WO2013136729A1

WO2013136729A1 - Manufacturing method for laminated board and printed wiring board

Info

Publication number: WO2013136729A1
Application number: PCT/JP2013/001432
Authority: WO
Inventors: 哲平伊藤; 大東　範行
Original assignee: 住友ベークライト株式会社; 日本電解株式会社
Priority date: 2012-03-16
Filing date: 2013-03-07
Publication date: 2013-09-19
Also published as: JP2013219337A; TW201352085A; CN104170532A; CN104170532B; JP5378620B2; TWI590718B; KR101528444B1; KR20140133910A

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 0.68µm/min and 1.25µm/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°C+1°C.

Description

LAMINATED BOARD AND PRINTED WIRING BOARD MANUFACTURING METHOD

The present invention relates to a method for manufacturing a laminated board and a printed wiring board.

With the demand for higher functionality of electronic equipment, etc., high-density integration of electronic parts, and further high-density mounting, etc. are progressing. In addition, miniaturization, thinning, high density, and multilayering are progressing.

The semi-additive method is beginning to be performed as a method for efficiently forming a high-density and high-pattern conductor circuit layer on a printed wiring board substrate. The printed wiring board manufacturing method using the semi-additive method is described in, for example, Patent Document 1 and Patent Document 2.

In the manufacturing methods described in

Patent Documents

1 and 2, first, a laminated board in which a copper foil is attached to one surface of an insulating layer is prepared, and a resist pattern is formed on the laminated board. Subsequently, a plating layer is filled in the openings of the resist pattern. Subsequently, the resist pattern is removed. Thereafter, the lower copper foil is etched using the plating layer pattern as a mask, thereby forming a conductor circuit composed of the plating layer and the copper foil.

JP 2003-69218 A JP 2003-60341 A

In the manufacturing process of

Patent Documents

1 and 2, a copper foil residue may be generated on a fine uneven portion formed on the surface of the insulating layer. Etching residue of the copper foil remaining between the conductor circuits causes a short circuit such as an insulation failure of the conductor circuit as the miniaturization progresses. For this reason, it is preferable to remove the etching residue of the copper foil on the surface of the insulating layer.

In order to remove the etching residue of the copper foil, it is necessary to etch the surface of the insulating layer excessively. However, if the insulating layer is etched excessively, the conductor circuit is also etched excessively, so that there are cases where abnormal formation of the conductor circuit, breakage or jumping of the conductor circuit occurs. It is difficult to maintain the wiring shape in a desired shape while performing excessive etching.

As described above, in the laminates of

Patent Documents

1 and 2, there is room for improvement in the balance between reducing the etching residue of the copper foil and maintaining the wiring shape.

According to the present invention,
A laminated plate used for an element mounting substrate, comprising an insulating layer and a copper foil located on at least one surface of the insulating layer, and obtained by forming a conductor circuit by etching the copper foil,
The laminate was placed in a sulfuric acid / hydrogen peroxide etching solution comprising 55.9 g / L of sulfuric acid and 19.6 cc / L of 34.5% hydrogen peroxide solution and having a liquid temperature of 30 ° C. ± 1 ° C. There is provided a laminate having an etching rate of the copper foil under the dipping conditions of 0.68 μm / min or more and 1.25 μm / min or less.

The inventors of the present invention have thought that by increasing the etching rate of the copper foil, it is possible to achieve both reduction of the etching residue of the copper foil and maintenance of the wiring shape.
As a result of further investigation, it has been found that the results of the etching rate evaluation method vary depending on the components of the etchant, the component concentration, and the liquid temperature.
Therefore, by using sulfuric acid, pure water, and hydrogen peroxide solution as the etchant, determining the concentration of the components, and further assuming that the liquid temperature is 30 ° C. ± 1 ° C. I found out.
Furthermore, the present inventors conducted various experiments on the copper etching rate under the preconditions. As a result, the lower limit value of the copper etching rate was set to 0.68 μm / min or more, whereby the etching residue of the copper foil was As a result, the inventors have found that the wiring shape is improved and the present invention has been completed.

Moreover, according to this invention, the process of preparing a laminated board provided with an insulating layer and the copper foil located in at least one surface of the said insulating layer, The process of forming a conductor circuit by selectively removing the said copper foil A method for manufacturing a printed wiring board is provided, wherein the laminated board is the laminated board described above.

According to the present invention, there is provided a laminated board in which the etching residue of copper foil is reduced and the wiring shape is good.

It is sectional drawing which shows typically an example of the manufacturing method of the printed wiring board of 1st Embodiment. It is sectional drawing which shows typically an example of the manufacturing method of the printed wiring board of 1st Embodiment. It is sectional drawing which shows typically an example of the manufacturing method of the printed wiring board of 2nd Embodiment. It is sectional drawing which shows typically an example of the manufacturing method of the printed wiring board of 2nd Embodiment. It is sectional drawing which shows typically an example of the manufacturing method of the printed wiring board of 2nd Embodiment. It is sectional drawing which shows typically an example of the manufacturing method of the printed wiring board of 3rd Embodiment. It is sectional drawing which shows typically the modification of the manufacturing method of the printed wiring board of 3rd Embodiment.

Hereinafter, embodiments of the present invention will be described with reference to the drawings. In all the drawings, the same reference numerals are given to the same components, and the description will be omitted as appropriate.

(First embodiment)
1 and 2 are cross-sectional views showing process steps of the method for manufacturing a printed wiring board according to the first embodiment.
First, an outline of the printed wiring board 101 of the present embodiment will be described.
The manufacturing method of the printed wiring board 101 of the present embodiment includes the following steps. First, a laminate (copper-clad laminate 100) including an insulating layer 102 and a copper foil (copper foil layer 104) located on at least one surface of the insulating layer 102 is prepared. Next, a conductor circuit (conductor circuit 119) is formed by selectively removing the copper foil. The printed wiring board 101 is used as an element mounting board.

The manufacturing method of the printed wiring board 101 of this Embodiment uses the laminated board (copper clad laminated board 100) obtained by forming a conductor circuit by etching a copper foil.
In the laminate (copper-clad laminate 100), the etching rate of the copper foil (copper foil layer 104) is composed of 55.9 g / L of sulfuric acid and 19.6 cc / L of 34.5% hydrogen peroxide, and a liquid. It is specified as 0.68 μm / min or more and 1.25 μm / min or less under the condition that the laminate is immersed in a sulfuric acid / hydrogen peroxide etching solution having a temperature of 30 ° C. ± 1 ° C.

In the copper clad laminate 100, the etching rate of the copper foil layer 104 is specified to be 0.68 μm / min or more. For this reason, in the manufacturing process of the printed wiring board 101, it can suppress that the copper foil layer 104 remains on the insulating layer 102 between the conductor circuits 119, and can make the wiring shape of the conductor circuit 119 favorable.

Hereinafter, details of the manufacturing process of the printed wiring board 101 of the present embodiment will be described.

First, as shown in FIG. 1A, a copper clad laminate 10 with a carrier foil in which a copper foil layer 104 and a carrier foil layer 106 are bonded to both surfaces of an insulating layer 102 is prepared. The copper clad laminate 10 with a carrier foil includes an insulating layer 102, a copper foil layer 104, and a carrier foil layer 106. A carrier foil layer 106 is attached to both surfaces of the insulating layer 102 together with the copper foil layer 104. In this embodiment, the copper foil layer 104 is formed on both surfaces of the insulating layer 102, but the copper foil layer 104 may be formed only on one surface of the insulating layer 102.

As the copper clad laminate 10 with carrier foil, for example, a peelable carrier foil layer 106 is laminated on at least one surface of the copper clad laminate 100. The copper clad laminate 100 (hereinafter sometimes referred to as a laminate) is not particularly limited. For example, a copper foil layer 104 is laminated on at least one surface of an insulating layer 102 having an insulating resin layer containing a base material. A thing can be used (a fiber base material is abbreviate | omitted in the figure). The laminate may be a single layer or may have a multilayer structure. That is, as a laminated board, you may be comprised only by the core layer, However, You may use what has the buildup layer formed on the core layer. For example, a laminate in which a plurality of prepregs are stacked can be used. The prepreg is not particularly limited, and can be obtained by, for example, a method of impregnating a base material such as glass cloth with a resin composition containing a curable resin, a curing agent, a filler, and the like. And as a laminated board, what superposed | stacked the ultra-thin metal foil with a carrier foil on at least one surface and heat-press-molded etc. can be used. Moreover, the same material as that of the core layer may be used for the interlayer insulating layer of the buildup layer, but the base material or the resin composition may be different. In the present embodiment, the insulating layer 102 corresponds to an insulating resin layer constituting a core layer or a build-up layer, and may be either a single layer or a multilayer structure. An example using a laminated board having a build-up layer will be described later in the second embodiment.

As the resin composition constituting the laminate and the interlayer insulating layer used in the present embodiment, a known resin used as an insulating material of a printed wiring board (hereinafter also referred to as an insulating resin composition) can be used. Usually, curable resins having good heat resistance and chemical resistance are mainly used. The said resin composition is not specifically limited, It is preferable that it is a resin composition containing the curable resin hardened | cured by heat and / or light irradiation at least.

