described in 2.

5. evaluate

Using the ultrathin copper foil with carrier foils obtaining in each embodiment and comparative example, carry out following evaluation.By scoring item Mesh is given in the lump with content, and acquired results are shown in Tables 1 and 2.

(1) mensure of Vickers hardness

The mensure of Vickers hardness is according to JIS Z2244, according to the following steps, micro- using Akashi Corporation manufacture Little hardometer (model MVK-2H) is carried out at 23 DEG C.As the sample of normality, using the newly formed band carrier to main body layers of copper The ultrathin copper foil of paper tinsel.Additionally, as the sample after heat treatment, using placement 1 in the baking oven (nitrogen atmosphere) being heated to 230 DEG C Formation after hour is to the ultrathin copper foil with carrier foils for the main body layers of copper.With regard to condition determination, to cutting sample in load speed Degree 3 μm/second, test load 5gf, formation impression under conditions of 15 seconds retention times, calculate Vickers according to the measurement result of impression Hardness, using the mean value of any 5 points recorded of Vickers hardness as this condition value.

(2) etch-rate (V1, V2)

1. the substrate being laminated with the ultrathin copper foil eliminating carrier foils on two sides is cut into 40mm × 80mm and obtains sample Piece.For sample strip, read to decimal point 2 with slide measure, calculate the piece area of sample strip.

4. prepare etching solution.

4-2：Pure water is put into beaker used in 4-1 so that total amount is 1000cc.

4-3：Stirred 3 minutes at 30 DEG C ± 1 DEG C with magnetic stirrer.

6. weight W1 of a sample strip till the body layer of ultrathin copper foil is possible to determine when the sample has been completely etched, was measured every 30 seconds (including substrate weight).

7. calculate etching weight (W0-W1)/(two sides area=m being impregnated²), with X-axis as etching period (second), with Y Axle is etching quality (g/m²) mapping.According to for the slope K 1 calculating using least square method between 0～150 second, calculate master Etch-rate V1 (μm/min)=K1 (the g/sec m of body layers of copper²) ÷ 8.92 (copper proportion g/cm³)×60(sec/min).

8., then, till the roughening layers of copper of ultrathin copper foil is possible to determine when the sample has been completely etched, measured a sample strip every 10 seconds Weight W2 (including substrate weight).

9. calculate etching weight (W0-W2)/(two sides area=m being impregnated²), with X-axis as etching period (second), with Y Axle is etching quality (g/m²) mapping.According to for the slope K 2 calculating using least square method between 0～30 second, calculate roughening Etch-rate V2 (μm/min)=K2 (the g/sec m of layers of copper²) ÷ 8.92 (copper proportion g/cm³)×60(sec/min).

(3) concavo-convex evaluation method

Using the SEM image (2000 times) observing the printed circuit board (PCB) gained obtaining in (4) described later from surface, to cloth Copper residual between line carries out binaryzation, and (Media Cybernetics company manufactures, image processing software；Image Pro Prus Ver5.1) calculate residual copper rate.

The original binaryzation of original binaryzation

	Embodiment 1	Comparative example 1
			Area (μm²)	0.7	43.4

Each symbol in Tables 1 and 2 is as follows.

◎：Less than 2

○：More than 2 and less than 10

×：More than 10

(4) insulating properties between fine rule

1. pair it is laminated with the surface of the substrate of the ultrathin copper foil eliminating carrier foils on two sides, with chemical grinding liquid (Mitsubishi Gas KCC manufactures, trade name：CPB-60) carry out soft etching at 5 seconds, 23 DEG C and remove cupric oxide.Then, utilize Hot roll laminator is by the UV light sensitivity dry film of 25 μm of thickness (Asahi Kasei Corporation manufactures, SUNFORT UFG-255) patch It is combined on substrate.Then, carry out describing have the glass mask of the pattern that minimum feature/distance between centers of tracks is 20/20 μm (TOPIC Co., Ltd. manufacture) position alignment.Then, to above-mentioned dry film, pass through exposure device (little wild survey device strain formula using above-mentioned glass mask Commercial firm EV-0800) it is exposed, and developed with aqueous sodium carbonate.It is consequently formed Etching mask.

