CN104170532A - Manufacturing method for laminated board and printed wiring board - Google Patents

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

The manufacture method of laminated sheet and printed circuit board (PCB)

Technical field

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

Background technology

The requirements such as multifunction along with electronic equipment, the high-density integrated of electronic unit, also have high-density installation etc. constantly to advance, small-sized slimming, densification and the multiple stratifications of further having advanced compared with the past such as printed circuit board (PCB) of the corresponding high-density installation of using in these.

As efficiently form the method for the conductor circuit layer that pattern precision is high with high density on the substrate of printed circuit board (PCB), come into effect semi-additive process.The manufacture method of the printed circuit board (PCB) of use semi-additive process is for example on the books in patent documentation 1 and patent documentation 2.

In patent documentation 1 and 2 manufacture methods of recording, first, prepare to be covered with in the one side of insulating barrier the laminated sheet of Copper Foil, on this laminated sheet, form corrosion-resisting pattern.Then, in the peristome of corrosion-resisting pattern, fill coating.Then, remove corrosion-resisting pattern.Afterwards, using the pattern of coating as mask, the Copper Foil of lower floor is carried out to etching, form thus the conductor circuit being formed by coating and Copper Foil.

Prior art document

Patent documentation

Patent documentation 1: TOHKEMY 2003-69218 communique

Patent documentation 2: TOHKEMY 2003-60341 communique

Summary of the invention

In the manufacture process of patent documentation 1 and 2, can partly produce at the formed micro concavo-convex in the surface of insulating barrier the residue of Copper Foil.Along with the propelling of miniaturization, the etch residue that remains in the Copper Foil between conductor circuit can form the reason of the short circuits such as defective insulation of conductor circuit.Therefore, preferably the etch residue of the lip-deep Copper Foil of insulating barrier is removed.

Want to remove the etch residue of Copper Foil, need the surface of over etching insulating barrier.Yet during over etching insulating barrier, conductor circuit also can be by over etching, formation that therefore conductor circuit occur is sometimes abnormal, the disconnection of conductor circuit, fly out.Being difficult to maintain wiring shape when implementing over etching is desired shape.

As mentioned above, in the laminated sheet of patent documentation 1 and 2, there is room for improvement with the balance aspect that maintains wiring shape in the etch residue that reduces Copper Foil.

According to the present invention, a kind of laminated sheet is provided,

Described laminated sheet possesses insulating barrier and is positioned at least Copper Foil of one side of aforementioned dielectric layer, thereby it is for forming by the aforementioned Copper Foil of etching the device mounting board that conductor circuit obtains,

Containing sulfuric acid 55.9g/L and 34.5% aquae hydrogenii dioxidi 19.6cc/L and liquid temperature, be that the etch-rate that floods the aforementioned Copper Foil under the condition of aforementioned layers pressing plate in the etching solution of sulfuric acid/hydroperoxide kind of 30 ℃ ± 1 ℃ is more than 0.68 μ m/min and below 1.25 μ m/min.

The inventor etc. think, by improving the etch-rate of Copper Foil, can realize and reduce the etch residue of Copper Foil and maintain taking into account of wiring shape.

Further the result of research is distinguished, in the evaluation method of etch-rate, according to the difference of the condition of the composition of etchant, constituent concentration and liquid temperature, result can be inconsistent.

Thereby find, etchant adopts sulfuric acid, pure water and aquae hydrogenii dioxidi, determines constituent concentration, and then liquid temperature is made as 30 ℃ ± 1 ℃, and the prerequisite using these conditions as evaluation method, can reduce the inconsistent of result.

And then the inventor etc. have carried out various experiments to the etch-rate of copper under precondition, found that, by making the lower limit of the etch-rate of copper be not less than 0.68 μ m/min, can reduce the etch residue of Copper Foil, it is good that wiring shape becomes, thereby completed the present invention.

In addition, according to the present invention, a kind of manufacture method of printed circuit board (PCB) is provided, the method comprises: prepare to possess insulating barrier and at least operation of the laminated sheet of the Copper Foil of one side that is positioned at aforementioned dielectric layer, and the operation that forms conductor circuit by the aforementioned Copper Foil of selective removal, aforementioned layers pressing plate is above-mentioned laminated sheet.

According to the present invention, provide etch residue minimizing, the wiring shape of Copper Foil to become good laminated sheet.

Accompanying drawing explanation

Fig. 1 is the cutaway view of an example of manufacture method that schematically shows the printed circuit board (PCB) of the 1st execution mode.

Fig. 2 is the cutaway view of an example of manufacture method that schematically shows the printed circuit board (PCB) of the 1st execution mode.

Fig. 3 is the cutaway view of an example of manufacture method that schematically shows the printed circuit board (PCB) of the 2nd execution mode.

Fig. 4 is the cutaway view of an example of manufacture method that schematically shows the printed circuit board (PCB) of the 2nd execution mode.

Fig. 5 is the cutaway view of an example of manufacture method that schematically shows the printed circuit board (PCB) of the 2nd execution mode.

Fig. 6 is the cutaway view of an example of manufacture method that schematically shows the printed circuit board (PCB) of the 3rd execution mode.

Fig. 7 is the cutaway view of variation of manufacture method that schematically shows the printed circuit board (PCB) of the 3rd execution mode.

Embodiment

Below, use accompanying drawing to describe embodiments of the present invention.In addition, in institute's drawings attached, same inscape is marked with identical Reference numeral, and suitably description thereof is omitted.

(the 1st execution mode)

Fig. 1 and Fig. 2 are the cutaway views of process of manufacture method that the printed circuit board (PCB) of the 1st execution mode is shown.

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 comprises following operation.First, prepare to possess insulating barrier 102 and at least laminated sheet (copper clad laminate 100) of the Copper Foil (copper foil layer 104) of one side that is positioned at insulating barrier 102.Then, by selective removal Copper Foil, form conductor circuit (conductor circuit 119).Printed circuit board (PCB) 101 is for device mounting board.

Thereby the manufacture method of the printed circuit board (PCB) of present embodiment 101 is used and is formed by etching Copper Foil the laminated sheet (copper clad laminate 100) that conductor circuit obtains.

In laminated sheet (copper clad laminate 100), under containing the condition that sulfuric acid 55.9g/L and 34.5% aquae hydrogenii dioxidi 19.6cc/L and liquid temperature are impregnate layer pressing plate in the etching solution of sulfuric acid/hydroperoxide kind of 30 ℃ ± 1 ℃, the etch-rate of Copper Foil (copper foil layer 104) is specific is that 0.68 μ m/min is above and below 1.25 μ m/min.

In copper clad laminate 100, the etch-rate of copper foil layer 104 is specific is more than 0.68 μ m/min.Therefore,, in the manufacture process of printed circuit board (PCB) 101, can suppress copper foil layer 104 and remain on the insulating barrier 102 between conductor circuit 119, and can make the wiring shape of conductor circuit 119 good.

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

First, as shown in Fig. 1 (a), prepare the copper clad laminate 10 with foils that two sides and foils layer 106 at insulating barrier 102 are together fitted with copper foil layer 104.Copper clad laminate 10 with foils possesses insulating barrier 102, copper foil layer 104 and foils layer 106.Two sides and copper foil layer 104 at insulating barrier 102 are together pasted with foils layer 106.Present embodiment is formed with copper foil layer 104 on the two sides of insulating barrier 102, but also can be only at the one side of insulating barrier 102, forms copper foil layer 104.

As the copper clad laminate 10 with foils, for example at least one face at copper clad laminate 100 is laminated with strippable foils layer 106.Copper clad laminate 100 (below sometimes also referred to as laminated sheet) is not particularly limited, for example, can uses the plate (having omitted fiber base material in figure) that is laminated with copper foil layer 104 containing at least one face of the insulating barrier 102 of the insulating resin layer of substrate having.Laminated sheet can be individual layer, also can have sandwich construction.That is, as laminated sheet, can only by sandwich layer, be formed, also can use the plate that is formed with lamination layer on sandwich layer.Laminated sheet is such as using stacked plate forming of multiple prepregs etc.Prepreg is not particularly limited, such as being impregnated into the medium method of the base materials such as glass cloth by the resin combination that makes to contain curable resin, curing agent and filler etc., obtains.Then,, as laminated sheet, can use in the stacked metal forming as thin as a wafer with foils of one side at least and heat plate that press molding forms etc.In addition, the interlayer insulating film of lamination layer can be used the material identical with sandwich layer, and base material or resin combination also can be different.In present embodiment, insulating barrier 102 is equivalent to form the insulating resin layer of sandwich layer or lamination layer, can be any in single or multiple lift structure.About using the example of the laminated sheet that possesses lamination layer, in the 2nd execution mode below, describe.

The known resin (below also referred to as insualtion resin composition) that the constituting layer pressing plate using in present embodiment and the resin combination of interlayer insulating film can be used as the insulating material of printed circuit board (PCB) to use, common main use thermal endurance, the curable resin that chemical proofing is good.Above-mentioned resin combination is not particularly limited, is preferably and at least comprises by heat and/or irradiation and the resin combination of curing curable resin.

As curable resin, such as listing: urea (urea) resin, melmac, maleimide compound, polyurethane resin, unsaturated polyester resin, the resin with benzoxazine ring, diallyl Na Dike imide compound, vinyl benzyl resin, vinyl benzyl ether resin, benzocyclobutane olefine resin, cyanate ester resin, epoxy resin etc.In the middle of these, curable resin preferred glass transition temperature reaches 200 ℃ of above combinations.For example preferably use can be above containing 2 or 3 officials of volution, hetero ring type, trihydroxy methyl type, biphenyl type, naphthalene type, anthracene type, phenolic varnish type epoxy resin, cyanate ester resin (prepolymer that contains cyanate ester resin), maleimide compound, benzocyclobutane olefine resin, there is the resin of benzoxazine ring.When using epoxy resin and/or cyanate ester resin, line expands and reduces, and thermal endurance improves significantly.In addition,, when the packing material of epoxy resin and/or cyanate ester resin and high filler loading capacity is combined, have advantages of that anti-flammability, thermal endurance, resistance to impact, high rigidity and electrical characteristics (low-k, low-dielectric loss angle tangent) are excellent.At this, think stable on heating raising be due to: after the curing reaction of above-mentioned curable resin, glass transition temperature reaches more than 200 ℃, the low molecular weight substances such as the heat decomposition temperature of the resin combination after solidifying raises, the reaction residues at more than 250 ℃ temperature reduce.And then, think the raising of anti-flammability be due to: be the curable resin of the fragrant same clan, so in its structure, the ratio of phenyl ring is high, thereby the easy charing of this phenyl ring (graphitization), produces charing part.

Above-mentioned resin combination can further contain fire retardant in the scope of not damaging effect of the present invention, from the viewpoint of environment, and preferred non-halogen fire retardant.As fire retardant, such as listing: organic phosphates fire retardant, organic Nitrogen-and Phosphorus-containing compound, nitrogen compound, silicone based flame retardant, metal hydroxides etc.As organic phosphates fire retardant, can list: the phosphine compounds such as HCA, the HCA-HQ that Sanko Co., Ltd. manufactures, HCA-NQ, the phosphorous benzoxazine compounds such as HFB-2006M that Showa Highpolymer Co., Ltd manufactures, the phosphate compounds such as PX200 that the OP930 that PPQ, Clariant (Japan) K.K. that Hokko Chemical Industry Co., Ltd. manufactures manufactures, great Ba KCC manufacture, the phosphorous epoxy resins such as FX289, FX310 that Toto Kasei KK manufactures, the phenoxy resin that the ERF001 that Toto Kasei KK manufactures etc. are phosphorous etc.As organic Nitrogen-and Phosphorus-containing compound, can list: SPB100, the SPE100 that the phosphoric ester amides compound ， Otsuka Chemical Co., Ltd such as SP670, the SP703 that Shikoku Chem manufactures manufacture, Co., Ltd.'s volt are shown in the phosphazene compounds such as FP-series of making manufacturing etc.As metal hydroxides, can list: Ube Material Industries, the magnesium hydroxides such as UD650, UD653 that Ltd. manufactures, the aluminium hydroxides such as HP-350 that the CL310 that Sumitomo Chemical Co manufactures, Showa Denko K. K manufacture etc.