Examples of the curable resin include urea (urea) resin, melamine resin, maleimide compound, polyurethane resin, unsaturated polyester resin, resin having a benzoxazine ring, bisallyl nadiimide compound, vinyl benzyl resin, vinyl benzyl ether resin, Examples include benzocyclobutene resin, cyanate resin, and epoxy resin. Among these, the curable resin is preferably a combination having a glass transition temperature of 200 ° C. or higher. For example, spiro ring-containing, heterocyclic, trimethylol type, biphenyl type, naphthalene type, anthran type, novolak type bifunctional or trifunctional epoxy resin, cyanate resin (including prepolymer of cyanate resin), maleimide compound, It is preferable to use a benzocyclobutene resin or a resin having a benzoxazine ring. When using an epoxy resin and / or a cyanate resin, the linear expansion is reduced and the heat resistance is remarkably improved. In addition, combining epoxy resin and / or cyanate resin with a high amount of fillers has the advantage of excellent flame retardancy, heat resistance, impact resistance, high rigidity, and electrical properties (low dielectric constant, low dielectric loss tangent) There is. Here, the improvement in heat resistance is that the glass transition temperature becomes 200 ° C. or higher after the curing reaction of the curable resin, the thermal decomposition temperature of the cured resin composition increases, and the reaction residue at 250 ° C. or higher. This is considered to be due to the reduction of the low molecular weight. Furthermore, the improvement in flame retardancy is attributed to the fact that the benzene ring is easily carbonized (graphitized) and a carbonized portion is generated because of the high proportion of the benzene ring due to its structure because of the aromatic curable resin. I think that.

The resin composition may further contain a flame retardant as long as the effects of the present invention are not impaired, but a non-halogen flame retardant is preferred from the environmental aspect. Examples of the flame retardant include an organic phosphorus flame retardant, an organic nitrogen-containing phosphorus compound, a nitrogen compound, a silicone flame retardant, and a metal hydroxide. Examples of organophosphorus flame retardants include phosphine compounds such as HCA, HCA-HQ, and HCA-NQ manufactured by Sanko Co., Ltd., and phosphorus-containing benzoxazine compounds such as HFB-2006M manufactured by Showa Polymer Co., Ltd. Phosphoric acid ester compounds such as PPQ manufactured by Clariant Co., Ltd., OP930 manufactured by Clariant Co., Ltd., PX200 manufactured by Daihachi Chemical Co., Ltd., phosphorus-containing epoxy resins such as FX289 and FX310 manufactured by Toto Kasei Co., Ltd. Examples thereof include phosphorus-containing phenoxy resins such as ERF001 manufactured by Co., Ltd. Examples of organic nitrogen-containing phosphorus compounds include phosphate ester compounds such as SP670 and SP703 manufactured by Shikoku Kasei Kogyo Co., Ltd., SPB100 and SPE100 manufactured by Otsuka Chemical Co., Ltd., and FP-series manufactured by Fushimi Seisakusho Co., Ltd. Examples thereof include phosphazene compounds. Examples of the metal hydroxide include magnesium hydroxide such as UD650 and UD653 manufactured by Ube Materials Co., Ltd., CL310 manufactured by Sumitomo Chemical Co., Ltd., aluminum hydroxide such as HP-350 manufactured by Showa Denko Co., Ltd., and the like. It is done.

Examples of the epoxy resin used in the resin composition include bisphenol A type epoxy resin, bisphenol F type epoxy resin, phenol novolac type epoxy resin, cresol novolac type epoxy resin, bisphenol A novolak type epoxy resin, biphenyl novolac type epoxy resin, Anthracene type epoxy resin, dihydroanthracene type epoxy resin, trifunctional phenol type epoxy resin, tetrafunctional phenol type epoxy resin, naphthalene type epoxy resin, biphenyl type epoxy resin, aralkyl modified epoxy resin, alicyclic epoxy resin, polyol type epoxy resin , Glycidylamine, glycidyl ester, butadiene epoxidized compounds, hydroxyl group-containing silicone resins and epichlorohydrin Obtained compounds. Among these, the epoxy resin is preferably a naphthalene type or arylalkylene type epoxy resin. The aryl alkylene type epoxy resin refers to an epoxy resin containing one or more combinations of an aromatic group and an alkylene group such as methylene in the repeating unit, and is excellent in heat resistance, flame retardancy, and mechanical strength. By using a naphthalene type or aryl alkylene type epoxy resin, moisture absorption solder heat resistance (solder heat resistance after moisture absorption) and flame retardancy can be improved in the resulting laminate. Naphthalene type epoxy includes DIC Corporation's HP-4700, HP-4770, HP-4032D, HP-5000, HP-6000, Nippon Kayaku Co., Ltd. NC-7300L, Nippon Steel Chemical Co., Ltd. ESN-375 manufactured by Nippon Kayaku Co., Ltd., NC-3000, NC-3000L, NC-3000-FH manufactured by Nippon Kayaku Co., Ltd., NC manufactured by Nippon Kayaku Co., Ltd. -7300L, ESN-375 manufactured by Nippon Steel Chemical Co., Ltd.

The cyanate resin used in the resin composition can be obtained, for example, by reacting a cyanogen halide compound with phenols. Specific examples of cyanate resins include novolak cyanate resins such as phenol novolac type cyanate resins and cresol novolak type cyanate resins, naphthol aralkyl type cyanate resins, dicyclopentadiene type cyanate resins, biphenyl type cyanate resins, and bisphenol A type cyanate resins. And bisphenol type cyanate resins such as bisphenol AD type cyanate resin and tetramethyl bisphenol F type cyanate resin.

Among these, it is particularly preferable to include a novolak type cyanate resin, a naphthol aralkyl type cyanate resin, a dicyclopentadiene type cyanate resin, and a biphenyl type cyanate resin. Furthermore, the resin composition preferably contains 10% by weight or more of this cyanate resin in the total solid content of the resin composition. Thereby, the heat resistance (glass transition temperature, thermal decomposition temperature) of a prepreg can be improved. Further, the thermal expansion coefficient of the prepreg (particularly, the thermal expansion coefficient in the thickness direction of the prepreg) can be reduced. When the thermal expansion coefficient in the thickness direction of the prepreg is lowered, the stress strain of the multilayer printed wiring can be reduced. Furthermore, in a multilayer printed wiring board having fine interlayer connection portions, the connection reliability can be greatly improved.

Among the novolak type cyanate resins used in the resin composition, a novolak type cyanate resin represented by the following formula (1) is preferable. A novolac cyanate resin represented by the formula (1) having a weight average molecular weight of 2,000 or more, more preferably 2,000 to 10,000, still more preferably 2,200 to 3,500, and a weight average molecular weight of 1500 or less, more It is preferably used in combination with a novolak-type cyanate resin represented by the formula (1) of 200 to 1,300 (hereinafter, “to” represents that it includes an upper limit value and a lower limit value unless otherwise specified). ). In the present embodiment, the weight average molecular weight is a value measured by a gel-permeation chromatography method in terms of polystyrene.

In formula (1), n represents an integer of 0 or more.
Moreover, as cyanate resin, the cyanate resin represented by following General formula (2) is also used suitably. Cyanate resins represented by the following general formula (2) include naphthols such as α-naphthol and β-naphthol, p-xylylene glycol, α, α'-dimethoxy-p-xylene, 1,4-di (2- It is obtained by condensing naphthol aralkyl resin obtained by reaction with hydroxy-2-propyl) benzene and cyanic acid. In the general formula (2), n is 1 or more, but is more preferably 10 or less. When n is 10 or less, the resin viscosity is not high, the impregnation property to the base material is good, and the deterioration of the performance as a laminate can be suppressed. In addition, intramolecular polymerization hardly occurs at the time of synthesis, and the liquid separation property at the time of washing with water can be improved, so that the yield can be prevented from being lowered.

In formula (2), R represents a hydrogen atom or a methyl group, R may be the same or different, and n represents an integer of 1 or more.

Further, as the cyanate resin, a dicyclopentadiene type cyanate resin represented by the following general formula (3) is also preferably used. In the dicyclopentadiene type cyanate resin represented by the following general formula (3), n in the following general formula (3) is more preferably 0 or more and 8 or less. When n is 8 or less, the resin viscosity is not high, the impregnation property to the base material is good, and the deterioration of the performance as a laminated board can be prevented. Moreover, by using a dicyclopentadiene type cyanate resin, it is excellent in low hygroscopicity and chemical resistance.

In the formula (3), n represents an integer of 0 to 8.

Moreover, the resin composition may further contain a curing accelerator. For example, if the curable resin is an epoxy resin or a cyanate resin, a curing accelerator for a phenol resin, an epoxy resin, or a cyanate resin can be used. The phenol resin is not particularly limited. For example, a phenol novolak resin, a cresol novolak resin, a bisphenol A novolak resin, an arylalkylene type novolak resin or the like novolak type phenol resin, an unmodified resole phenol resin, tung oil, linseed oil, walnut oil Examples thereof include resol type phenol resins such as oil-modified resol phenol resins modified with the above. As said phenol resin, a phenol novolak or a cresol novolak resin is preferable. Among these, biphenyl aralkyl-modified phenol novolac resin is preferable from the viewpoint of moisture absorption solder heat resistance.
One of these can be used alone, or two or more having different weight average molecular weights can be used in combination, or one or two or more of these prepolymers can be used in combination.