2., then, using ultrathin copper foil layer as power supply layer electrode, carry out 3A/dm², electro-coppering (the open country pharmacy difficult to understand of 25 minutes Co., Ltd. manufactures 81-HL), form the pattern of the thin copper film of about 20 μm of thickness.Then, using stripping machine, using MEA Solution (Mitsubishi Gas Chemical Co., Ltd manufactures R-100) peels off aforementioned Etching mask.

3. then, the ultrathin copper foil as power supply layer is removed by fast-etching (with etch-rate identical etching solution) Layer, forms L/S=20/20 μm of pattern (pattern-like etching).Thus obtain printed circuit board (PCB).

4., as test specimen, using replacing solder resist stacking insulating resin sheet, (Sumitomo Bakelite Co manufactures, BLA- 3700GS) solidify, at 220 DEG C of temperature, the sample obtaining, comment under conditions of 130 DEG C of temperature, humidity 85%, applied voltage 10V Insulaion resistance under the continuous wet environment of valency.In addition, resistance value 10⁶Below Ω is evaluated as fault.

Symbol is as follows.

◎：More than 300 hours fault-free

○：150～broke down less than 300 hours

×：Broke down less than 150 hours

(5) wiring shape (or circuit linearity)

1. sample is using the printed circuit board (PCB) obtaining in above-mentioned (4).

2. the profile of circuit bottom when pair observing the circuit after etching using microscope from surface is evaluated.This Outward, to using micro- sem observation etching after circuit section when wiring shape evaluate.

Symbol is as follows.

◎：When surface is observed, the profile of circuit bottom appears as straight line.And the bottom of bottom does not have in section Expand outwardly.

○：When surface is observed, the profile of circuit bottom appears as straight line.And the bottom of bottom in section Little.

×：When surface is observed, the profile of circuit bottom appears as curvilinear part.And bottom in section The bottom in portion is big.

(6) grain size (μm)

Grain size is measured according to JIS H0501.Step is as follows.

1. pair it is laminated with the substrate of the ultrathin copper foil eliminating carrier foils on two sides, using FIB (focused ion bundle) processing After device is processed, shoots SIM (Scanning Ion Microscope) and observe photo.

2. the standard photographs of comparison method according to specified in JIS H0501 calculate captured by the section of photo crystal grain Degree.It should be noted that because the accompanying drawing of this standard is only given to grain size 0.010mm obtaining with 75 times of observations, therefore pouring Drink multiplying power when most similar figure and observation and calculate.

[table 1]

[table 2]

In addition, certainly above-mentioned embodiment and multiple variation can be combined in the range of its content is not runed counter to. Additionally, being illustrated to the structure in each portion etc. in above-mentioned embodiment and variation, and its structure etc. can meet Carry out various changes in the scope of the present invention.

The application advocate by March 16th, 2012 submit to Japanese patent application laid be willing to 2012-059742 based on excellent First weigh, the disclosure of which is fully incorporated so far.

Claims

1. a kind of laminate, it possesses insulating barrier and is located at the Copper Foil of at least one side of described insulating barrier, and it is used for by etching Described Copper Foil and formed conductor circuit from obtained from device mounting board,

Described etching be containing sulfuric acid 55.9g/L and 34.5% aquae hydrogenii dioxidi 19.6cc/L and liquid temperature be 30 DEG C ± 1 DEG C Impregnate described laminate in the etching solution of sulfuric acid/hydroperoxide kind, the etch-rate of described Copper Foil be 0.68 μm/more than min and 1.25 μm/below min,

The Vickers hardness of the described Copper Foil after heating at 230 DEG C, 1 hour is more than 180Hv and below 240Hv.

2. laminate according to claim 1, wherein, the Vickers of the described Copper Foil before and after the heating of following condition The difference of hardness is more than 0Hv and below 50Hv,

Condition：Heating-up temperature is 230 DEG C, and the heat time is 1 hour.

3. laminate according to claim 1 and 2, wherein, the thickness of described Copper Foil is more than 0.1 μm and less than 5 μm.

4. laminate according to claim 1, wherein, the section of the described Copper Foil after heating at 230 DEG C, 1 hour Grain size is less than 2.0 μm.

5. a kind of manufacture method of printed circuit board (PCB), the method includes：

Prepare the operation possessing insulating barrier and the laminate of the Copper Foil of at least one side positioned at described insulating barrier, and

The operation of conductor circuit is formed by Copper Foil described in selective removal,

Described laminate is the laminate any one of Claims 1 to 4.