As the epoxy resin using in above-mentioned resin combination, for example can list: bisphenol A type epoxy resin, bisphenol f type epoxy resin, phenol novolak type epoxy resin, cresols phenolic resin varnish type epoxy resin, bisphenol-A phenolic varnish type epoxy resin, biphenyl phenolic resin varnish type epoxy resin, anthracene type epoxy resin, dinitro anthracene type epoxy resin, 3 officials' energy phenol aldehyde type epoxy resins, 4 officials' energy phenol aldehyde type epoxy resins, naphthalene type epoxy resin, biphenyl type epoxy resin, aralkyl modified epoxy, alicyclic epoxy resin, polyalcohol type epoxy resin, glycidyl amine, ethylene oxidic ester, two keys of butadiene etc. carry out the compound that epoxidation obtains, the compound obtaining with reacting of chloropropylene oxide by hydroxyl organic siliconresin class etc.In the middle of these, epoxy resin is preferably naphthalene type, aryl alkylene type epoxy resin.Aryl alkylene type epoxy resin refers to that repetitive comprises the more than one epoxy resin of combination of the alkylidenes such as aromatic group and methylene, and its thermal endurance, anti-flammability and mechanical strength are excellent.By using naphthalene type, aryl alkylene type epoxy resin, in gained laminated sheet, can improve moisture absorption welding heat resistance (the welding heat resistance after moisture absorption) and anti-flammability.As naphthalene type epoxy resin, can list: HP-4700, HP-4770, HP-4032D, HP-5000, HP-6000 that Dainippon Ink Chemicals manufactures, the NC-7300L that Nippon Kayaku K. K manufactures, the ESN-375 that Nippon Steel Chemical Co., Ltd manufactures etc.; As aryl alkylene type epoxy resin, can list: NC-3000, NC-3000L, NC-3000-FH that Nippon Kayaku K. K manufactures, the NC-7300L that Nippon Kayaku K. K manufactures, the ESN-375 that Nippon Steel Chemical Co., Ltd manufactures etc.

The cyanate ester resin using in above-mentioned resin combination for example can be by making cyanogen halides compound react and obtain with phenols.Object lesson as cyanate ester resin, such as listing: the phenolic varnish type cyanate ester resins such as phenol phenolic varnish type cyanate ester resin, cresols phenolic varnish type cyanate ester resin, the bisphenol type cyanate ester resins such as 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 cyanate resin etc.

In the middle of these, particularly preferably contain phenolic varnish type cyanate ester resin, naphthols aralkyl-type cyanate ester resin, dicyclopentadiene-type cyanate ester resin, biphenyl type cyanate ester resin.And then all solids composition that resin combination preferably contains with respect to resin combination is this more than 10 % by weight cyanate ester resin.Thus, can improve the thermal endurance (glass transition temperature, heat decomposition temperature) of prepreg.And can reduce the thermal coefficient of expansion (the particularly thermal coefficient of expansion of the thickness direction of prepreg) of prepreg.When the thermal coefficient of expansion of the thickness direction of prepreg reduces, can alleviate the ess-strain of multilayer board.And then, in thering is the multilayer board of fine interlayer connecting portion, can significantly improve its connection reliability.

As particularly suitable material in the middle of the phenolic varnish type cyanate ester resin using in above-mentioned resin combination, can enumerate the represented phenolic varnish type cyanate ester resin of following formula (1).By weight average molecular weight, be preferably more than 2000, more preferably 2,000～10,000, more preferably 2,200～3, the phenolic varnish type cyanate ester resin that 500 formula (1) is represented and weight average molecular weight be below 1500, more preferably 200～1, the represented phenolic varnish type cyanate ester resin of 300 formula (1) is used in combination (following, "～" represents to comprise higher limit and lower limit in case of no particular description).In addition, weight average molecular weight is the value that the gel permeation chromatography by polystyrene conversion records in the present embodiment.

[Chemical formula 1]

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

In addition, as cyanate ester resin, the represented cyanate ester resin of the following general formula of suitable use (2) also.The represented cyanate ester resin of following general formula (2) makes naphthols aralkyl resin and cyanic acid condensation and obtains, described naphthols aralkyl resin is by the aphthols such as alpha-Naphthol or betanaphthol and terephthaldehyde's base glycol, α, the reactions such as α '-dimethoxy-paraxylene, Isosorbide-5-Nitrae-bis-(2-hydroxyl-2-propyl group) benzene obtain.The n of general formula (2) is more than 1, more preferably below 10.N is 10 when following, and resin viscosity can not increase, good to the dipping of base material, can suppress the reduction as the performance of laminated sheet.In addition, be not easy to occur molecule inner injection and close when synthetic, minute fluidity during washing improves, and can prevent the reduction of output.

[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.

In addition, as cyanate ester resin, the represented dicyclopentadiene-type cyanate ester resin of the following general formula of suitable use (3) also.More preferably, the n of following general formula (3) is more than 0 and below 8 to the represented dicyclopentadiene-type cyanate ester resin of following general formula (3).N is 8 when following, and resin viscosity can not increase, good to the dipping of base material, can prevent the reduction as the performance of laminated sheet.In addition,, 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.

In addition, resin combination can further contain curing accelerator.For example, if curable resin is epoxy resin, cyanate ester resin, can use the curing accelerator of phenolic resins, epoxy resin, cyanate ester resin.Phenolic resins is not particularly limited, such as listing: the phenolic varnish type phenolic resins such as phenol novolac resin, cresols novolac resin, bisphenol-A phenolic varnish gum, aryl alkylene type novolac resin, unmodified resol, with tung oil, linseed oil, the modification of walnut wet goods resol type phenol resins such as oily modification resol etc.As above-mentioned phenolic resins, preferred phenol novolaks or cresols novolac resin.Wherein from the viewpoint of moisture absorption, weld the preferred biphenyl aralkyl modified phenol novolac resin of heat resistance.

Can use separately a kind in them, also two or more kinds may be used has the material of different weight average molecular weight, also one kind or two or more above-mentioned resin and their prepolymer can be used in combination.

Above-mentioned curing accelerator is not particularly limited, such as listing: zinc naphthenate, cobalt naphthenate, tin octoate, cobalt octoate, bis-acetylacetonate are closed cobalt (II), praseodynium closes the organic metal salts such as cobalt (III); The tertiary amines such as triethylamine, tri-butylamine, diazabicyclo [2,2,2] octane; Glyoxal ethyline, 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-ethyl-4-methylimidazole, 1-cyano ethyl-2-undecyl imidazole, 2-phenyl-4-methyl-5-hydroxyl imidazoles, 2-phenyl-4,5-dihydroxy imidazoles, 2,3-dihydro-1H-pyrrolo-(1, the 2-a) imidazoles such as benzimidazole; The phenolic compounds such as phenol, bisphenol-A, nonyl phenol; The organic acids such as acetic acid, benzoic acid, salicylic acid, p-methyl benzenesulfonic acid, salt compound etc. or its mixture.Can use separately a kind of derivative that comprises them, also can be used together two or more of derivative that comprises them.

In addition,, from stable on heating aspect, in above-mentioned curable resin, can contain maleimide compound.Maleimide compound so long as have the compound of 1 above dimaleoyl imino in 1 molecule, is not particularly limited.As its object lesson, can list: N-phenylmaleimide, N-hydroxy phenyl maleimide, two (4-maleimide phenyl) methane, 2, two { 4-(the 4-maleimide phenoxy group)-phenyl } propane, two (3 of 2-, 5-dimethyl-4-maleimide phenyl) methane, two (3-ethyl-5-methyl-4-maleimide phenyl) methane, two (3,5-diethyl-4-maleimide phenyl) methane, polyphenylene methane maleimide, the prepolymer of these maleimide compounds or the prepolymer of maleimide compound and amines etc.

In addition,, from the aspect of the adaptation with metal forming, in above-mentioned curable resin, can contain phenoxy resin, polyvinyl alcohol resin, polyimides, polyamide, polyamidoimide, polyethersulfone resin, polyphenylene oxide resin.

As phenoxy resin, such as listing: have bis-phenol skeleton phenoxy resin, have naphthalene skeleton phenoxy resin, there is the phenoxy resin of biphenyl backbone etc.In addition also can use, the phenoxy resin of the structure with multiple these skeletons.

In the middle of these, phenoxy resin is preferably used the phenoxy resin with biphenyl backbone and bisphenol S skeleton.Thus, the rigidity having by biphenyl backbone, can improve the glass transition temperature of phenoxy resin, and by the existence of bisphenol S skeleton, can improve the adaptation of phenoxy resin and metal.As a result, can realize the stable on heating raising of insulating barrier 102, and when manufacturing multilager base plate, can improve the adaptation of wiring portion (conductor circuit 118) and insulating barrier 102.In addition, phenoxy resin is also preferably used the phenoxy resin with bisphenol-A skeleton and Bisphenol F skeleton.Thus, when manufacturing multilager base plate, can further improve the adaptation of wiring portion and insulating barrier 102.

Commercially available product as phenoxy resin, can list: FX280 and FX293 that Toto Kasei KK manufactures, Japan Epoxy Resins Co., YX8100, YX6954, YL6974, YL7482, YL7553, YL6794, YL7213 and YL7290 etc. that Ltd. manufactures.Molecular weight to phenoxy resin is not particularly limited, and weight average molecular weight is preferably 5,000～70, and 000, more preferably 10,000～60,000.

While using phenoxy resin, its content is not particularly limited, is preferably 1～40 % by weight of resin combination integral body, more preferably 5～30 % by weight.

Commercially available product as polyvinyl alcohol resin, can list: Denka butyral4000-2,5000-A, 6000-C and 6000-EP that Deuki Kagaku Kogyo Co., Ltd manufactures, the S-LEC BH series that Sekisui Chemical Co., Ltd manufactures, BX is serial, KS is serial, BL is serial and BM is serial etc.Especially, particularly preferably glass transition temperature is 80 ℃ of above resins.

Commercially available product as polyimides, polyamide, polyamidoimide, can list: " VYLOMAX HR11NN (registered trade mark) " and " HR-16NN " " HR15ET " that Toyo Boseki K.K manufactures, the polyamidoimide " KS-9300 " that Hitachi Chemical Co., Ltd. manufactures etc.Can list: " the NEOPULIM C-1210 " that Mitsubishi Gas Chemical Co., Ltd manufactures, soluble polyimide " RIKACOAT SN20 (registered trade mark) " and " RIKACOAT PN20 (registered trade mark) " that New Japan Chem Co., Ltd manufactures, the Polyetherimide " ULTEM (registered trade mark) " that GE Plastics Japan Ltd. manufactures, " V8000 " and " V8002 " and " V8005 " that Dainippon Ink Chemicals manufactures, " BPAM155 " that Nippon Kayaku K. K manufactures etc.

As the commercially available product of polyethersulfone resin, can use known material, such as listing: PES4100P, PES4800P, PES5003P and PES5200P etc. that Sumitomo Chemical Co manufactures.

As polyphenylene oxide resin, for example can list: poly-(2,6-dimethyl-1,4-phenylate), poly-(2,6-diethyl-Isosorbide-5-Nitrae-phenylate), poly-(2-methyl-6-ethyl-1,4-phenylate), poly-(2-methyl-6-propyl group-1,4-phenylate), poly-(2,6-dipropyl-Isosorbide-5-Nitrae-phenylate), poly-(2-ethyl-6-propyl group-Isosorbide-5-Nitrae-phenylate) etc.As commercially available product, " NORYL PX9701 (registered trade mark) " (the number-average molecular weight Mn=14 that for example has GE Plastics Japan Ltd. to manufacture, 000), " NORYL640-111 (registered trade mark) " (number-average molecular weight Mn=25,000) and " SA202 " (number-average molecular weight Mn=20 of manufacturing of Asahi Kasei Corporation, 000) etc., can their low-molecular-weights be used by known method.