The curing accelerator is not particularly limited. For example, organic metals such as zinc naphthenate, cobalt naphthenate, tin octylate, cobalt octylate, bisacetylacetonate cobalt (II), trisacetylacetonate cobalt (III), and the like. Salts, tertiary amines such as triethylamine, tributylamine, diazabicyclo [2,2,2] octane, 2-methylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 2-ethyl-4-ethylimidazole 1-benzyl-2-methylimidazole, 1-benzyl-2-phenylimidazole, 2-undecylimidazole, 1-cyanoethyl-2-ethyl-4-methylimidazole, 1-cyanoethyl-2-undecylimidazole, 2-phenyl-4-methyl Imidazoles such as 5-hydroxyimidazole, 2-phenyl-4,5-dihydroxyimidazole, 2,3-dihydro-1H-pyrrolo (1,2-a) benzimidazole, phenolic compounds such as phenol, bisphenol A, nonylphenol, Examples include acetic acid, benzoic acid, salicylic acid, organic acids such as p-toluenesulfonic acid, onium salt compounds, and the like, or mixtures thereof. One of these can be used alone, including derivatives thereof, or two or more of these can be used in combination.

The curable resin may contain a maleimide compound from the viewpoint of heat resistance. The maleimide compound is not particularly limited as long as it is a compound having one or more maleimide groups in one molecule. Specific examples thereof include N-phenylmaleimide, N-hydroxyphenylmaleimide, bis (4-maleimidophenyl) methane, 2,2-bis {4- (4-maleimidophenoxy) -phenyl} propane, bis (3,5 -Dimethyl-4-maleimidophenyl) methane, bis (3-ethyl-5-methyl-4-maleimidophenyl) methane, bis (3,5-diethyl-4-maleimidophenyl) methane, polyphenylmethanemaleimide, these maleimide compounds Or a prepolymer of a maleimide compound and an amine compound.

The curable resin may contain a phenoxy resin, a polyvinyl alcohol resin, a polyimide, a polyamide, a polyamideimide, a polyethersulfone resin, or a polyphenylene ether resin from the viewpoint of adhesion to the metal foil. .

Examples of the phenoxy resin include a phenoxy resin having a bisphenol skeleton, a phenoxy resin having a naphthalene skeleton, and a phenoxy resin having a biphenyl skeleton. A phenoxy resin having a structure having a plurality of these skeletons can also be used.
Among these, it is preferable to use a phenoxy resin having a biphenyl skeleton and a bisphenol S skeleton as the phenoxy resin. Thereby, the glass transition temperature of the phenoxy resin can be increased due to the rigidity of the biphenyl skeleton, and the adhesion between the phenoxy resin and the metal can be improved due to the presence of the bisphenol S skeleton. As a result, the heat resistance of the insulating layer 102 can be improved, and the adhesion of the wiring portion (conductor circuit 118) to the insulating layer 102 can be improved when a multilayer substrate is manufactured. It is also preferable to use a phenoxy resin having a bisphenol A skeleton and a bisphenol F skeleton as the phenoxy resin. Thereby, the adhesiveness to the insulating layer 102 of a wiring part can further be improved at the time of manufacture of a multilayer substrate.

Examples of commercially available phenoxy resins include FX280 and FX293 manufactured by Toto Kasei Co., Ltd., YX8100, YX6954, YL6974, YL7482, YL7553, YL6793, YL7213, and YL7290 manufactured by Japan Epoxy Resin Co., Ltd. The molecular weight of the phenoxy resin is not particularly limited, but the weight average molecular weight is preferably 5,000 to 70,000, and more preferably 10,000 to 60,000.
When the phenoxy resin is used, its content is not particularly limited, but it is preferably 1 to 40% by weight, more preferably 5 to 30% by weight based on the entire resin composition.

Examples of commercially available polyvinyl alcohol resins include Denka Butylal 4000-2, 5000-A, 6000-C and 6000-EP manufactured by Denki Kagaku Kogyo Co., Ltd., S-Rec BH Series, BX Series, KS manufactured by Sekisui Chemical Co., Ltd. Series, BL series, BM series and the like. Particularly preferred are those having a glass transition temperature of 80 ° C. or higher.

Commercially available products of polyimide, polyamide, and polyamideimide include “Viromax HR11NN (registered trademark)” and “HR-16NN” and “HR15ET” manufactured by Toyobo Co., Ltd., and polyamide imide “KS” manufactured by Hitachi Chemical Co., Ltd. -9300 "and the like. “Neoprim C-1210” manufactured by Mitsubishi Gas Chemical Company, Inc., soluble polyimide “Rika Coat SN20 (registered trademark)” and “Rika Coat PN20 (registered trademark)” manufactured by Shin Nippon Rika Co., Ltd., GE Plastics Co., Ltd. Polyetherimide “Ultem (registered trademark)” manufactured by DIC Corporation, “V8000” and “V8002” and “V8005” manufactured by DIC Corporation: “BPAM155” manufactured by Nippon Kayaku Co., Ltd. and the like.

As a commercial item of polyethersulfone resin, a well-known thing can be used, for example, PES4100P, PES4800P, PES5003P, and PES5200P by Sumitomo Chemical Co., Ltd. can be mentioned.

Examples of polyphenylene ether resins include poly (2,6-dimethyl-1,4-phenylene) oxide, poly (2,6-diethyl-1,4-phenylene) oxide, and poly (2-methyl-6-ethyl-). 1,4-phenylene) oxide, poly (2-methyl-6-propyl-1,4-phenylene) oxide, poly (2,6-dipropyl-1,4-phenylene) oxide, poly (2-ethyl-6- And propyl-1,4-phenylene) oxide. Examples of commercially available products include Japanese G.P. E. “Noryl PX9701 (registered trademark)” (number average molecular weight Mn = 14,000), “Noryl 640-111 (registered trademark)” (number average molecular weight Mn = 25,000) manufactured by Plastic, and “SA202” manufactured by Asahi Kasei Corporation (Number average molecular weight Mn = 20,000) and the like, and these can be used by reducing the molecular weight by a known method.

Among these, reactive oligophenylene oxide having a terminal modified with a functional group is preferable. Thereby, compatibility with the curable resin is improved, and a three-dimensional cross-linked structure between the polymers can be formed, so that the mechanical strength is excellent. For example, 2,2 ′, 3,3 ′, 5,5′-hexamethylbiphenyl-4,4′-diol-2,6-dimethylphenol polycondensate described in JP-A-2006-28111 and A reaction product with chloromethylstyrene is mentioned.
Such reactive oligophenylene oxide can be produced by a known method. Commercial products can also be used. For example, OPE-2st 2200 (manufactured by Mitsubishi Gas Chemical Co., Inc.) can be preferably used.
The weight average molecular weight of the reactive oligophenylene oxide is preferably 2,000 to 20,000, and more preferably 4,000 to 15,000. When the weight average molecular weight of reactive oligophenylene oxide exceeds 20,000, it becomes difficult to dissolve in a volatile solvent. On the other hand, when the weight average molecular weight is less than 2,000, the crosslink density becomes too high, which adversely affects the elastic modulus and flexibility of the cured product.

The amount of the curable resin in the resin composition used in the present embodiment is not particularly limited as long as it is appropriately adjusted according to the purpose, but the curable resin is 10 to 10% in the total solid content of the resin composition. It is preferably 90% by weight, more preferably 20 to 70% by weight, still more preferably 25 to 50% by weight.
When an epoxy resin and / or cyanate resin is used as the curable resin, the epoxy resin is preferably 5 to 50% by weight in the total solid content of the resin composition, and the epoxy resin is preferably 5% by weight. Preferably it is ˜25% by weight. The total solid content of the resin composition is preferably 5 to 50% by weight of the cyanate resin, and more preferably 10 to 25% by weight of the cyanate resin.

It is preferable from the viewpoint of low thermal expansion and mechanical strength that the resin composition contains an inorganic filler. The inorganic filler is not particularly limited, but for example, silicates such as talc, fired clay, unfired clay, mica, glass, oxides such as titanium oxide, alumina, silica, fused silica, calcium carbonate, magnesium carbonate, hydrous Carbonates such as talcite, aluminum hydroxide, boehmite (AlO (OH), boehmite commonly referred to as “pseudo” boehmite (ie, Al 2 O 3 .xH 2 O, where x = 1 to 2), magnesium hydroxide, calcium hydroxide Metal hydroxides such as barium sulfate, calcium sulfate, calcium sulfite, sulfates or sulfites, zinc borate, barium metaborate, aluminum borate, calcium borate, sodium borate, etc. borate, aluminum nitride Boron nitride, silicon nitride, carbon nitride nitride, etc., titanium titanate Lithium, and titanium salt such as barium titanate. It is possible to use one kind among these alone, it can be used in combination of two or more.

Among these, magnesium hydroxide, aluminum hydroxide, boehmite, silica, fused silica, talc, calcined talc, and alumina are preferable. Silica is particularly preferable in terms of low thermal expansion and insulation reliability, and spherical fused silica is more preferable. Moreover, aluminum hydroxide is preferable in terms of flame resistance. Moreover, in this Embodiment, since it is a base material which is easy to impregnate even if it is an inorganic filler, the quantity of an inorganic filler can be increased in the said resin composition. When the inorganic filler has a high concentration in the resin composition, the drill wearability is deteriorated, but when the inorganic filler is boehmite, the drill wearability is preferable.

The particle diameter of the inorganic filler is not particularly limited, but an inorganic filler having a monodispersed average particle diameter can be used, or an inorganic filler having a polydispersed average particle diameter can be used. Furthermore, one or two or more inorganic fillers having an average particle size of monodisperse and / or polydisperse may be used in combination. The average particle size of the inorganic filler is not particularly limited, but is preferably 0.1 μm to 5.0 μm, and particularly preferably 0.1 μm to 3.0 μm. If the particle size of the inorganic filler is less than the lower limit, the viscosity of the resin composition becomes high, which may affect workability during prepreg production. When the upper limit is exceeded, phenomena such as sedimentation of the inorganic filler may occur in the resin composition. The average particle diameter can be measured using a laser diffraction / scattering particle size distribution measuring device (manufactured by Shimadzu Corporation, general equipment such as SALD-7000).

The content of the inorganic filler is not particularly limited, but is preferably 10 to 90% by weight, further 30 to 80% by weight, and further 50 to 75% by weight based on the total solid content of the resin composition. It is preferable. In the case where the resin composition contains a cyanate resin and / or a prepolymer thereof, the content of the inorganic filler is preferably 50 to 75% by weight in the total solid content of the resin composition. If the inorganic filler content exceeds the above upper limit, the fluidity of the resin composition may be extremely poor, which may be undesirable, and if it is less than the lower limit, the strength of the insulating layer made of the resin composition is not sufficient, It may not be preferable.

The resin composition used in the present embodiment can also contain a rubber component. For example, preferable examples of the rubber particles that can be used in the present embodiment include core-shell type rubber particles and crosslinked acrylonitrile butadiene rubber particles. Cross-linked styrene butadiene rubber particles, acrylic rubber particles, silicone particles and the like.

The core-shell type rubber particles are rubber particles having a core layer and a shell layer. For example, a two-layer structure in which an outer shell layer is formed of a glassy polymer and an inner core layer is formed of a rubbery polymer, or Examples include a three-layer structure in which the outer shell layer is made of a glassy polymer, the intermediate layer is made of a rubbery polymer, and the core layer is made of a glassy polymer. The glassy polymer layer is made of, for example, a polymer of methyl methacrylate, and the rubbery polymer layer is made of, for example, a butyl acrylate polymer (butyl rubber). Specific examples of the core-shell type rubber particles include Staphyloid AC3832, AC3816N (trade name, manufactured by Ganz Kasei Co., Ltd.), and Metabrene KW-4426 (trade name, manufactured by Mitsubishi Rayon Co., Ltd.). Specific examples of the crosslinked acrylonitrile butadiene rubber (NBR) particles include XER-91 (average particle size 0.5 μm, manufactured by JSR Corporation).

Specific examples of the crosslinked styrene butadiene rubber (SBR) particles include XSK-500 (average particle diameter 0.5 μm, manufactured by JSR Corporation). Specific examples of the acrylic rubber particles include methabrene W300A (average particle size 0.1 μm), W450A (average particle size 0.2 μm) (manufactured by Mitsubishi Rayon Co., Ltd.), and the like.

The silicone particles are not particularly limited as long as they are rubber elastic fine particles formed of organopolysiloxane. For example, fine particles made of silicone rubber (organopolysiloxane crosslinked elastomer) itself, and a core portion made of silicone mainly composed of two-dimensional crosslinking. Examples thereof include core-shell structured particles coated with silicone mainly composed of a three-dimensional crosslinking type. Silicone rubber fine particles include KMP-605, KMP-600, KMP-597, KMP-594 (manufactured by Shin-Etsu Chemical Co., Ltd.), Trefil E-500, Trefil E-600 (manufactured by Toray Dow Corning Co., Ltd.), etc. Commercial products can be used.

The above resin composition may further contain a coupling agent. The coupling agent improves the wettability of the interface between the curable resin and the inorganic filler, thereby uniformly fixing the resin and the inorganic filler to the base material, heat resistance, especially solder heat resistance after moisture absorption Is added to improve the quality.

Although the said coupling agent is not specifically limited, For example, an epoxy silane coupling agent, a cationic silane coupling agent, an aminosilane coupling agent, a titanate coupling agent, a silicone oil type coupling agent etc. are mentioned. Thereby, the wettability with the interface of an inorganic filler can be made high, and thereby heat resistance can be improved more.
The amount of the coupling agent to be added is not particularly limited, but is preferably 0.05 to 3 parts by weight, particularly preferably 0.1 to 2 parts by weight with respect to 100 parts by weight of the inorganic filler. If the content is less than the lower limit, the inorganic filler cannot be sufficiently coated, and thus the effect of improving the heat resistance may be reduced. If the content exceeds the upper limit, the reaction is affected, and the bending strength is reduced. There is a case.

The resin composition used in the present embodiment includes an antifoaming agent, a leveling agent, an ultraviolet absorber, a foaming agent, an antioxidant, a flame retardant, a flame retardant aid such as silicone powder, and an ion scavenger as necessary. You may add additives other than the said components, such as.

The above resin composition preferably contains at least an epoxy resin, a cyanate resin, and an inorganic filler, from the viewpoint of easily realizing low linear expansion, high rigidity, and high heat resistance of the prepreg. Among them, the solid content of the resin composition preferably contains 5 to 50% by weight of epoxy resin, 5 to 50% by weight of cyanate resin, and 10 to 90% by weight of inorganic filler, and further contains 5 to 50% of epoxy resin. Preferably, it contains ˜25 wt%, cyanate resin 10˜25 wt%, and inorganic filler 30˜80 wt%.

The prepreg used in the present embodiment is obtained by impregnating or coating a base material with a varnish of a resin composition. As the base material, well-known ones used for various types of laminates for electrical insulating materials are used. Can be used. Examples of the material for the substrate include inorganic fibers such as E glass, D glass, NE glass, T glass, S glass, and Q glass, organic fibers such as polyimide, polyester, and tetrafluoroethylene, and mixtures thereof. It is done. These base materials have shapes such as woven fabric, non-woven fabric, low-ink, chopped strand mat, surfacing mat, etc., and the material and shape are selected depending on the intended use and performance of the molded product, and can be used alone or as required. It can be used from more than a variety of materials and shapes. The thickness of the base material is not particularly limited, but usually about 0.01 to 0.5 mm is used, and the surface is treated with a silane coupling agent or the like, or mechanically opened and flattened. These are suitable in terms of heat resistance, moisture resistance and processability. The prepreg is usually impregnated or coated with a resin so that the resin content is 20 to 90% by weight after drying, and is heated and dried at a temperature of 120 to 220 ° C. for 1 to 20 minutes. A semi-cured state (B stage state) can be obtained. Furthermore, a laminated sheet can be obtained by laminating 1 to 20 sheets of this prepreg and laminating them by heating and pressing in a configuration in which an ultrathin copper foil with a carrier foil is disposed on both sides thereof. The thickness of the plurality of prepreg layers varies depending on the application, but a thickness of 0.03 to 2 mm is usually preferable. As a laminating method, a normal laminating method can be applied. For example, a multistage press, a multistage vacuum press, continuous molding, an autoclave molding machine or the like is used, and the temperature is usually 100 to 250 ° C., the pressure is 0.2 to 10 MPa, and the heating time is used. Lamination can be performed under conditions of 0.1 to 5 hours, or lamination can be performed under conditions of lamination conditions of 50 to 150 ° C., 0.1 to 5 MPa, and vacuum pressure of 1.0 to 760 mmHg using a vacuum laminating apparatus.

Further, the ultrathin copper foil with a carrier foil (copper foil layer 104) is formed with a bumpy electrodeposited layer (called burnt plating on the roughened surface of the ultrathin copper foil; see, for example, JP-A-9-195096). Or roughening surface treatment by oxidation treatment, reduction treatment, etching, or the like. Thereby, a bumped portion (hereinafter also referred to as a roughened foot portion) is formed on one surface of the bulk portion of the copper foil layer 104.

Further, in the present embodiment, as the copper foil layer 104, copper containing an additive metal component such as nickel or aluminum in addition to copper foil made of copper (excluding contaminants inevitably mixed in the manufacturing process) is used. Foil may be used (in this case, the copper content is not particularly limited, but is preferably 90% by weight or more, more preferably 95% by weight or more based on the total weight of all metal components constituting the copper foil layer 104). It is preferably 99% by weight or more, and the additive metal component may be used alone or in combination of two or more. Further, instead of the copper foil layer 104, a metal foil such as a nickel foil or an aluminum foil may be used.

Here, a detailed method of forming a peelable type copper foil used for the copper foil layer 104 will be described.
The method for producing the copper foil used in the present embodiment is not particularly limited. For example, in the case of producing a peelable type copper foil having a carrier, a metal that becomes a release layer on a carrier foil having a thickness of 10 to 50 μm, etc. An inorganic compound or organic compound layer is formed, and a copper foil is formed on the release layer by plating. As the plating solution, for example, copper sulfate or copper pyrophosphate can be used. Further, various additives may be added to the bath in consideration of the physical properties and smoothness of the copper foil. Note that the peelable type metal foil is a metal foil having a carrier and is a metal foil that can be peeled off by the carrier.

In the formation of the present embodiment, the formation of the copper foil on the release layer can be performed by, for example, cathodic electrolysis using a copper sulfate plating bath containing gelatin and chloride ions as additives. The copper sulfate plating bath contains, for example, 15 to 35 ppm of gelatin having an average molecular weight of 5000 or less. Further, the copper sulfate plating bath contains, for example, a chloride ion concentration of 0.1 to 100 ppm, preferably 0.5 to 50 ppm, particularly preferably 1 to 25 ppm.
In this case, the formation of the copper foil is performed by using the carrier foil on which the release layer is formed as a cathode, performing electrolytic treatment using the copper sulfate plating bath, and copper plating on the release layer. According to such a method for forming a copper foil, it is possible to form a copper foil that has an appropriate mechanical strength even after high-temperature heating, is excellent in etching properties, and is excellent in handling properties. Such an effect results from the fact that the crystals constituting the copper foil can be made finer by adding gelatin.