In the middle of these, preferably end by functional group modification the oligomeric phenylate of reactivity.Make thus to improve with the compatibility of curable resin, can form the three-dimensional crosslinking structure between polymer, so mechanical strength is excellent.For example can enumerate in TOHKEMY 2006-28111 communique, record 2,2', 3,3', 5,5'-hexamethyl biphenyl-4,4'-glycol-2, the product of 6-xylenol condensation polymer and 1-chloro-4-methyl-benzene.

The oligomeric phenylate of this reactivity can be manufactured by known method.In addition, also can use commercially available product.For example can use aptly OPE-2st2200 (Mitsubishi Gas Chemical Co., Ltd's manufacture).

The weight average molecular weight of reactive oligomeric phenylate is preferably 2,000～20, and 000, more preferably 4,000～15,000.The weight average molecular weight of reactive oligomeric phenylate surpasses at 20,000 o'clock, becomes and is difficult to be dissolved in volatile solvent.And weight average molecular weight is less than at 2,000 o'clock, crosslink density is too high, thereby can be to the modulus of elasticity of solidfied material, flexible generation harmful effect.

The amount of the curable resin in the resin combination using in present embodiment is suitably adjusted according to its object, be not particularly limited, all solids composition with respect to resin combination, curable resin is preferably 10～90 % by weight, more preferably 20～70 % by weight, are further preferably 25～50 % by weight.

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

From the aspect of low-thermal-expansion and mechanical strength, in preferred above-mentioned resin combination, contain inorganic filling material.Inorganic filling material is not particularly limited, such as listing: talcum, calcined clay, the silicate such as calcined clay, mica, glass not; The oxides such as titanium oxide, aluminium oxide, silicon dioxide, fused silica; The carbonate such as calcium carbonate, magnesium carbonate, Hydrotalcite; Aluminium hydroxide, boehmite (AlO (OH), are commonly referred to boehmite (that is, the Al of " vacation " boehmite ₂o ₃xH ₂o, here, x=1～2)), the metal hydroxides such as magnesium hydroxide, calcium hydroxide; Sulfate or the sulphite such as barium sulfate, calcium sulfate, calcium sulfite; The borates such as Firebrake ZB, barium metaborate, aluminium borate, line borate, Boratex; The nitride such as aluminium nitride, boron nitride, silicon nitride, carbonitride; The titanate such as strontium titanates, barium titanate etc.Can use separately a kind in them, also two or more kinds may be used.

Preferred magnesium hydroxide, aluminium hydroxide, boehmite, silicon dioxide, fused silica, talcum, fired talc, aluminium oxide in the middle of these.From the aspect of low heat expansion and insulating reliability, silicon dioxide particularly preferably, further preferred spherical fused silica.In addition, from the aspect of flame resistance, preferred aluminium hydroxide.In addition, even therefore the base material that uses inorganic filling material also easily to flood in present embodiment can make the amount of the inorganic filling material in above-mentioned resin combination more.When the inorganic filling material in resin combination is high concentration, bit wear characteristic variation, is preferred but bit wear characteristic improves while being boehmite from the viewpoint of inorganic filling material.

Particle diameter to inorganic filling material is not particularly limited, and can use the monodispersed inorganic filling material of average grain diameter, also can use the polydisperse inorganic filling material of average grain diameter.And then, also can be used together one kind or two or more average grain diameter list and disperse and/or polydisperse inorganic filling material.Average grain diameter to inorganic filling material is not particularly limited, and is preferably 0.1 μ m～5.0 μ m, is particularly preferably 0.1 μ m～3.0 μ m.When the particle diameter of inorganic filling material is less than aforementioned lower limit, the viscosity of resin combination uprises, and the workability during therefore sometimes to making prepreg exerts an influence.In addition, while surpassing aforementioned higher limit, occur in sometimes in resin combination the phenomenons such as inorganic filling material precipitation.It should be noted that, average grain diameter can be used laser diffraction/diffuse transmission type particle size distribution device (conventional equipments such as SALD-7000 that Shimadzu Seisakusho Ltd. manufactures) to measure.

Content to inorganic filling material is not particularly limited, and all solids composition with respect to above-mentioned resin combination, is preferably 10～90 % by weight, and more preferably 30～80 % by weight, are further preferably 50～75 % by weight.While containing cyanate ester resin and/or its prepolymer in above-mentioned resin combination, with respect to all solids composition of resin combination, the content of above-mentioned inorganic filling material is preferably 50～75 % by weight.When inorganic filling material content surpasses above-mentioned higher limit, the mobility of the resin combination extreme difference that becomes sometimes, therefore not preferred, while being less than above-mentioned lower limit, the intensity of the insulating barrier sometimes being formed by resin combination is insufficient, not preferred.

In addition, the resin combination using in present embodiment also can compounding rubber constituent, for example, preferred example as the rubber grain that can use in the present embodiment, can list: core-shell-type rubber grain, crosslink propylene nitrile butadiene rubber particle, cross-linked styrene butadiene rubber particle, acrylic rubber particle, organic silicon granule etc.

Core-shell-type rubber grain is the rubber grain with sandwich layer and shell, for example, can list: outer field shell is by the rubber grain of 2 layers of structure that glassy polymers forms, the sandwich layer of internal layer consists of rubber-like polymer; Or outer field shell by glassy polymers form, intermediate layer is by rubber grain of the 3-tier architecture that rubber-like polymer forms, sandwich layer consists of glassy polymers etc.Glassy polymers layer such as the polymer by methyl methacrylate etc. forms, and rubber-like polymer layer is such as by formations such as butyl acrylate things (butyl rubber).Object lesson as core-shell-type rubber grain, can list: Stafiloid AC3832, AC3816N (Ltd. manufactures for trade name, Ganz Chemical Co.), METABLEN KW-4426 (trade name, Mitsubishi Rayon Co., Ltd. manufactures).As the object lesson of crosslink propylene nitrile butadiene rubber (NBR) particle, can enumerate XER-91 (average grain diameter 0.5 μ m, JSR Corporation manufacture) etc.

As the object lesson of cross-linked styrene butadiene rubber (SBR) particle, can enumerate XSK-500 (average grain diameter 0.5 μ m, JSR Corporation manufacture) etc.As the object lesson of acrylic rubber particle, can list: METABLEN W300A (average grain diameter 0.1 μ m), W450A (average grain diameter 0.2 μ m) (Mitsubishi Rayon Co., Ltd. manufactures) etc.

Organic silicon granule is so long as the caoutchouc elasticity particulate being formed by organopolysiloxane, be not particularly limited, such as listing: the particulate itself being formed by organic silicon rubber (organopolysiloxane cross-linked elastomer) and the core shell structure particle that forms with the core that the silicone covering of three-dimensional cross-linked type main body is formed by the organosilicon of the crosslinked main body of two dimension etc.As organic silicon rubber particulate, can use: the commercially available products such as KMP-605, KMP-600, KMP-597, KMP-594 (manufacture of KCC of SHIN-ETSU HANTOTAI), Trefil E-500, Trefil E-600 (Dow Corning Toray Co., Ltd. manufactures).

In above-mentioned resin combination, can further contain coupling agent.Coupling agent compounding for following object: by improving the wetability at the interface of curable resin and inorganic filling material, make resin and inorganic filling material be bonded to equably base material, improve the welding heat resistance after thermal endurance, particularly moisture absorption.

Above-mentioned coupling agent is not particularly limited, such as listing: epoxy silane coupling agent, cationic silane coupling agent, amino silicane coupling agent, titante coupling agent, silicone oil type coupling agent etc.Thus, the wetability with the interface of inorganic filling material can be improved, thermal endurance can be further improved thus.

Addition to above-mentioned coupling agent is not particularly limited, and with respect to inorganic filling material 100 weight portions, is preferably 0.05～3 weight portion, is particularly preferably 0.1～2 weight portion.When content is less than aforementioned lower limit, reduce sometimes because abundant coating inorganic filling material causes improving stable on heating effect, while surpassing aforementioned higher limit, reaction is exerted an influence, bending strength etc. can reduce sometimes.

In the resin combination using in present embodiment, can add as required the mentioned components such as flame retardant, ion capturing agent such as defoamer, levelling agent, ultra-violet absorber, blowing agent, antioxidant, fire retardant, organosilicon powder additive in addition.

From easily realizing the aspect of the low linear expansion of prepreg, high rigidization and high heat-resistingization, above-mentioned resin combination preferably at least contains epoxy resin, cyanate ester resin and inorganic filling material.In the middle of, solid constituent with respect to resin combination, the inorganic filling material that preferably contains the epoxy resin of 5～50 % by weight, the cyanate ester resin of 5～50 % by weight and 10～90 % by weight, further preferably contains the inorganic filling material of the epoxy resin of 5～25 % by weight, the cyanate ester resin of 10～25 % by weight and 30～80 % by weight.

The prepreg using in present embodiment is that dipping or the varnish of coating resin combination form in base material, as base material, can use the well-known material with laminated sheets for various insulating materials.Example as the material of base material, can list: the inorganic matter fibers such as E glass, D glass, NE glass, T glass, S glass or Q glass; The organic fibers such as polyimides, polyester or tetrafluoroethene and their mixture etc.These base materials have such as weaving cotton cloth, nonwoven fabrics, rove, the short shapes such as felt, surperficial felt of cutting, and material and shape are selected according to the purposes of target molding, performance, can use as required and separately or use material of more than two kinds and shape.Thickness to base material is not particularly limited, conventionally use the material of 0.01～0.5mm left and right, from the aspect of thermal endurance, moisture-proof, processability, be suitably with silane coupler etc. and carried out surface-treated material, implemented machinery and melt fine processing and the material of flattening.In addition, prepreg can obtain conventionally as follows: to base material dipping or coated with resins, make its resin containing ratio reach 20～90 % by weight after dry, at the temperature of 120～220 ℃, heat drying is 1～20 minute, makes semi-cured state (B scalariform state), obtains thus.And then common stacked 1～20 this prepreg, further heat and pressurizes and stacked to dispose formation with the ultrathin copper foil of foils on its two sides, can obtain laminated sheet thus.The thickness of multi-disc layer of prepreg according to purposes and difference, is suitably the thickness of 0.03～2mm conventionally.As laminating method, can apply the gimmick of common laminated sheet, stacked such as using multistage compacting, multi-stage vacuum compacting, progressive forming, autoclave forming machine etc. conventionally to carry out under 100～250 ℃ of temperature, pressure 0.2～10MPa, the condition of 0.1～5 hour heating time, or can use vacuum lamination apparatus etc. to carry out lamination under the condition of 50～150 ℃ of lamination, 0.1～5MPa, vacuum pressure 1.0～760mmHg.

In addition, the alligatoring face with the ultrathin copper foil of the ultrathin copper foil (copper foil layer 104) of foils can (be called as plating spot through the electrodeposit layer based on forming convex.Such as referring to Japanese kokai publication hei 9-195096), the alligatoring face of oxidation processes, reduction processing, etching etc. processes.Thus, the one side in the main part of copper foil layer 104 forms band bossing (below also referred to as alligatoring foot portions (roughened part)).