When the average molecular weight of gelatin is 5000 or less, recrystallization of the thin copper layer due to heating can be suppressed. Thereby, miniaturization of the crystal after heating is realized. Although the reason for this has not been fully elucidated, by making the molecular weight of gelatin below a certain value, it becomes easier for gelatin to be taken into the grain boundaries during plating, and as a result, it is possible to suppress the progress of recrystallization. This is probably because of this. The average molecular weight of gelatin is preferably 500 to 5000, and more preferably 1000 to 5000. By setting the average molecular weight of gelatin to 500 or more, it is possible to suppress the gelatin added to the copper sulfate plating bath from being decomposed in an acidic solution and decomposed into an organic compound such as a low molecular weight amino acid. Thereby, it can suppress that the effect of preventing recrystallization by gelatin being taken in into a crystal grain boundary at the time of plating falls.

The gelatin concentration in the copper sulfate plating bath is preferably 15 to 35 ppm. When the gelatin concentration is 15 ppm or more, the effect of suppressing recrystallization by heating can be sufficiently obtained. For this reason, it becomes possible to maintain a fine crystal state after heating. When the gelatin concentration is 35 ppm or less, it is possible to suppress an increase in internal stress of the copper foil formed by plating. Thereby, it can suppress that an ultra-thin copper foil with a carrier foil curls, and a malfunction generate | occur | produces at the time of conveyance.

As the copper sulfate plating bath, for example, a sulfuric acid copper sulfate plating bath containing copper sulfate pentahydrate, sulfuric acid, gelatin and chlorine is preferably used. The concentration of copper sulfate pentahydrate in the copper sulfate plating bath is preferably 50 g / L to 300 g / L, more preferably 100 g / L to 200 g / L. The concentration of sulfuric acid is preferably 40 g / L to 160 g / L, more preferably 80 g / L to 120 g / L. The concentration of gelatin is as described above. The chloride ion concentration is preferably 1 to 20 ppm, more preferably 3 to 10 ppm. The solvent for the plating bath is usually water. The temperature of the plating bath is preferably 20 to 60 ° C., more preferably 30 to 50 ° C. The current density during the electrolytic treatment is preferably 1 to 15 A / dm 2, more preferably 2 to 10 A / dm 2.

When forming the copper foil, strike plating using a so-called good plating bath can be used before the electrolytic treatment using the copper sulfate plating bath to prevent the generation of pinholes. Examples of the plating bath used for strike plating include a copper pyrophosphate plating bath, a copper citrate plating bath, a copper citrate nickel plating bath, and the like.

As the copper pyrophosphate plating bath, for example, a plating bath containing copper pyrophosphate and potassium pyrophosphate is suitable. The concentration of copper pyrophosphate in the copper pyrophosphate plating bath is preferably 60 g / L to 110 g / L, more preferably 70 g / L to 90 g / L. The concentration of potassium pyrophosphate is preferably 240 g / L to 470 g / L, more preferably 300 g / L to 400 g / L. The solvent for the plating bath is usually water. The pH of the plating bath is preferably 8.0 to 9.0, more preferably 8.2 to 8.8. In order to adjust the pH value, ammonia water or the like may be added (hereinafter the same). The temperature of the plating bath is preferably 20 to 60 ° C., more preferably 30 to 50 ° C. The current density during the electrolytic treatment is preferably 0.5 to 10 A / dm ² , more preferably 1 to 7 A / dm ² . The electrolytic treatment time is preferably 5 to 40 seconds, more preferably 10 to 30 seconds.

As the copper citrate plating bath, for example, a plating bath containing copper sulfate pentahydrate and trisodium citrate dihydrate is suitable. The concentration of copper sulfate pentahydrate in the copper citrate plating bath is preferably 10 g / L to 50 g / L, more preferably 20 g / L to 40 g / L. The concentration of trisodium citrate dihydrate is preferably 20 g / L to 60 g / L, more preferably 30 g / L to 50 g / L. The solvent for the plating bath is usually water. The pH of the plating bath is preferably 5.5 to 7.5, more preferably 6.0 to 7.0. The temperature of the plating bath is preferably 20 to 60 ° C., more preferably 30 to 50 ° C. The current density during the electrolytic treatment is preferably 0.5 to 8 A / dm ² , more preferably 1 to 4 A / dm ² . The electrolytic treatment time is preferably 5 to 40 seconds, more preferably 10 to 30 seconds.

As the copper nickel citrate plating bath, for example, a plating bath containing copper sulfate pentahydrate, nickel sulfate hexahydrate and trisodium citrate dihydrate is suitable. The concentration of copper sulfate pentahydrate in the copper nickel citrate plating bath is preferably 10 g / L to 50 g / L, more preferably 20 g / L to 40 g / L. The concentration of nickel sulfate hexahydrate is preferably 1 g / L to 10 g / L, more preferably 3 g / L to 8 g / L. The concentration of trisodium citrate dihydrate is preferably 20 g / L to 60 g / L, more preferably 30 g / L to 50 g / L. The solvent for the plating bath is usually water. The pH of the plating bath is preferably 5.5 to 7.5, more preferably 6.0 to 7.0. The temperature of the plating bath is preferably 20 to 60 ° C., more preferably 30 to 50 ° C. The current density during the electrolytic treatment is preferably 0.5 to 8 A / dm ² , more preferably 1 to 4 A / dm ² . The electrolytic treatment time is preferably 5 to 40 seconds, more preferably 10 to 30 seconds.

The release layer is an inorganic compound or organic compound layer such as a metal oxide, and a known layer can be used as long as it can be peeled off even when subjected to heat treatment at 100 to 300 ° C. during lamination. As the metal oxide, for example, zinc, chromium, nickel, copper, molybdenum, an alloy system, or a mixture of a metal and a metal compound is used. As an organic compound, it is preferable to use what consists of 1 type, or 2 or more types selected from a nitrogen-containing organic compound, a sulfur-containing organic compound, and carboxylic acid.

The nitrogen-containing organic compound is preferably a nitrogen-containing organic compound having a substituent. Specifically, 1,2,3-benzotriazole (hereinafter referred to as “BTA”) which is a triazole compound having a substituent, carboxybenzotriazole (hereinafter referred to as “CBTA”), N ′, N '-Bis (benzotriazolylmethyl) urea (hereinafter referred to as “BTD-U”), 1H-1,2,4-triazole (hereinafter referred to as “TA”) and 3-amino-1H— 1,2,4-triazole (hereinafter referred to as “ATA”) or the like is preferably used.

Examples of the sulfur-containing organic compound include mercaptobenzothiazole (hereinafter referred to as “MBT”), thiocyanuric acid (hereinafter referred to as “TCA”), 2-benzimidazolethiol (hereinafter referred to as “BIT”), and the like. It is preferable to use it.

As the carboxylic acid, it is particularly preferable to use a monocarboxylic acid, and it is particularly preferable to use oleic acid, linoleic acid, linolenic acid or the like.

As described above, a desired orientation is realized on the upper surface of the copper foil layer 104 of the present embodiment by appropriately controlling the manufacturing method such as increasing the electrolytic density or reducing the film thickness. be able to.

Further, at least the lower surface 22 (the surface in contact with one surface of the insulating layer 102) of the copper foil layer 104 used in this embodiment is used to make the adhesion between the copper foil layer 104 and the insulating layer 102 at a practical level or higher. The surface treatment may be performed. Examples of the surface treatment for the metal foil used for the copper foil layer 104 include rust prevention treatment, chromate treatment, silane coupling treatment, or a combination thereof. Any surface treatment means can be appropriately selected in accordance with the resin material constituting the insulating layer 102.

The rust prevention treatment is performed by forming a thin film on a metal foil by sputtering, electroplating, or electroless plating, for example, any one of metals such as nickel, tin, zinc, chromium, molybdenum, and cobalt, or an alloy thereof. Can be applied. From the viewpoint of cost, electroplating is preferable. In order to facilitate the precipitation of metal ions, a complexing agent such as citrate, tartrate or sulfamic acid can be added in the required amount. The plating solution is usually used in an acidic region and is performed at a temperature of room temperature (for example, 25 ° C.) to 80 ° C. The plating conditions are appropriately selected from the range of current density of 0.1 to 10 A / dm ² , energization time of 1 to 60 seconds, preferably 1 to 30 seconds. The amount of the rust-proofing metal varies depending on the type of metal, but is preferably 10 to 2000 μg / dm ^{2 in} total. If the rust preventive treatment is too thick, it may cause etching inhibition and deterioration of electrical characteristics, and if it is too thin, it may cause a reduction in peel strength with the resin.

Moreover, when the cyanate resin is contained in the resin composition constituting the insulating layer 102, it is preferable that the rust prevention treatment is performed with a metal containing nickel. This combination is useful in that there is little reduction in peel strength in the heat resistance deterioration test and moisture resistance deterioration test.

As the chromate treatment, an aqueous solution containing hexavalent chromium ions is preferably used. The chromate treatment can be performed by a simple immersion treatment, but is preferably performed by a cathode treatment. Sodium dichromate is preferably used under the conditions of 0.1 to 50 g / L, pH 1 to 13, bath temperature 0 to 60 ° C., current density 0.1 to 5 A / dm ² , and electrolysis time 0.1 to 100 seconds. It can also carry out using chromic acid or potassium dichromate instead of sodium dichromate. Further, the chromate treatment is preferably performed on the rust preventive treatment. Thereby, the adhesiveness of an insulating resin composition layer (insulating layer 102) and metal foil (copper foil layer 104) can be improved more.