In addition, in the present embodiment, as copper foil layer 104, except the Copper Foil (except the tramp material of inevitably sneaking in manufacturing process) being formed by copper, can also be that the Copper Foil that contains the interpolation metal ingredients such as nickel, aluminium (in this situation, is not particularly limited the content of copper, with respect to the total value of weight that forms whole metal ingredients of copper foil layer 104, more than being preferably 90 % by weight, more preferably more than 95 % by weight, more preferably more than 99 % by weight.In addition, as adding metal ingredient, can use separately a kind ofly, also can be used together multiple).In addition, also can use the metal formings such as nickel foil, aluminium foil to replace copper foil layer 104.

At this, the detailed formation method of the peelable release Copper Foil using in copper foil layer 104 is described.

Manufacture method as the Copper Foil using in present embodiment, be not particularly limited, for example, when manufacture has the peelable release Copper Foil of carrier, in the foils of thickness 10～50 μ m, form inorganic compound or organic compound layer as the metal of peel ply etc., by plating, on this peel ply, form Copper Foil.As plating liquid, such as using copper sulphate or cupric pyrophosphate etc. to carry out.In addition, consider physical property, the flatness of Copper Foil, can in above-mentioned bath, add various additives.In addition, peelable release metal forming refers to and has 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 processed to carry out by being used as copper sulphate plating bath that additive contains gelatin and chloride ion to carry out catholyte, thereby carries out.It is the gelatin below 5000 that copper sulphate plating bath for example contains 15～35ppm mean molecule quantity.In addition, for copper sulphate plating bath, for example, as chloride ion concentration, contain 0.1～100ppm, be preferably 0.5～50ppm, be particularly preferably 1～25ppm.

In this situation, the formation of Copper Foil by using be formed with peel ply foils as negative electrode and use above-mentioned copper sulphate plating bath to carry out electrolytic treatments copper facing on peel ply and carry out.According to the formation method of this Copper Foil, even if can form, after high-temperature heating, also there is the also Copper Foil of excellence of appropriate mechanical strength, etching excellence and treatability.This effect is by making the crystal miniaturization that forms Copper Foil bring by adding gelatin.

The mean molecule quantity of gelatin is 5000 when following, the recrystallization of the thin copper layer that can suppress to be caused by heating.Realize thus the miniaturization of the crystal after heating.About its reason, not yet fully understand fully, can think that by making the molecular weight of gelatin be below certain value, gelatin easily enters crystal grain boundary when plating, and result can suppress recrystallization and carry out.The mean molecule quantity of gelatin is preferably 500～5000, and more preferably 1000～5000.By making the mean molecule quantity of gelatin, be more than 500, the gelatin that can suppress to add in copper sulphate plating bath is decomposed and is decomposed into the organic compounds such as low-molecular-weight amino acid in acid solution.Thus, can suppress to prevent that by making gelatin enter crystal grain boundary when the plating effect of recrystallization from reducing.

The concentration of the gelatin in copper sulphate plating bath is preferably 15～35ppm.The concentration of gelatin is 15ppm when above, can fully obtain the inhibition of the recrystallization to being caused by heating.Therefore, can after heating, maintain micro crystal state.The concentration of gelatin is 35ppm when following, and the internal stress of the Copper Foil that can suppress to form by plating increases.Thus, ultrathin copper foil that can inhibition zone foils is curling and rough sledding occurs when conveyance.

As copper sulphate plating bath, the sulfuric acid copper sulphate plating bath that for example suitable use contains copper sulfate pentahydrate, sulfuric acid, gelatin and chlorine.The concentration of the copper sulfate pentahydrate in copper sulphate plating 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 generally water.The temperature of plating bath is preferably 20～60 ℃, more preferably 30～50 ℃.Current density during electrolytic treatments is preferably 1～15A/dm ², 2～10A/dm more preferably ².

While forming Copper Foil, state in the use copper sulphate plating bath and carry out before electrolytic treatments, in order to prevent the generation of pin hole, can use the so-called strike plating (strike plating) that has adopted the plating bath that covering power is good.The plating bath of using as strike plating, such as listing: cupric pyrophosphate plating bath, copper citrate plating bath, copper citrate nickel plating bath etc.

As cupric pyrophosphate plating bath, for example, be suitably the plating bath that contains cupric pyrophosphate and potassium pyrophosphate.The concentration of the cupric pyrophosphate in cupric pyrophosphate plating bath is preferably 60g/L～110g/L, more preferably 70g/L～90g/L.The concentration of potassium pyrophosphate is preferably 240g/L～470g/L, more preferably 300g/L～400g/L.The solvent of plating bath is generally water.The pH of plating bath is preferably 8.0～9.0, and more preferably 8.2～8.8.Can add in order to regulate pH value (lower same) such as ammoniacal liquor.The temperature of plating bath is preferably 20～60 ℃, more preferably 30～50 ℃.Current density during electrolytic treatments is preferably 0.5～10A/dm ², 1～7A/dm more preferably ².The electrolytic treatments time is preferably 5～40 seconds, more preferably 10～30 seconds.

As copper citrate plating bath, for example, be suitably the plating bath that contains copper sulfate pentahydrate and citrate trisodium dihydrate.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 is generally water.The pH of plating bath is preferably 5.5～7.5, and more preferably 6.0～7.0.The temperature of plating bath is preferably 20～60 ℃, more preferably 30～50 ℃.Current density during electrolytic treatments is preferably 0.5～8A/dm ², 1～4A/dm more preferably ².The electrolytic treatments time is preferably 5～40 seconds, more preferably 10～30 seconds.

As copper citrate nickel plating bath, for example, be suitably the plating bath that contains copper sulfate pentahydrate, nickel sulfate hexahydrate compound and citrate 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 is 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.The solvent of plating bath is generally water.The pH of plating bath is preferably 5.5～7.5, and more preferably 6.0～7.0.The temperature of plating bath is preferably 20～60 ℃, more preferably 30～50 ℃.Current density during electrolytic treatments is preferably 0.5～8A/dm ², 1～4A/dm more preferably ².The electrolytic treatments time is 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 the heat treatment standing between 100～300 ℃ when stacked also can be peeled off and can use known material.As metal oxide, for example, can use the mixture of zinc, chromium, nickel, copper, molybdenum, alloy system, metallide.As organic compound, preferably use by the one kind or two or more material forming being selected from organic compounds containing nitrogen, organic compounds containing sulfur and carboxylic acid.

Above-mentioned organic compounds containing nitrogen is preferably has substituent organic compounds containing nitrogen.Particularly, preferably be used as and there is 1 of substituent triazole compounds, 2,3-BTA (hereinafter referred to as " BTA "), carboxyl benzotriazole (hereinafter referred to as " CBTA "), N', two (BTA ylmethyl) ureas (hereinafter referred to as " BTD-U ") of N'-, 1H-1,2,4-triazole (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 (hereinafter referred to as " TCA ") and 2-benzimidazole mercaptan (hereinafter referred to as " BIT ") etc.

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

By as above improving electrolysis density or attenuate thickness etc., control suitably manufacture method, can realize desired orientation at the upper surface of the copper foil layer 104 of present embodiment.

At least lower surface 22 of the copper foil layer 104 using in present embodiment in addition, (face contacting with the one side of insulating barrier 102) can be in order to make the adaptation of copper foil layer 104 and insulating barrier 102 reach realistic scale or higher above and implement surface treatment.As the surface treatment of the metal forming for using in copper foil layer 104, such as listing, antirust processing, chromate are processed, the combination of any or they in silane coupled processing etc.Can coordinate the resin material that forms insulating barrier 102 to select suitably arbitrary surfaces to process means.

Above-mentioned antirust processing example is as implemented by utilizing sputter, plating, chemical plating to form film in metal forming the alloy of any or they in the metals such as nickel, tin, zinc, chromium, molybdenum, cobalt.Preferred plating from the viewpoint of cost.For metal ion is easily separated out, also can add the complexing agent such as citrate, tartrate, sulfamic acid of aequum.Plating liquid is used at acidic region conventionally, for example, at the temperature of room temperature (25 ℃)～80 ℃, carries out.Plating condition is from current density 0.1～10A/dm ², 1～60 second conduction time, be preferably in the scope of 1～30 second and suitably select.The amount of antirust processing metal is according to the kind of metal and difference is suitably 10～2000 μ g/dm by summation meter ².When antirust processing is blocked up, can cause that etching inhibition and electrical characteristics reduce, cross when thin, can form the main cause that the peel strength with resin reduces.

In addition,, while containing cyanate ester resin in the resin combination that forms insulating barrier 102, the metal that preferred antirust processing and utilizing contains nickel carries out.Under this combination, the peel strength in heat-resisting deterioration test, moisture-proof deterioration test reduces few, is useful.

As above-mentioned chromate, process, preferably use the aqueous solution that contains hexavalent chromium.Chromate is processed and also can be undertaken by simple impregnation process, preferably by cathode treatment, is undertaken.Preferably at sodium dichromate 0.1～50g/L, pH1～13, bath temperature 0～60 ℃, current density 0.1～5A/dm ², carry out under the electrolysis time condition of 0.1～100 second.Also can replace sodium dichromate to carry out with chromic acid or potassium bichromate.In addition, above-mentioned chromate is processed preferably stack enforcement in above-mentioned antirust processing.Can further improve thus the adaptation of insualtion resin composition layer (insulating barrier 102) and metal forming (copper foil layer 104).

As the silane coupler using in above-mentioned silane coupled processing, for example can use 3-glycidoxypropyltrime,hoxysilane, 2-(3, 4-epoxycyclohexyl) the epoxy functional silane such as ethyl trimethoxy silane, 3-TSL 8330, N-2-(amino-ethyl) 3-TSL 8330, the amino functional silane such as N-2-(amino-ethyl) 3-aminopropyl methyl dimethoxysilane, vinyltrimethoxy silane, ethenylphenyl trimethoxy silane, the alkene functional silanes such as vinyl three (2-methoxy ethoxy) silane, the acrylic functional silane such as 3-acryloxy propyl trimethoxy silicane, the methacrylic functional silanes such as 3-methacryloxypropyl trimethoxy silane, the Mercaptofunctional silane such as 3-sulfydryl propyl trimethoxy silicane etc.These can use separately, also can mix multiple use.These coupling agents are dissolved in water equal solvent and use with the concentration of 0.1～15g/L, by silane coupler being adsorbed in metal forming in metal forming gained solution coating or electro-deposition at the temperature of room temperature～50 ℃.These silane couplers are carried out condensation bonding and in metal forming, are formed overlay film by the hydroxyl of the antirust processing metal with metal foil surface.After silane coupled processing, by heating, ultraviolet ray irradiation etc., make described bonding stabilisation.In heat treated, for example, preferably the temperature of 100～200 ℃, carry out 2～60 seconds being dried.Ultraviolet ray is irradiated preferably at for example wavelength 200～400nm, 200～2500mJ/cm ²scope carry out.In addition, silane coupled processing is preferably carried out the outermost layer of metal forming.While containing cyanate ester resin in the insualtion resin composition that forms insulating barrier 102, preferably with the coupling agent of amino silane class, process.This peel strength being combined in heat-resisting deterioration test, moisture-proof deterioration test reduces less, is useful.

In addition, as the silane coupler using in silane coupled processing, be preferably by preferably 60～200 ℃, more preferably 80～150 ℃ heating and with the material that forms the insualtion resin composition generation chemical reaction of insulating barrier 102.Thus, there is chemical reaction in the functional group in above-mentioned insualtion resin composition and the functional group of silane coupler, can obtain more excellent adaptation.For example, for the insualtion resin composition that contains epoxy radicals, preferably use the silane coupler that contains amino functional silane.This be due to, epoxy radicals and amino easily form firmly chemical bond because of heat, this key is extremely stable with respect to heat, moisture.As the combination of formation chemical bond like this, can exemplify: epoxy radicals-amino, epoxy radicals-epoxy radicals, epoxy radicals-sulfydryl, epoxy radicals-hydroxyl, epoxy radicals-carboxyl, epoxy radicals-cyanate radical, amino-hydroxyl, amino-carboxyl, amino-cyanate radical etc.

In addition, insulating resin as the insualtion resin composition using in present embodiment, preferably using is liquid epoxy resin at normal temperatures, in this situation, viscosity during due to melting significantly reduces, therefore the wetability at bonding interface place improves, the chemical reaction of become easy initial ring epoxy resins and silane coupler, and result can obtain firmly peel strength.Particularly, bisphenol A type epoxy resin, bisphenol f type epoxy resin, the phenol novolak type epoxy resin of preferred epoxide equivalent 200 left and right.

In addition,, when insualtion resin composition contains curing agent, as curing agent, particularly preferably use heat-curing type potentiality curing agent.; when chemical reaction occurs for the functional group in insualtion resin composition and the functional group of silane coupler, preferably select curing agent to make the functional group in insualtion resin composition lower than insualtion resin composition, start to be cured the temperature of reacting with the reaction temperature of the functional group of silane coupler.Thus, preferentially and optionally carry out the reacting of functional group of functional group in insualtion resin composition and silane coupler, metal forming (copper foil layer 104) further improves with the adaptation of insualtion resin composition layer (insulating barrier 102).Thermohardening type potentiality curing agent as the insualtion resin composition for containing epoxy resin, such as listing: the solid dispersion-heating for dissolving type curing agent such as dicyandiamide, dihydrazide compound, imidazolium compounds, amine-epoxy adduct, urea compounds, salt, boron chloride amine salt class, block carboxylic acid compound isoreactivity group block type curing agent.

Above, by the prepreg that utilizes preceding method to make to contain insualtion resin composition, with stacked integrated with the ultrathin copper foil of foils, can obtain the copper clad laminate 10 with foils as shown in Fig. 1 (a).Then,, as shown in Fig. 1 (b), by peeling off foils layer 106, can obtain having on the two sides of insulating barrier 102 copper clad laminate 100 of copper foil layer 104.It should be noted that, be not limited to which, copper foil layer 104 is formed at least one side of insulating barrier 102, in addition, can be formed on whole or a part of insulating barrier 102.In addition, the copper foil layer 104 of present embodiment preferably has main part and alligatoring foot portions.

At this, laminated sheet (copper clad laminate 100) is elaborated.

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

In the present embodiment, by making the etch-rate of copper foil layer 104 be not less than lower limit, can reduce the etch residue of copper foil layer 104, and can make wiring shape good.In addition,, by making the etch-rate of Copper Foil not higher than higher limit, the sidewall that can be suppressed at copper foil layer 104 forms breach and connects up and reduce with the adaptation of insulating barrier.That is,, when being etched to the alligatoring foot portions of copper foil layer 104, the main part that can be suppressed at copper foil layer 104 produces abnormal contraction.

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

1. become 40mm * 80mm to obtain sample strip substrate (copper clad laminate 100) severing that is laminated with the ultrathin copper foil of having removed foils (foils layer 106) on two sides.For sample strip, with vernier caliper, read to after decimal point 2, the sheet area of calculating sample strip.

2. on horizontal drying line, sample strip is carried out to 80 ℃ of dry processing of 1 minute * 3 times.

3. the initial stage weight W 0 of working sample sheet (comprising substrate weight).

4. prepare etching solution.

4-1: weigh 60g95% sulfuric acid (manufacture of He Guangchun medicine Co., Ltd., superfine), put into the beaker of 1L.

4-2: pure water is dropped into the beaker using in 4-1, making total amount is 1000cc.

4-3: stir 3 minutes at 30 ℃ ± 1 ℃ with magnetic stirrer.

4-4: weigh 20cc34.5% aquae hydrogenii dioxidi (Kanto Kagaku K. K. manufactures, deer one-level), put into the beaker that 4-1 is used, making total amount is after 1020cc, stirs 3 minutes at 30 ℃ ± 1 ℃.Can obtain thus the etching solution of sulfuric acid 55.9g/L and 34.5% aquae hydrogenii dioxidi 19.6cc/L.

5. impregnated sample sheet in above-mentioned etching solution (liquid temperature: 30 ℃ ± 1 ℃, stirring condition: magnetic stirrer, 250rmp).

6. until the main part of ultrathin copper foil, by etching completely, was measured the weight W 1 (comprising substrate weight) of a sample strip every 30 seconds.

7. calculate etching weight (W0-W1)/(two sides area=m flooding ²), take X-axis as etching period (second), take Y-axis as etching quality (g/m ²) mapping.Between 0～150 second, use least square method to calculate slope K.

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

Etch-rate (μ m/min)=K (g/secm ²) ÷ 8.92 (copper proportion g/cm ³) * 60 (sec/min)

More than the difference of Vickers hardness before and after the heat treated of the condition of 230 ℃, 1 hour, copper foil layer 104 is preferably 0Hv and below 50Hv, more preferably below the above 30Hv of 0Hv.By making the difference of Vickers hardness of copper foil layer 104 not higher than higher limit, can suppress slack-off because heating is carried out the recrystallization of copper foil layer 104, grain size increases the etch-rate causing, or can suppress the strain accumulation of the thin circuit after etching.At this, more than the absolute value of the difference of the Vickers hardness of the copper foil layer 104 before and after the heat treated of the condition of 230 ℃, 1 hour preferably adopts 0Hv and below 50Hv, more than more preferably adopting 0Hv and below 30Hv.

In addition, more than the Vickers hardness of copper foil layer 104 after 230 ℃, 1 hour heat treated is preferably 180Hv and below 240Hv, more preferably more than 185Hv and below 235Hv.By making the Vickers hardness after heating, be more than 180Hv, can suppress because heating makes the recrystallization of thin copper layer (copper foil layer 104), grain size to be increased, can suppress linear reduction of circuit after etching.And be below 240Hv by making the Vickers hardness after heating, in the time of can suppressing to become the processing causing really up to the mark and fragile due to thin copper layer, crack, and can improve the cold-hot impact of formed fine wiring.

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

That is, the mensuration of Vickers hardness is according to JIS Z2244, and according to the following steps, the micro-hardness tester (model MVK-2H) that uses Akashi Corporation to manufacture carries out at 23 ℃.(1) after the ultrathin copper foil with foils that is formed into copper foil layer is placed to 1 hour in being heated to the baking oven (nitrogen atmosphere) of 230 ℃, cut into 10 * 10mm square.(2) cutting sample is formed to impression under 3 μ m/ seconds of loading speed, test load 5gf, the condition of 15 seconds retention times, according to the measurement result of impression, calculate Vickers hardness.(3) value using the mean value of the Vickers hardness of any 5 recording as the Vickers hardness of present embodiment.

In addition, as sample, also can use the ultrathin copper foil with foils that has just been formed into copper foil layer and has not carried out heat treated.

In addition, in copper foil layer 104, the grain size of the section after 230 ℃, 1 hour heat treated is preferably below 2.0 μ m, more preferably below 0.5 μ m, more preferably more than 0.25 μ m and below 0.5 μ m.By making the grain size of copper foil layer 104 not higher than higher limit, can suppress linear reduction of circuit after etching.By making the grain size of copper foil layer 104 be not less than lower limit, can suppress the internal stress (tensile stress) before heating after thin copper layer plating and become too high, the ultrathin copper foil of inhibition zone supporter is whole curling and rough sledding occurs when conveyance.

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.Concrete step is as follows.First, with FIB (focused ion beam, focused ion beam) processing unit (plant), laminated sheet (copper clad laminate 100) is processed, taken SIM (Scanning Ion Microscope) and observe photo.According to the standard photographs of the comparison method of stipulating in JIS H0501, calculate the grain size of the section of captured photo.

Present embodiment is by reducing the grain size of copper foil layer 104, reduces the variation of the Vickers hardness after heating, and improves the etch-rate etc. of alligatoring foot portions, can improve the etch-rate of copper foil layer 104 (particularly main part).In addition, the etch-rate of alligatoring foot portions is conventionally slow than the etch-rate of main part, for example, can improve by reducing electrolysis density.

The thickness of copper foil layer 104 can be set arbitrarily according to purposes.For example,, more than the thickness of copper foil layer 104 is preferably 0.1 μ m and below 5 μ m, more preferably more than 1 μ m and below 4 μ m.By making the thickness of copper foil layer 104 in above-mentioned scope, can form good fine circuits.

Then,, as shown in Fig. 1 (c), on copper clad laminate 100, form the through hole 108 that the surperficial from it interlayer that is through to lower surface connects use.The method that forms through hole 108 can be used various known means, for example, during the through hole 108 more than forming aperture 100 μ m, angle from productivity ratio, be suitably the means of using drill bit etc., during through hole 108 below forming 100 μ m, be suitably the means of the Solid State Lasers such as gas laser, YAG such as using carbonic acid gas, excimers.

Although also can be at least to giving catalysis core on copper foil layer 104, present embodiment above and on the internal face of through hole 108 is given catalysis core to whole of copper foil layer 104.As this catalysis core, be not particularly limited, for example can use precious metal ion, palladium colloid.Then, using this catalysis core to form chemical deposit as core, and before this chemical plating is processed, also can be to carrying out on the surface of copper foil layer 104, through hole 108 such as the desmear etc. that utilizes liquid.As desmear, process, be not particularly limited, can use following known method: use the damp process of the oxidizing agent solution etc. with organic substance decomposing effect, and the dry processes such as plasma method etc. that the strong active material (plasma, free radical etc.) of the object direct irradiation oxidation as object removed to organic substance residue.Desmear as damp process is processed, and particularly, can list after the swelling processing of implementing resin surface, utilizes alkali treatment to carry out etching, then carries out the method for neutralisation treatment etc.

Then,, as shown in Fig. 1 (d), on the copper foil layer 104 of having given catalysis core and on the inwall of through hole 108, by chemical plating, process the lamellar chemical deposit 110 of shape.This chemical deposit 110 is electrically connected to the copper foil layer on the upper surface of insulating barrier 102 104 with the copper foil layer 104 on its lower surface.Chemical plating can be used such as the material that contains copper sulphate, formalin, complexing agent, NaOH etc.In addition, after chemical plating, the heat treated of preferably implementing 100～250 ℃ makes plating film stabilisation.From forming the aspect of the overlay film that can suppress oxidation, the particularly preferably heat treated of 120～180 ℃.In addition, the thickness of the average thickness of chemical deposit 110 for carrying out follow-up plating, for example, be that 0.1～1 μ m left and right is enough to.In addition, the inside of through hole 108 can filled conductive paste or insulation paste, can be electroplated and be filled by pattern.

Then,, as shown in Fig. 1 (e), on the chemical deposit 110 being arranged on copper foil layer 104, form the resist layer 112 of the patterns of openings with regulation.This patterns of openings is equivalent to conductor circuit pattern described later.Therefore, resist layer 112 arranges to cover the mode in the inverter circuit formation region on copper foil layer 104.In other words, resist layer 112 be not formed on through hole 108 and copper foil layer 104 on conductor circuit form region.As resist layer 112, be not particularly limited, can use known material, can use liquid state and dry film.When forming fine wiring, as resist layer 112, preferably use photosensitive dry film etc.Want to form resist layer 112, for example, stacked photosensitive dry film on chemical deposit 110, forms region to inverter circuit and exposes and make its photocuring, by developing solution dissolution, remove unexposed portion.In addition, residual curing photosensitive dry film becomes resist layer 112.The suitable employing of thickness of resist layer 112 and afterwards the thickness equal extent of the conductor of plating (coating 114) or thicker thickness.