Examples of the silane coupling agent used in the silane coupling treatment include epoxy-functional silanes such as 3-glycidoxypropyltrimethoxysilane and 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-amino Amino-functional silanes such as propyltrimethoxysilane, N-2- (aminoethyl) 3-aminopropyltrimethoxysilane, N-2- (aminoethyl) 3-aminopropylmethyldimethoxysilane, vinyltrimethoxysilane, vinylphenyl Olefin-functional silanes such as trimethoxysilane and vinyltris (2-methoxyethoxy) silane, acrylic-functional silanes such as 3-acryloxypropyltrimethoxysilane, and methacryl-functional silanes such as 3-methacryloxypropyltrimethoxysilane, 3 - And mercapto-functional silanes such as Le mercaptopropyl trimethoxysilane is used. These may be used alone or in combination. These coupling agents are used by dissolving in a solvent such as water at a concentration of 0.1 to 15 g / L, and applying the obtained solution to a metal foil at a temperature of room temperature to 50 ° C. Adsorb the silane coupling agent on the foil. A coating film is formed on the metal foil by these silane coupling agents being condensed and bonded to the hydroxyl group of the rust-preventing metal on the surface of the metal foil. After the silane coupling treatment, such bonding is stabilized by heating, ultraviolet irradiation or the like. In the heat treatment, for example, drying at a temperature of 100 to 200 ° C. for 2 to 60 seconds is preferable. The ultraviolet irradiation is preferably performed in a wavelength range of 200 to 400 nm and 200 to 2500 mJ / cm ² , for example. The silane coupling treatment is preferably performed on the outermost layer of the metal foil. When the insulating resin composition constituting the insulating layer 102 contains a cyanate resin, it is preferably treated with an aminosilane-based coupling agent. This combination is useful with little reduction in peel strength in the heat resistance deterioration test and moisture resistance deterioration test.

Further, the silane coupling agent used for the silane coupling treatment preferably reacts with the insulating resin composition constituting the insulating layer 102 by heating at 60 to 200 ° C., more preferably 80 to 150 ° C. It is preferable. Thereby, the functional group in the said insulating resin composition and the functional group of a silane coupling agent react chemically, and it becomes possible to obtain the more excellent adhesiveness. For example, it is preferable to use a silane coupling agent containing an amino-functional silane for an insulating resin composition containing an epoxy group. This is because the epoxy group and amino group easily form a strong chemical bond by heat, and this bond is extremely stable against heat and moisture. As a combination for forming a chemical bond in this way, epoxy group-amino group, epoxy group-epoxy group, epoxy group-mercapto group, epoxy group-hydroxyl group, epoxy group-carboxyl group, epoxy group-cyanato group, amino group-hydroxyl group And amino group-carboxyl group, amino group-cyanato group and the like.

In addition, it is preferable to use an epoxy resin that is liquid at room temperature as the insulating resin of the insulating resin composition used in this embodiment, and in this case, the viscosity at the time of melting is greatly reduced, so that the wettability at the adhesion interface is improved In addition, a chemical reaction between the epoxy resin and the silane coupling agent is likely to occur, and as a result, a strong peel strength can be obtained. Specifically, bisphenol A type epoxy resin, bisphenol F type epoxy resin, and phenol novolac type epoxy resin having an epoxy equivalent of about 200 are preferable.

Further, when the insulating resin composition contains a curing agent, it is particularly preferable to use a thermosetting latent curing agent as the curing agent. That is, when the functional group in the insulating resin composition and the functional group of the silane coupling agent chemically react, the reaction temperature of the functional group in the insulating resin composition and the functional group of the silane coupling agent is the same as that of the insulating resin composition. It is preferable to select the curing agent so that it is lower than the temperature at which the curing reaction is initiated. Thereby, the reaction between the functional group in the insulating resin composition and the functional group of the silane coupling agent is preferentially and selectively performed, and the metal foil (copper foil layer 104) and the insulating resin composition layer (insulating layer 102) The adhesion of becomes higher. Examples of the thermosetting latent curing agent for the insulating resin composition containing an epoxy resin include solid dispersion-heat-dissolving curing agents such as dicyandiamide, dihydrazide compounds, imidazole compounds, and amine-epoxy adducts, urea compounds, onium salts, Examples thereof include reactive group block type curing agents such as boron trichloride / amine salts and block carboxylic acid compounds.

As described above, the prepreg containing the insulating resin composition and the ultrathin copper foil with the carrier foil are laminated and integrated by the above-described method, whereby the copper clad laminate 10 with the carrier foil as shown in FIG. Can be obtained. Subsequently, as shown in FIG. 1 (b), the copper clad laminate 100 having the copper foil layers 104 on both surfaces of the insulating layer 102 is obtained by peeling off the carrier foil layer 106. Note that the present invention is not limited thereto, and the copper foil layer 104 may be formed on at least one surface of the insulating layer 102 or may be formed on the entire surface or a part of the insulating layer 102. Moreover, it is preferable that the copper foil layer 104 of this Embodiment has a bulk part and a roughening foot part.

Here, the details of the laminate (copper-clad laminate 100) will be described.

The etching rate of the copper foil layer 104 (thin layer copper foil) under the above-described conditions is 0.68 μm / min or more and 1.25 μm / min or less, more preferably 0.68 μm / min or more and 1.24 μm / min. Or less, more preferably 0.69 μm / min or more and 1.23 μm / min or less. The etching rate of the copper foil layer 104 described here particularly indicates only the etching rate of the bulk portion.

In the present embodiment, by setting the etching rate of the copper foil layer 104 to the lower limit value or more, the etching residue of the copper foil layer 104 can be reduced and the wiring shape can be improved. In addition, by setting the etching rate of the copper foil to the upper limit value or less, it is possible to prevent a notch from being formed in the side wall of the copper foil layer 104 and to reduce the adhesion between the wiring and the insulating layer. That is, when etching up to the roughened foot portion of the copper foil layer 104, it is possible to suppress the occurrence of abnormal constriction in the bulk portion of the copper foil layer 104.

In this Embodiment, the etching rate of the bulk part of copper foil can be measured with the following method.
1. A substrate (copper-clad laminate 100) on which the ultrathin copper foil from which the carrier foil (carrier foil layer 106) has been removed is laminated on both sides is cut into 40 mm × 80 mm to obtain sample pieces. Read the sample piece with a caliper to 2 digits after the decimal point, and calculate the area of the sample piece.
2. The sample piece is dried at 80 ° C. for 1 minute × 3 times in a horizontal drying line.
3. The initial weight W0 of the sample piece is measured (however, including the substrate weight).
4). Adjust the etchant.
4-1: Weigh 60 g of 95% sulfuric acid (special grade, manufactured by Wako Pure Chemical Industries, Ltd.) and place in a 1 L beaker.
4-2: Put pure water into the beaker used in 4-1 to make a total of 1000 cc.
4-3: Stir with a magnetic stirrer at 30 ° C. ± 1 ° C. for 3 minutes.
4-4: Weigh 20 cc of 34.5% hydrogen peroxide water (Kanto Chemical Co., Ltd., deer grade 1), put it in the beaker used in 4-1, make a total of 1020 cc, then 3 minutes at 30 ° C ± 1 ° C Stir. As a result, an etching solution containing 55.9 g / L of sulfuric acid and 19.6 cc / L of 34.5% hydrogen peroxide water is obtained.
5. The sample piece is immersed in the etching solution (liquid temperature 30 ° C. ± 1 ° C., stirring condition magnetic stirrer, 250 rpm).
6). The weight W1 of the sample piece is measured every 30 seconds (including the substrate weight) until the bulk portion of the ultrathin copper foil is completely etched.
7). The etching weight (W0-W1) / (area of both surfaces immersed = m ² ) is calculated, and the etching time (seconds) is plotted on the X axis and the etching mass (g / m ² ) is plotted on the Y axis. The slope K is calculated using the method of least squares between 0 and 150 seconds.

The conversion formula of the etching rate of this Embodiment is shown.
Etching rate (μm / min) = K (g / sec · m ² ) ÷ 8.92 (copper specific gravity g / cm ³ ) × 60 (sec / min)

The difference in Vickers hardness of the copper foil layer 104 before and after heat treatment at 230 ° C. for 1 hour is preferably 0 Hv or more and 50 Hv or less, more preferably 0 Hv or more and 30 Hv or less. By setting the difference in Vickers hardness of the copper foil layer 104 to the upper limit value or less, the recrystallization of the copper foil layer 104 proceeds by heating and the crystal grain size is increased, thereby suppressing the etching rate from being slowed or after etching. It is possible to suppress accumulation of distortion of the fine circuit. Here, the absolute value of the difference in Vickers hardness of the copper foil layer 104 before and after the heat treatment at 230 ° C. for 1 hour is preferably 0 Hv or more and 50 Hv or less, more preferably 0 Hv or more and 30 Hv or less. .

Further, the copper foil layer 104 has a Vickers hardness after heat treatment at 230 ° C. for 1 hour, preferably from 180 Hv to 240 Hv, more preferably from 185 Hv to 235 Hv. By setting the Vickers hardness after heating to 180 Hv or more, it is possible to suppress recrystallization of the thin copper layer (copper foil layer 104) due to heating and to increase the crystal grain size, or to reduce circuit linearity after etching. Can be suppressed. On the other hand, by setting the Vickers hardness after heating to 240 Hv or less, it is possible to suppress the occurrence of cracks during handling due to the thin copper layer becoming too hard and brittle, and cooling the formed fine wiring Impact resistance can be improved.