Then,, as shown in Fig. 2 (a), at least on the patterns of openings inside of resist layer 112 and chemical deposit 110, by electroplating processes, form coating 114.Now copper foil layer 104 plays power supply layer.Present embodiment can be at the upper surface of insulating barrier 102, the inwall of through hole 108 and lower surface thereof arrange coating 114 continuously.Plating as such, is not particularly limited, the known method that can use common printed circuit board (PCB) to use, such as under the state that can use in impregnated in the plating liquids such as copper sulphate to methods such as this plating liquid galvanizations.Thickness to coating 114 is not particularly limited, and can use as circuit conductor, for example, be preferably the scope of 1～100 μ m, more preferably the scope of 5～50 μ m.Coating 114 can be both individual layer, also can have sandwich construction.Material as coating 114, is not particularly limited, such as using copper, copper alloy, 42 alloys, nickel, iron, chromium, tungsten, gold, scolding tin etc.

Then,, as shown in Fig. 2 (b), use alkaline stripper, sulfuric acid or the commercially available removal resist layers 112 such as anticorrosive additive stripping liquid controlling.

Then,, as shown in Fig. 2 (c), remove chemical deposit 110 and copper foil layer 104 beyond the region be formed with coating 114.Remove the gimmick of this copper foil layer 104 and for example use soft etching (fast-etching, flash etching) etc.Can form thus the pattern of the conductor circuit 118 of the stacked formation of copper foil layer 104 and metal level 116 (chemical deposit 110 and coating 114).

At this, below the etching solution using in the soft etching of present embodiment is described.As etching solution, be not particularly limited, while using the etching solution of existing diffusion speed limit type, in any case the fluid exchange of the fine part of wiring all can variation, therefore there is the tendency of circuit formative variation.Therefore, etching solution it is desirable to use reacting with reaction speed limit but not the type that diffusion speed limit is carried out of copper and etching solution.If copper reacts for reaction speed limit with etching solution, even if further strengthen diffusion, etch-rate can not change yet.That is, the etch-rate at the good Yu Cha position, position of fluid exchange can not produce difference.As this reaction speed limit etching solution, for example, can list and take hydrogen peroxide and liquid that acid of halogen-containing element is not main component.Owing to using hydrogen peroxide as oxidant, therefore by its concentration of management, can carry out tight etch-rate and control.In addition, if sneak into halogens in etching solution, solubilizing reaction easily becomes diffusion speed limit.As not halogen-containing acid, can use nitric acid, sulfuric acid, organic acid etc., due to the cheap sulfuric acid that is preferably.And then when sulfuric acid and hydrogen peroxide are main component, from etch-rate, liquid stabilising aspect, preferably concentration is separately 5～300g/L, 5～200g/L.Such as listing ammonium persulfate, sodium peroxydisulfate, sodium peroxydisulfate class etc.

As engraving method, can adopt variety of way.Such as both copper clad laminate 100 being impregnated in the etching solution in liquid storage containers such as being contained in beaker, also can etching solution be coated to copper foil layer 104 with spray pattern.

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

In addition, as shown in Fig. 2 (d-1), can be to cover on insulating barrier 102 and the mode of a part for conductor circuit 118 forms solder mask 120.As solder mask 120, for example can contain packing material or the base material of insulating properties excellence, use the heat-resistant resin compositions such as photoresist, curable resin and thermoplastic resin.Then, can on the conductor circuit 118 of peristome that is provided with solder mask 120, further form the 1st coating 122 and the 2nd coating 124.Metal level 116 can be made thus to 2 layers of above sandwich construction.As these the 1st coating 122 and the 2nd coating 124, can adopt Gold plated Layer.As gold-plated method, for existing known method, be not particularly limited, such as just like lower method etc.: carry out the chemical nickel plating of 0.1～10 μ m left and right and carry out carrying out the chemical gilding about 0.1～2 μ m after the immersion gold plating of 0.01～0.5 μ m left and right on coating 114.From above, can obtain the printed circuit board (PCB) 202 shown in (d-1) of Fig. 2.

In addition, as shown in Fig. 2 (d-2), also can be at surrounding's formation the 1st coating 122 of conductor circuit 118 and the 2nd coating 124 and do not form solder mask 120.As these the 1st coating 122 and the 2nd coating 124, for example, can adopt the duplexer of nickel coating and Gold plated Layer.From above, can obtain the printed circuit board (PCB) 204 shown in (d-2) of Fig. 2.

In addition, can on these printed circuit board (PCB)s 200,202 and 204, not shown semiconductor chip be installed and obtain semiconductor device.

(the 2nd execution mode)

Then, the manufacture method of the printed circuit board (PCB) of the 2nd execution mode is described.

Fig. 3～Fig. 5 is the cutaway view of step of manufacturing process of manufacture method that the printed circuit board (PCB) of the 3rd execution mode is shown.The manufacture method of the printed circuit board (PCB) of the 3rd execution mode is for example: use the printed circuit board (PCB) 200,202 and 204 obtaining in the 2nd execution mode as internal layer circuit substrate, further form lamination layer on this internal layer circuit substrate.

First, as internal layer circuit substrate, adopt the printed circuit board (PCB) 200 obtaining in Fig. 2 (c).The internal layer circuit of this printed circuit board (PCB) 200 (conductor circuit 118) is implemented to roughening treatment.At this, roughening treatment refers to implements liquid processing and plasma treatment etc. to conductor circuit surface.As roughening treatment, for example, can use and utilize redox Darkening process, or utilize the liquid processing etc. of the known coarsening solution of Sulfuric-acid-hydrogen-peroxide class.Thus, can improve the adaptation that forms the interlayer dielectic of insulating barrier 130 and the conductor circuit 118 of printed circuit board (PCB) 200.In addition, the printed circuit board (PCB) 200 that internal layer circuit substrate also can replace obtaining in the 2nd execution mode is used by plated-through-hole method, lamination method etc. and is laminated with prepreg or not containing the common multilayer board of the resin combination layer of base material etc., is not particularly limited.Conductor circuit layer as internal layer circuit can form by existing known circuit forming method.In addition, in multilayer board, also can carry out drill bit processing, laser processing etc. by the duplexer to as its sandwich layer (duplexer that stacked a plurality of prepregs obtain) and metal-coated laminated board and form through hole, then, by plating etc., the internal layer circuit on two sides is electrically connected to.

Then,, as shown in Fig. 3 (a), in the both sides of the printed circuit board (PCB) 200 on conductor circuit surface alligatoring, configure respectively insulating barrier 130 (prepreg) and with the copper foil layer 105 (with the ultrathin copper foil of foils) of foils layer 107.Then,, as shown in Fig. 3 (b), by being heated to pressurized treatments, the duplexer that they are overlapped into forms multilayer layer pressing plate.Then,, as shown in Fig. 3 (c), peel off and remove foils layer 107.

Then,, as shown in Fig. 3 (d), a part of removing insulating barrier 130 and copper foil layer 105 forms hole 109.109 the bottom surface in hole, a surperficial part for conductor circuit 118 is exposed.Gimmick as forming this hole 109, is not particularly limited, such as using following gimmick etc.: use the Solid State Lasers such as gas laser, the YAG such as carbonic acid gas, excimers to form the blind via hole (blind via hole) below the 100 μ m of aperture.In addition, although hole 109 is expressed as non-through hole in (d) of Fig. 3, can be also through hole.In addition, during for through hole, can use Ear Mucosa Treated by He Ne Laser Irradiation to form, also can use drill bit processing machine to form.

Then, as shown in Fig. 4 (a), the lamellar chemical deposit 111 of shape on the aforementioned conductor circuit 118 of giving catalysis core, on the inwall in hole 109 and on copper foil layer 105.Chemical deposit 111 forms with the same operation of aforementioned chemical deposit 110.Before this chemical plating, as previously mentioned, can utilize the desmears such as desmear of liquid to process.In addition, the thickness of the thickness of chemical deposit 110 for carrying out follow-up plating, is that 0.1～1 μ m left and right is enough to.In addition, the inside of hole 109 (blind via hole) can filled conductive paste or insulation paste, can be electroplated and be filled by pattern.

Then, on chemical deposit 110, form the resist layer 113 with the patterns of openings that is equivalent to conductor circuit pattern.In other words, by forming resist layer 113, shelter inverter circuit forming portion.As this resist layer 113, can use the layer same with aforementioned resist layer 112.The suitable employing of thickness of resist layer 113 and afterwards the thickness equal extent of the conductor circuit of plating or thicker thickness.

Then, as shown in Fig. 4 (c), at the inner coating 132 that forms of patterns of openings of resist layer 113.This coating 132 both can be formed on the conductor circuit 118 of 109 inside, hole, also can be formed on the chemical deposit 111 of above-mentioned patterns of openings inside.The plating that forms coating 132 can be used the gimmick same with aforementioned coating 114.The thickness of this coating 132 can be used as circuit conductor, for example, be preferably the scope of 1～100 μ m, more preferably the scope of 5～50 μ m.

Then,, as shown in Fig. 5 (a), carry out peeling off of resist layer 113 with the same operation of aforementioned resist layer 112.Then,, as shown in Fig. 5 (b), by soft etching (fast-etching), remove copper foil layer 105 and chemical deposit 111 equally with aforementioned copper foil layer 104.Can form thus the conductor circuit pattern being formed by copper foil layer 105, chemical deposit 111 and coating 132.In addition, on conductor circuit 118, can form path and the pad being electrically connected to it by coating 132.From above, can obtain printed circuit board (PCB) 201.

In addition, as shown in Fig. 5 (c-1), can be on insulating barrier 130, on the coating 132 of conductor circuit pattern and in a part for the coating 132 of pad, form solder mask 121.As solder mask 121, can use the layer same with aforementioned solder mask 120.Then, can on the coating 132 of peristome that is provided with solder mask 121, further form the 1st coating 123 and the 2nd coating 125 for example being formed by nickel coating and Gold plated Layer.From above, can obtain the printed circuit board (PCB) 203 shown in (c-1) of Fig. 5.

In addition, as shown in Fig. 5 (c-2), can be at the surrounding of conductor circuit pattern and aforementioned the 1st coating 123 of surrounding's formation of pad and the 2nd coating 125 and do not form solder mask 121.From above, can obtain the printed circuit board (PCB) 205 shown in (c-2) of Fig. 5.In the 2nd execution mode, also can obtain the effect same with the 1st execution mode.

(the 3rd execution mode)

Then, the manufacturing process of the printed circuit board (PCB) 101 of the 3rd execution mode is elaborated.

As shown in Fig. 6 (a), prepare the copper clad laminate 10 with foils.Then, as shown in Fig. 6 (b), peel off etc., from the copper clad laminate 10 with foils, remove foils layer 106.Then,, as shown in Fig. 6 (c), on the copper foil layer 104 staying, form the resist layer 112 of the patterns of openings with regulation.In the patterns of openings of resist layer 112 He on copper foil layer 104, by plating, form coating (metal level 115) (Fig. 6 (d)).Then,, as shown in Fig. 6 (e), remove resist layer 112.Thus can be on copper foil layer 104 selectivity form the pattern of the metal level 115 of regulation.Then, as shown in Fig. 6 (f), by for example soft etching, remove the copper foil layer 104 in the region not covered by metal level 115.After the removing step of this copper foil layer 104, can be formed by the copper foil layer 104 staying and metal level 115 pattern of conductor circuit 119.By above operation, can obtain the printed circuit board (PCB) 101 of the 3rd execution mode.In the 3rd execution mode, also can obtain the effect same with the 1st execution mode.

(the 4th execution mode)

Then, the manufacturing process of the printed circuit board (PCB) 101 of the 4th execution mode is elaborated.

First, as shown in Fig. 7 (a), prepare the copper clad laminate 10 with foils.In the copper clad laminate 10 with foils, on the two sides of insulating barrier 102, be all pasted with foils layer 106 together with copper foil layer 104.Then,, as shown in Fig. 7 (b), from the copper clad laminate 10 with foils, peel off foils layer 106.Then,, as shown in Fig. 7 (c), on whole of copper foil layer 104, by plating, form metal level 115 (coating).Then,, as shown in Fig. 7 (d), on plane metal level 115, form the resist layer 112 of the patterns of openings with regulation.Then,, as shown in Fig. 7 (e), by for example etching, remove metal level 115 and copper foil layer 104 in the patterns of openings of this resist layer 112.Then, as shown in Fig. 7 (f), remove resist layer 112.Can form thus the pattern of the conductor circuit 119 being formed by copper foil layer 104 and metal level 115.By above operation, can obtain the printed circuit board (PCB) 101 of the 4th execution mode.In the 4th execution mode, also can obtain the effect same with the 1st execution mode.

As above,, according to present embodiment, can provide manufacture method and this printed circuit board (PCB) with fine circuits processing, the shape of fine circuits and the printed circuit board (PCB) of insulating reliability excellence of the ultrathin copper foil of foils.

The manufacture method of the printed circuit board (PCB) of present embodiment not only can be applied to form on the two sides of use in printed circuit board substrate the situation of conductor circuit layer, can also be applied to only at the one side of use in printed circuit board substrate, form the situation of conductor circuit layer.In addition, can also be applied to using the situation of two-face printing circuit board as the multilayer board of the 3rd execution mode of inner layer circuit board as shown in Fig. 2 (c).Therefore, the manufacture method of the printed circuit board (PCB) by present embodiment, can manufacture any in single-clad board, two-face printing circuit board and multilayer board.

Embodiment

Below manufacture the ultrathin copper foil with foils of the present invention and use the copper clad laminate of this Copper Foil, the execution mode of the manufacture method of printed circuit board (PCB) of the present invention is described.At this, centered by the situation of foils use electrolytic copper foil, describe.Based on embodiment and comparative example, the present invention is described in detail, but the present invention is not limited thereto.

In the situation that not recording especially, " part " expression " weight portion ", " % " expression " % by weight " of below recording.

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

Below the manufacture of the ultrathin copper foil with foils is described.

(Production Example 1)

As foils (support metal paper tinsel), on the glassy surface of the thick electrolytic copper foil of 18 μ m, form successively peel ply and ultrathin copper foil layer.Create conditions as follows.

First, by foils at acid elution groove (sulfuric acid: 30g/L), dipping is removed surperficial oil content, oxidation overlay film etc. for 5 seconds.Then, use the formation groove (30 ℃ of nickel sulfate hexahydrate compound: 30g/L, sodium molybdate dihydrate: 3g/L, citrate trisodium dihydrate: 30g/L, liquid temperatures) of peel ply with current density 20A/dm ²electrolytic treatments 5 seconds forms peel ply on the glassy surface of foils.Then, on peel ply, form main part (hereinafter referred to as main body copper layer).Main body copper layer forms as follows.First, use plating bath (40 ℃ of cupric pyrophosphate: 80g/L, potassium pyrophosphate: 320g/L, ammoniacal liquor: 2ml/L, liquid temperatures) with current density 2.0A/dm ²electrolytic treatments 15 seconds forms the 1st main body copper layer on peel ply.Then, use plating bath (copper sulfate pentahydrate: 160g/L, sulfuric acid: 100g/L, gelatin (Nippi, Inc. manufacture, trade name PBH, weight average molecular weight (MW) 5000): 40 ℃ of 15ppm, chloride ion: 5ppm, liquid temperatures) with current density 3.5A/dm ²electrolytic treatments 150 seconds forms the 2nd main body copper layer on the 1st main body copper layer.Form thus main body copper layer.Then, use plating bath (30 ℃ of copper sulfate pentahydrate: 150g/L, sulfuric acid: 100g/L, liquid temperatures) with current density 30A/dm ²after electrolytic treatments 3 seconds with current density 5A/dm ²electrolytic treatments 70 seconds forms alligatoring foot portions (hereinafter referred to as alligatoring copper layer) on main body copper layer.Then, use antirust treatment trough (28 ℃ of sodium dichromate dihydrate: 3.5g/L, liquid temperatures) with current density 0.5A/dm ²electrolytic treatments is carried out antirust processing for 2.5 seconds.Then, be immersed in the aqueous solution of N-phenyl amino propyl trimethoxy silicane 1wt% and carry out surface treatment.Then, at 80 ℃, be dried 10 minutes.Form thus the ultrathin copper foil with foils of Production Example 1.

(Production Example 2)

Except the creating conditions of main body copper layer with the same ultrathin copper foil forming with foils of Production Example 1.

In this Production Example, main body copper layer forms as follows.First, use plating bath (40 ℃ of copper sulfate pentahydrate: 30g/L, citrate trisodium dihydrate: 40g/L, liquid temperatures) with current density 2.0A/dm ²electrolytic treatments 15 seconds forms the 1st main body copper layer on peel ply.Then, use plating bath (copper sulfate pentahydrate: 160g/L, sulfuric acid: 100g/L, gelatin (Nippi, Inc. manufacture, trade name PBF, weight average molecular weight (MW) 3000): 40 ℃ of 20ppm, chloride ion: 5ppm, liquid temperatures) with current density 3.5A/dm ²electrolytic treatments 150 seconds forms the 2nd main body copper layer on the 1st main body copper layer.Form thus main body copper layer.

(Production Example 3)

Except the creating conditions of main body copper layer with the same ultrathin copper foil forming with foils of Production Example 1.

In this Production Example, main body copper layer forms as follows.First, use plating bath (40 ℃ of copper sulfate pentahydrate: 30g/L, citrate trisodium dihydrate: 40g/L, liquid temperatures) with current density 2.0A/dm ²electrolytic treatments 15 seconds forms the 1st main body copper layer on peel ply.Then, use 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): 40 ℃ of 25ppm, chloride ion: 5ppm, liquid temperatures) with current density 3.5A/dm ²electrolytic treatments 150 seconds forms the 2nd main body copper layer on the 1st main body copper layer.Form thus main body copper layer.

(Production Example 4)

Except the creating conditions of main body copper layer with the same ultrathin copper foil forming with foils of Production Example 1.

In this Production Example, main body copper layer forms as follows.First, use plating bath (40 ℃ of copper sulfate pentahydrate: 30g/L, nickel sulfate hexahydrate compound: 5g/L, citrate trisodium dihydrate: 40g/L, liquid temperatures) with current density 2.0A/dm ²electrolytic treatments 15 seconds forms the 1st main body copper layer on peel ply.Then, use 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): 40 ℃ of 35ppm, chloride ion: 5ppm, liquid temperatures) with current density 3.5A/dm ²electrolytic treatments 150 seconds forms the 2nd main body copper layer on the 1st main body copper layer.Form thus main body copper layer.

(Production Example 5)

Except the creating conditions of main body copper layer with the same ultrathin copper foil forming with foils of Production Example 1.

In this Production Example, main body copper layer forms as follows.First, use plating bath (40 ℃ of copper sulfate pentahydrate: 30g/L, nickel sulfate hexahydrate compound: 5g/L, citrate trisodium dihydrate: 40g/L, liquid temperatures) with current density 2.0A/dm ²electrolytic treatments 15 seconds forms the 1st main body copper layer on peel ply.Then, use plating bath (copper sulfate pentahydrate: 160g/L, sulfuric acid: 100g/L, gelatin (Nippi, Inc. manufacture, trade name PBH, weight average molecular weight (MW) 5000): 40 ℃ of 30ppm, chloride ion: 5ppm, liquid temperatures) with current density 3.5A/dm ²electrolytic treatments 150 seconds forms the 2nd main body copper layer on the 1st main body copper layer.Form thus main body copper layer.

(Production Example 6)

As foils (support metal paper tinsel), on the glassy surface of the thick electrolytic copper foil of 18 μ m, form successively peel ply and ultrathin copper foil layer.Create conditions as follows.

First, by foils at acid elution groove (sulfuric acid: 50g/L), dipping is removed surperficial oil content, oxidation overlay film etc. for 15 seconds.Then, in the formation groove (carboxyl benzotriazole solution: 40 ℃ of reagent, liquid temperatures) of peel ply, dipping is 15 seconds, on the glossy surface of foils, forms peel ply.Then, use plating bath (copper sulfate pentahydrate: 150g/L, sulfuric acid: 150g/L, gelatin (Nippi, Inc. manufacture, trade name PBH, weight average molecular weight (MW) 5000): 40 ℃ of 15ppm, chloride ion: 5ppm, liquid temperatures) with current density 10A/dm ²electrolytic treatments 180 seconds forms main body copper layer on peel ply.Then, use plating bath (30 ℃ of copper sulfate pentahydrate: 150g/L, sulfuric acid: 100g/L, liquid temperatures) with current density 30A/dm ²after electrolytic treatments 3 seconds with current density 5A/dm ²electrolytic treatments 70 seconds forms alligatoring copper layer on main body copper layer.Then, use antirust treatment trough (28 ℃ of sodium dichromate dihydrate: 3.5g/L, liquid temperatures) with current density 0.5A/dm ²electrolytic treatments is carried out antirust processing for 2.5 seconds.Then the aqueous solution that, is immersed in N-phenyl amino propyl trimethoxy silicane 1wt% carries out surface treatment.Then, at 80 ℃, be dried 10 minutes.Form thus the ultrathin copper foil with foils of Production Example 6.

(Production Example 7)

Except the creating conditions of main body copper layer with the same ultrathin copper foil forming with foils of Production Example 1.

In this Production Example, main body copper layer forms as follows.First, use plating bath (40 ℃ of copper sulfate pentahydrate: 30g/L, citrate trisodium dihydrate: 40g/L, liquid temperatures) with current density 2.0A/dm ²electrolytic treatments 15 seconds forms the 1st main body copper layer on peel ply.Then, use plating bath (40 ℃ of copper sulfate pentahydrate: 160g/L, sulfuric acid: 100g/L, chloride ion: 5ppm, liquid temperatures) with current density 3.5A/dm ²electrolytic treatments 150 seconds forms the 2nd main body copper layer on the 1st main body copper layer.Form thus main body copper layer.

(Production Example 8)

Except the creating conditions of main body copper layer with the same ultrathin copper foil forming with foils of Production Example 1.

In this Production Example, main body copper layer forms as follows.First, use plating bath (40 ℃ of copper sulfate pentahydrate: 30g/L, citrate trisodium dihydrate: 40g/L, liquid temperatures) with current density 2.0A/dm ²electrolytic treatments 15 seconds forms the 1st main body copper layer on peel ply.Then, use plating bath (copper sulfate pentahydrate: 160g/L, sulfuric acid: 100g/L, gelatin (Nippi, Inc. manufacture, trade name PBF, weight average molecular weight (MW) 3000): 40 ℃ of 20ppm, liquid temperatures) with current density 3.5A/dm ²electrolytic treatments 150 seconds forms the 2nd main body copper layer on the 1st main body copper layer.Form thus main body copper layer.

(Production Example 9)

Except the creating conditions of main body copper layer with the same ultrathin copper foil forming with foils of Production Example 1.

In this Production Example, main body copper layer forms as follows.First, use plating bath (40 ℃ of copper sulfate pentahydrate: 30g/L, citrate trisodium dihydrate: 40g/L, liquid temperatures) with current density 2.0A/dm ²electrolytic treatments 15 seconds forms the 1st main body copper layer on peel ply.Then, use plating bath (copper sulfate pentahydrate: 160g/L, sulfuric acid: 100g/L, gelatin (Nippi, Inc. manufacture, trade name AP, weight average molecular weight (MW) 8000): 40 ℃ of 30ppm, chloride ion: 5ppm, liquid temperatures) with current density 3.5A/dm ²electrolytic treatments 150 seconds forms the 2nd main body copper layer on the 1st main body copper layer.Form thus main body copper layer.

(Production Example 10)

Except the creating conditions of main body copper layer with the same ultrathin copper foil forming with foils of Production Example 1.