In the present embodiment, the Vickers hardness can be measured by, for example, the following method.
That is, the measurement of Vickers hardness is performed at 23 ° C. using a micro hardness meter (model number MVK-2H) manufactured by Akashi Corporation according to JIS Z 2244 according to the following procedure. (1) The ultrathin copper foil with carrier foil formed up to the copper foil layer is left in an oven (nitrogen atmosphere) heated to 230 ° C. for 1 hour, and then cut into 10 × 10 mm squares. (2) An indentation is made on the cut sample under conditions of a load speed of 3 μm / second, a test load of 5 gf, and a holding time of 15 seconds, and Vickers hardness is calculated from the measurement result of the indentation. (3) Let the average value which measured the Vickers hardness of arbitrary 5 points | pieces be the value of the Vickers hardness of this Embodiment.
In addition, as a sample, it is also possible to use an ultrathin copper foil with a carrier foil that has just been formed up to the copper foil layer and has not been subjected to heat treatment.

Further, in the copper foil layer 104, the crystal grain size of the cross section after heat treatment at 230 ° C. for 1 hour is preferably 2.0 μm or less, more preferably 0.5 μm or less, and further preferably 0.25 μm or more and 0. .5 μm or less. By setting the crystal grain size of the copper foil layer 104 to the upper limit value or less, it is possible to prevent the circuit linearity after etching from being lowered. By setting the crystal grain size of the copper foil layer 104 to the lower limit value or more, it is possible to suppress the internal stress (tensile stress) before heating after the thin copper layer plating from becoming too high, and the entire ultrathin copper foil with support is curled. As a result, it is possible to suppress the occurrence of problems during conveyance.

In the present embodiment, the crystal grain size of the copper foil layer 104 can be measured by the following method.
That is, the crystal grain size of the copper foil layer 104 was measured according to JIS H 0501. The specific procedure is as follows. First, a laminated board (copper-clad laminated board 100) is processed with a FIB (focused ion beam) processing apparatus, and a SIM (Scanning Ion Microscope) observation photograph is taken. The crystal grain size of the cross section of the photograph taken is calculated from the standard photograph of the comparative method specified in JIS H 0501.

In the present embodiment, the copper foil layer 104 (particularly, by reducing the crystal grain size of the copper foil layer 104, reducing the change in Vickers hardness after heating, increasing the etching rate of the roughened foot portion, etc.) The etching rate of the bulk portion can be increased. In addition, the etching rate of the roughened foot portion is usually slower than that of the bulk portion, but can be increased by reducing the electrolytic density, for example.

The film thickness of the copper foil layer 104 can be arbitrarily set according to the application. For example, the film thickness of the copper foil layer 104 is preferably 0.1 μm or more and 5 μm or less, and more preferably 1 μm or more and 4 μm or less. By setting the film thickness of the copper foil layer 104 within the above range, a good fine circuit can be formed.

Next, as shown in FIG. 1C, a through hole 108 for interlayer connection penetrating from the upper surface to the lower surface is formed in the copper clad laminate 100. Various known means can be used as a method of forming the through hole 108. For example, when forming the through hole 108 having a hole diameter of 100 μm or more, means using a drill or the like is used from the viewpoint of productivity. In order to form the through-hole 108 of 100 μm or less, means using a gas laser such as carbon dioxide or excimer, or a solid laser such as YAG is suitable.

Next, at least a catalyst nucleus can be provided on the copper foil layer 104, but in this embodiment, the catalyst nucleus is provided on the entire surface of the copper foil layer 104 and on the inner wall surface of the through hole 108. The catalyst nucleus is not particularly limited. For example, a noble metal ion or palladium colloid can be used. Subsequently, an electroless plating layer is formed using this catalyst nucleus as a nucleus. Before the electroless plating treatment, for example, smear removal with a chemical solution or the like may be performed on the surface of the copper foil layer 104 or the through hole 108. good. The desmear treatment is not particularly limited, and is a wet method using an oxidant solution having an organic substance decomposing action, and an organic substance by irradiating a target object with active species (plasma, radical, etc.) having a strong oxidizing action directly. A known method such as a dry method such as a plasma method for removing the residue can be used. Specific examples of the wet desmear treatment include a method in which the resin surface is subjected to a swelling treatment, etched by an alkali treatment, and then subjected to a neutralization treatment.

Next, as shown in FIG. 1 (d), a thin electroless plating layer 110 is formed on the copper foil layer 104 provided with catalyst nuclei and the inner walls of the through holes 108 by electroless plating. The electroless plating layer 110 electrically connects the copper foil layer 104 on the upper surface of the insulating layer 102 and the copper foil layer 104 on the lower surface thereof. For electroless plating, for example, one containing copper sulfate, formalin, complexing agent, sodium hydroxide or the like can be used. In addition, it is preferable to stabilize the plating film by performing a heat treatment at 100 to 250 ° C. after the electroless plating. A heat treatment at 120 to 180 ° C. is particularly preferable in that a film capable of suppressing oxidation can be formed. Further, the average thickness of the electroless plating layer 110 may be any thickness that allows the next electroplating to be performed. For example, about 0.1 to 1 μm is sufficient. Further, the inside of the through hole 108 may be filled with a conductive paste or an insulating paste, or may be filled with electric pattern plating.

Next, as shown in FIG. 1 (e), a resist layer 112 having a predetermined opening pattern is formed on the electroless plating layer 110 provided on the copper foil layer 104. This opening pattern corresponds to a conductor circuit pattern described later. Therefore, the resist layer 112 is provided so as to cover the non-circuit formation region on the copper foil layer 104. In other words, the resist layer 112 is not formed in the conductive circuit formation region on the through hole 108 and the copper foil layer 104. The resist layer 112 is not particularly limited, and a known material can be used, but liquid and dry films can be used. In the case of forming fine wiring, it is preferable to use a photosensitive dry film or the like as the resist layer 112. In order to form the resist layer 112, for example, a photosensitive dry film is laminated on the electroless plating layer 110, the non-circuit formation region is exposed and photocured, and the unexposed portion is dissolved and removed with a developer. The remaining cured photosensitive dry film becomes the resist layer 112. It is preferable that the thickness of the resist layer 112 be equal to or greater than the thickness of the conductor (plating layer 114) to be subsequently plated.

Next, as shown in FIG. 2A, a plating layer 114 is formed by electroplating at least inside the opening pattern of the resist layer 112 and on the electroless plating layer 110. At this time, the copper foil layer 104 serves as a power feeding layer. In the present embodiment, the plating layer 114 may be provided continuously over the upper surface of the insulating layer 102, the inner wall of the through hole 108, and the lower surface thereof. Such electroplating is not particularly limited, but a known method used in ordinary printed wiring boards can be used. For example, in a state where the plating solution is immersed in a plating solution such as copper sulfate, an electric current is supplied to the plating solution. A method such as flowing a stream can be used. The thickness of the plating layer 114 is not particularly limited as long as it can be used as a circuit conductor. For example, the thickness is preferably in the range of 1 to 100 μm, and more preferably in the range of 5 to 50 μm. The plating layer 114 may be a single layer or may have a multilayer structure. The material of the plating layer 114 is not particularly limited, and for example, copper, copper alloy, 42 alloy, nickel, iron, chromium, tungsten, gold, solder, or the like can be used.

Next, as shown in FIG. 2B, the resist layer 112 is removed using an alkaline stripping solution, sulfuric acid, a commercially available resist stripping solution, or the like.

Next, as shown in FIG. 2C, the electroless plating layer 110 and the copper foil layer 104 other than the region where the plating layer 114 is formed are removed. As a technique for removing the copper foil layer 104, for example, soft etching (flash etching) or the like is used. Thereby, the pattern of the conductor circuit 118 comprised by laminating | stacking the copper foil layer 104 and the metal layer 116 (the electroless-plating layer 110 and the plating layer 114) can be formed.

Here, the etching solution used for the soft etching of this embodiment will be described below. The etching solution is not particularly limited. However, when a conventional diffusion-controlled etching solution is used, circuit formation tends to be deteriorated because the exchange of the solution is inevitably worsened for fine portions of the wiring. For this reason, it is desirable to use an etching solution in which the reaction between copper and the etching solution proceeds not at a diffusion rate but at a reaction rate. If the reaction between copper and the etchant is reaction-controlled, the etching rate does not change even if diffusion is further increased. That is, there is no difference in etching rate between a place where the liquid exchange is good and a place where the liquid exchange is bad. As such a reaction-limited etching solution, for example, one containing hydrogen peroxide and an acid not containing a halogen element as main components can be mentioned. Since hydrogen peroxide is used as the oxidizing agent, strict etching rate control becomes possible by managing the concentration. If a halogen element is mixed in the etching solution, the dissolution reaction tends to be diffusion-limited. As the acid not containing halogen, nitric acid, sulfuric acid, organic acid, and the like can be used, but sulfuric acid is preferable because it is inexpensive. Further, when sulfuric acid and hydrogen peroxide are the main components, the respective concentrations are preferably 5 to 300 g / L and 5 to 200 g / L from the viewpoints of etching rate and liquid stability. Examples thereof include ammonium persulfate, sodium persulfate, and sodium persulfate.