In this Production Example, main body copper layer forms as follows.First, use plating bath (40 ℃ of copper sulfate pentahydrate: 30g/L, citrate trisodium dihydrate: 40g/L, liquid temperatures) with current density 2.0A/dm ²electrolytic treatments 15 seconds forms the 1st main body copper layer on peel ply.Then, use plating bath (copper sulfate pentahydrate: 160g/L, sulfuric acid: 100g/L, gelatin (Nippi, Inc. manufacture, trade name PBF, weight average molecular weight (MW) 3000): 40 ℃ of 5ppm, chloride ion: 5ppm, liquid temperatures) with current density 3.5A/dm ²electrolytic treatments 150 seconds forms the 2nd main body copper layer on the 1st main body copper layer.Form thus main body copper layer.

2. the manufacture of resin varnish

In methylethylketone, dissolve and mix naphthalene ether type epoxy (Dainippon Ink Chemicals manufactures, HP-6000) 20 weight portions, (Dainippon Ink Chemicals manufactures naphthalene type epoxy resin, HP4032D) 5 weight portions, (Lonza Japan Ltd. manufactures cyanate ester resin, PT-30) 17 weight portions, bimaleimide resin (K.I Kasei Co., Ltd. manufacture, BMI-70) 7.5 % by weight, (Tokuyama Corp manufactures NSS-5N to silica dioxide granule, average grain diameter 70nm) 7 weight portions, spherical silicon dioxide (Admatechs Co., Ltd. manufacture SO-25R, average grain diameter 0.5 μ m) 35.5 weight portions, (Shin-Etsu Chemial Co., Ltd manufactures organic silicon granule, KMP600, average grain diameter 5 μ m) 7.5 weight portions, zinc octoate 0.01 weight portion, (Shin-Etsu Chemial Co., Ltd manufactures epoxy silane, KBM-403E) 0.5 weight portion.Then, using high-speed stirring apparatus to stir and being adjusted to nonvolatile component is 70 % by weight, makes resin varnish.

3. the manufacture of prepreg

As fiber base material, use glass woven fabric (Nitto Boseki Co. Ltd's manufacture, T glass woven fabric, WTX-1078, basic weight 48g/m ², thickness 45 μ m), the aforementioned resin varnish making of dip coated, in the heating furnace of 180 ℃ dry 2 minutes, obtains the prepreg of thickness 0.05mm.

4. the manufacture of copper clad laminate

Stacked 4 aforementioned prepregs that obtain, the stacked ultrathin copper foil with foils on its two sides (2 μ m), by carry out 60 minutes (heating 60 minutes after arriving 200 ℃) heating press molding at 200 ℃ of pressure 3MPa, temperature, obtain having on two sides the copper clad laminate of Copper Foil.In addition, the ultrathin copper foil with foils using in each embodiment and comparative example is recorded as table 1 and table 2.

5. evaluate

Use the ultrathin copper foil with foils obtaining in each embodiment and comparative example, carry out following evaluation.Assessment item and content are provided in the lump, and acquired results is shown in table 1 and table 2.

(1) mensuration of Vickers hardness

The mensuration of Vickers hardness is according to JIS Z2244, and according to the following steps, the micro-hardness tester (model MVK-2H) that uses Akashi Corporation to manufacture carries out at 23 ℃.As the sample of normality, use the ultrathin copper foil with foils that has just been formed into main body copper layer.In addition,, as the sample after heat treatment, use in being heated to the baking oven (nitrogen atmosphere) of 230 ℃ and place 1 hour ultrathin copper foil with foils that is formed into main body copper layer afterwards.About condition determination, cutting sample is formed to impression under 3 μ m/ seconds of loading speed, test load 5gf, the condition of 15 seconds retention times, according to the measurement result of impression, calculate Vickers hardness, the value using the mean value of the Vickers hardness of any 5 recording as this condition.

(2) etch-rate (V1, V2)

1. become 40mm * 80mm to obtain sample strip the substrate severing that is laminated with the ultrathin copper foil of having removed foils on two sides.For sample strip, with vernier caliper, read to after decimal point 2, the sheet area of calculating sample strip.

2. on horizontal drying line, sample strip is carried out to 80 ℃ of dry processing of 1 minute * 3 times.

3. the initial stage weight W 0 of working sample sheet (comprising substrate weight).

4. prepare etching solution.

4-1: weigh 60g95% sulfuric acid (manufacture of He Guangchun medicine Co., Ltd., superfine), put into the beaker of 1L.

4-2: pure water is dropped into the beaker using in 4-1, making total amount is 1000cc.

4-3: stir 3 minutes at 30 ℃ ± 1 ℃ with magnetic stirrer.

4-4: weigh 20cc34.5% aquae hydrogenii dioxidi (Kanto Kagaku K. K. manufactures, deer one-level), put into the beaker that 4-1 is used, making total amount is after 1020cc, stirs 3 minutes at 30 ℃ ± 1 ℃.Can obtain thus the etching solution of sulfuric acid 55.9g/L and 34.5% aquae hydrogenii dioxidi 19.6cc/L.

5. impregnated sample sheet in above-mentioned etching solution (liquid temperature: 30 ℃ ± 1 ℃, stirring condition: magnetic stirrer, 250rmp).

6. until the body layer of ultrathin copper foil, by etching completely, was measured the weight W 1 (comprising substrate weight) of a sample strip every 30 seconds.

7. calculate etching weight (W0-W1)/(two sides area=m flooding ²), take X-axis as etching period (second), take Y-axis as etching quality (g/m ²) mapping.According to the slope K 1 for using least square method to calculate between 0～150 second, calculate etch-rate V1 (the μ m/min)=K1 (g/secm of main body copper layer ²) ÷ 8.92 (copper proportion g/cm ³) * 60 (sec/min).

8. then, until the alligatoring copper layer of ultrathin copper foil, by etching completely, was measured the weight W 2 (comprising substrate weight) of a sample strip every 10 seconds.

9. calculate etching weight (W0-W2)/(two sides area=m flooding ²), take X-axis as etching period (second), take Y-axis as etching quality (g/m ²) mapping.According to the slope K 2 for using least square method to calculate between 0～30 second, calculate etch-rate V2 (the μ m/min)=K2 (g/secm of alligatoring copper layer ²) ÷ 8.92 (copper proportion g/cm ³) * 60 (sec/min).

(3) concavo-convex evaluation method

Use from directly over observe the SEM image (2000 times) of the printed circuit board (PCB) gained obtaining (4) described later, to the copper between wiring is residual, carries out binaryzation (Media Cybernetics company manufacture, image processing software; Image Pro Prus ver5.1) calculate residual copper rate.

The original binaryzation of original binaryzation

?	Embodiment 1	Comparative example 1
			Area (μ m 2)	0.7	43.4

Each symbol in table 1 and table 2 is as follows.

◎: below 2

Zero: be greater than below 2 and 10

*: more than 10

(4) insulating properties between fine rule

1. pair on two sides, be laminated with the surface of the substrate of the ultrathin copper foil of having removed foils, with chemical grinding liquid, (Mitsubishi Gas Chemical Co., Ltd manufactures, trade name: CPB-60) at 5 seconds, 23 ℃, carry out soft etching and remove cupric oxide.Then, utilize hot-roll lamination machine that the UV-radiation-sensitive dry film of thickness 25 μ m (Asahi Kasei Corporation's manufacture, SUNFORT UFG-255) is fitted on substrate.Then, describe the position alignment of the glass mask that minimum feature/distance between centers of tracks is the pattern of 20/20 μ m (TOPIC Co., Ltd. manufactures).Then,, to above-mentioned dry film, use above-mentioned glass mask to expose by exposure device (the little Ye Ce device EV-0800 of Co., Ltd.), and develop with aqueous sodium carbonate.Form thus Etching mask.

2. then, using ultrathin copper foil layer as power supply layer electrode, carry out 3A/dm ², the electro-coppering (Ao Ye Pharmaceutical Co., Ltd manufactures 81-HL) of 25 minutes, form the pattern of the copper wiring of thickness approximately 20 μ m.Then, use stripping machine, utilize monoethanolamine solution (Mitsubishi Gas Chemical Co., Ltd manufactures R-100) to peel off aforementioned Etching mask.

3. then, by fast-etching (etching solution identical with etch-rate), remove the ultrathin copper foil layer as power supply layer, form the pattern (pattern-like etching) of L/S=20/20 μ m.Obtain thus printed circuit board (PCB).

4. as test piece, use to replace the stacked insulating resin sheet of solder resist (Sumitomo Bakelite Co manufactures, BLA-3700GS) to solidify the sample obtaining at 220 ℃ of temperature, in 130 ℃ of temperature, humidity 85%, apply under the condition of voltage 10V and evaluate the insulation resistance under continuous wet environment.In addition, resistance value 10 ⁶Ω is evaluated as fault below.

Symbol is as follows.

◎: 300 hours above fault-free

Zero: 150～be less than 300 hours to break down

*: be less than 150 hours and break down

(5) wiring shape (or circuit is linear)

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

Pair use microscope from directly over the profile of circuit bottom while observing the circuit etching evaluate.In addition, the wiring shape when using the section of the circuit after microscopic examination etching is evaluated.

Symbol is as follows.

◎: from directly over while observing, the profile of circuit bottom appears as straight line.And the bottom of bottom does not expand outwardly in section.

Zero: from directly over while observing, the profile of circuit bottom appears as straight line.And the bottom of bottom is little in section.

*: from directly over while observing, the profile of circuit bottom appears as curvilinear part.And the bottom of bottom is large in section.

(6) grain size (μ m)

According to JIS H0501, measure grain size.Step is as follows.

1. pair on two sides, be laminated with the substrate of the ultrathin copper foil of having removed foils, use after FIB (focused ion beam) processing unit (plant) processes, take SIM (Scanning Ion Microscope) and observe photo.

2. according to the standard photographs of the comparison method of stipulating in JIS H0501, calculate the grain size of the section of captured photo.It should be noted that, because the accompanying drawing of this standard is only given to 75 times of observable grain size 0.010mm, multiplying power when therefore consideration is the most similarly schemed and observes and calculating.

[table 1]

[table 2]

In addition, certain above-mentioned execution mode and a plurality of variation can be held within it in the scope of not runing counter to and combine.In addition in above-mentioned execution mode and variation, structure of each portion etc. is illustrated, and its structures etc. can be carried out various changes in meeting scope of the present invention.

The application advocates to take that the Japanese patent application laid of submitting on March 16th, 2012 is willing to that 2012-059742 is as basic priority, and all introducings are so far for its disclosure.

Claims (6)

1. a laminated sheet, at least Copper Foil of one side that it possesses insulating barrier and is positioned at described insulating barrier, thus it is for forming by Copper Foil described in etching the device mounting board that conductor circuit obtains,

Containing sulfuric acid 55.9g/L and 34.5% aquae hydrogenii dioxidi 19.6cc/L and liquid temperature, be that the etch-rate that floods the described Copper Foil under the condition of described laminated sheet in the etching solution of sulfuric acid/hydroperoxide kind of 30 ℃ ± 1 ℃ is more than 0.68 μ m/min and below 1.25 μ m/min.

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

Condition: heating-up temperature is 230 ℃, be 1 hour heating time.

3. laminated sheet according to claim 1 and 2, wherein, the thickness of described Copper Foil is that 0.1 μ m is above and below 5 μ m.

4. according to the laminated sheet described in any one in claim 1～3, wherein, the Vickers hardness of the described Copper Foil after 230 ℃, 1 hour heat treated is more than 180Hv and below 240Hv.

5. according to the laminated sheet described in any one in claim 1～4, wherein, the section grain size of the described Copper Foil after 230 ℃, 1 hour heat treated is below 2.0 μ m.

6. a manufacture method for printed circuit board (PCB), the method comprises:

Preparation possesses insulating barrier and is positioned at least operation of the laminated sheet of the Copper Foil of one side of described insulating barrier, and

By Copper Foil described in selective removal, form the operation of conductor circuit,

Described laminated sheet is the laminated sheet described in any one in claim 1～5.