Various modes can be adopted as the etching method. For example, the copper clad laminate 100 may be immersed in an etching solution stored in a liquid storage container such as a beaker, or the etching solution may be applied to the copper foil layer 104 by a shower method.

As described above, by appropriately selecting the etching rate of the copper foil layer 104, a conductor circuit 118 having a desired shape can be obtained. As described above, the printed wiring board 200 in which the conductor circuit 118 is formed on both surfaces of the insulating layer 102 is obtained.

As shown in FIG. 2D-1, a solder resist layer 120 may be formed so as to cover the insulating layer 102 and a part of the conductor circuit 118. As the solder resist layer 120, for example, a filler or a substrate excellent in insulating properties may be included, and a heat-resistant resin composition such as a photosensitive resin, a curable resin, and a thermoplastic resin is used. Next, the first plating layer 122 and the second plating layer 124 may be further formed on the conductor circuit 118 provided with the opening of the solder resist layer 120. Thereby, the metal layer 116 may have a multilayer structure of two or more. As the first plating layer 122 and the second plating layer 124, a gold plating layer can be adopted. The gold plating method may be a conventionally known method, and is not particularly limited. For example, electroless nickel plating is performed on the plating layer 114 to about 0.1 to 10 μm, and displacement gold plating is performed to 0.01 to 0. There is a method of performing electroless gold plating about 0.1 to 2 μm after about 5 μm. As a result, the printed wiring board 202 shown in FIG. 2D-1 is obtained.
In addition, as shown in FIG. 2D-2, the first plating layer 122 and the second plating layer 124 may be formed around the conductor circuit 118 without forming the solder resist layer 120. . As these 1st plating layer 122 and 2nd plating layer 124, you may employ | adopt the laminated body of a nickel plating layer and a gold plating layer, for example. Thus, the printed wiring board 204 shown in FIG. 2 (d-2) is obtained.

Also, a semiconductor device (not shown) can be mounted on these printed

wiring boards

200, 202, and 204 to obtain a semiconductor device.

(Second Embodiment)
Next, the manufacturing method of the printed wiring board of 2nd Embodiment is demonstrated.
3 to 5 are cross-sectional views showing the steps of the manufacturing process of the printed wiring board manufacturing method according to the third embodiment. The printed wiring board manufacturing method of the third embodiment uses, for example, the printed

wiring boards

200, 202, and 204 obtained in the second embodiment as inner layer circuit boards, and builds on the inner layer circuit boards. An up layer is further formed.

First, the printed wiring board 200 obtained in FIG. 2C is adopted as the inner layer circuit board. The inner layer circuit (conductor circuit 118) of the printed wiring board 200 is subjected to a roughening process. Here, the roughening treatment means performing a chemical treatment, a plasma treatment, or the like on the surface of the conductor circuit. As the roughening treatment, for example, a blackening treatment using oxidation reduction or a chemical solution treatment using a known roughening solution of sulfuric acid-hydrogen peroxide system can be used. Thereby, the adhesiveness of the interlayer insulation material which comprises the insulating layer 130, and the conductor circuit 118 of the printed wiring board 200 can be improved. In addition, the inner layer circuit board is not particularly limited in place of the printed wiring board 200 obtained in the second embodiment, but the resin composition does not include a prepreg or a base material by a plated through hole method, a build-up method, or the like. A normal multilayer printed wiring board in which physical layers and the like are laminated can also be used. The conductor circuit layer serving as the inner layer circuit may be formed by a conventionally known circuit forming method. In multilayer printed wiring boards, through-holes are formed by drilling, laser processing, etc. on the laminate (a laminate obtained by laminating multiple prepregs) and metal-clad laminate as the core layer. Then, the inner circuit on both sides can be electrically connected by plating or the like.

Next, as shown in FIG. 3A, an insulating layer 130 (prepreg) and a copper foil layer 105 with a carrier foil layer 107 (carrier foil) are formed on both sides of a printed wiring board 200 with a roughened conductor circuit surface, respectively. With ultra-thin copper foil). Next, as shown in FIG. 3B, a multilayer laminate is formed by subjecting the laminate in which these layers are stacked to heat and pressure. Subsequently, as shown in FIG. 3C, the carrier foil layer 107 is peeled and removed.

Next, as shown in FIG. 3D, a part of the insulating layer 130 and the copper foil layer 105 is removed to form a hole 109. A part of the surface of the conductor circuit 118 is exposed at the bottom surface of the hole 109. The method of forming the hole 109 is not particularly limited, and for example, a method of forming a blind via hole having a hole diameter of 100 μm or less using a gas laser such as carbon dioxide or excimer or a solid laser such as YAG is used. it can. Although the hole 109 is shown as a non-through hole in FIG. 3D, it may be a through hole. In the case of a through hole, it may be formed by laser irradiation or using a drilling machine.

Next, as shown in FIG. 4A, a thin electroless plating layer 111 is formed on the conductor circuit 118 provided with the above-described catalyst nucleus, on the inner wall of the hole 109, and on the copper foil layer 105. The electroless plating layer 111 is formed in the same manner as the electroless plating layer 110 described above. Before this electroless plating, as described above, desmear treatment such as smear removal with a chemical solution may be performed. Further, the thickness of the electroless plating layer 110 may be any thickness that allows subsequent electroplating to be performed, and about 0.1 to 1 μm is sufficient. Further, the inside of the hole 109 (blind via hole) can be filled with a conductive paste or an insulating paste, or may be filled with electric pattern plating.

Next, a resist layer 113 having an opening pattern corresponding to the conductor circuit pattern is formed on the electroless plating layer 110. In other words, the non-circuit forming portion is masked by forming the resist layer 113. As this resist layer 113, the thing similar to the above-mentioned resist layer 112 can be used. The thickness of the resist layer 113 is preferably set to be approximately the same as or thicker than that of the conductor circuit to be subsequently plated.

Next, as shown in FIG. 4C, a plating layer 132 is formed inside the opening pattern of the resist layer 113. The plating layer 132 may be formed on the conductor circuit 118 inside the hole 109 or may be formed on the electroless plating layer 111 inside the opening pattern. The electroplating for forming the plating layer 132 can use the same technique as that for the plating layer 114 described above. The thickness of the plating layer 132 may be used as a circuit conductor. For example, the thickness is preferably in the range of 1 to 100 μm, and more preferably in the range of 5 to 50 μm.

Next, as shown in FIG. 5A, the resist layer 113 is peeled in the same manner as the resist layer 112 described above. Next, as shown in FIG. 5B, the copper foil layer 105 and the electroless plating layer 111 are removed by soft etching (flash etching) in the same manner as the copper foil layer 104 described above. Thereby, the conductor circuit pattern comprised from the copper foil layer 105, the electroless-plating layer 111, and the plating layer 132 can be formed. Further, vias and pads that are electrically connected to the conductor circuit 118 can be formed by the plating layer 132. The printed wiring board 201 is obtained as described above.

As shown in FIG. 5C-1, a solder resist layer 121 may be formed on the insulating layer 130, the conductive circuit pattern plating layer 132, and a part of the pad plating layer 132. As the solder resist layer 121, the same thing as the above-mentioned solder resist layer 120 can be used. Next, a first plating layer 123 and a second plating layer 125 made of, for example, a nickel plating layer and a gold plating layer are further formed on the plating layer 132 in which the opening of the solder resist layer 121 is provided. May be. Thus, the printed wiring board 203 shown in FIG. 5C-1 is obtained.
Further, as shown in FIG. 5 (c-2), the first plating layer 123 and the second plating layer 125 described above are formed around the conductor circuit pattern and the pad without forming the solder resist layer 121. May be formed. As a result, the printed wiring board 205 shown in FIG. 5C-2 is obtained. Also in the second embodiment, the same effect as the first embodiment can be obtained.

(Third embodiment)
Next, details of the manufacturing process of the printed wiring board 101 according to the third embodiment will be described.
As shown to Fig.6 (a), the copper clad laminated board 10 with a carrier foil is prepared. Subsequently, as shown in FIG. 6 (b), the carrier foil layer 106 is removed from the copper clad laminate 10 with the carrier foil by peeling off. Subsequently, as shown in FIG. 6C, a resist layer 112 having a predetermined opening pattern is formed on the remaining copper foil layer 104. A plating layer (metal layer 115) is formed by plating in the opening pattern of the resist layer 112 and on the copper foil layer 104 (FIG. 6D). Subsequently, as shown in FIG. 6E, the resist layer 112 is removed. Thereby, the pattern of the predetermined metal layer 115 can be selectively formed on the copper foil layer 104. Thereafter, as shown in FIG. 6F, the copper foil layer 104 in the region not covered with the metal layer 115 is removed by, for example, soft etching. After such a step of removing the copper foil layer 104, the pattern of the conductor circuit 119 can be formed by the remaining copper foil layer 104 and the metal layer 115. Through the above steps, the printed wiring board 101 of the third embodiment is obtained. In the third embodiment, the same effect as in the first embodiment can be obtained.

(Fourth embodiment)
Next, details of the manufacturing process of the printed wiring board 101 according to the fourth embodiment will be described.
First, as shown to Fig.7 (a), the copper clad laminated board 10 with carrier foil is prepared. In the copper clad laminate 10 with a carrier foil, a carrier foil layer 106 is attached to both surfaces of the insulating layer 102 together with the copper foil layer 104. Then, as shown in FIG.7 (b), the carrier foil layer 106 is peeled from the copper clad laminated board 10 with carrier foil. Subsequently, as shown in FIG. 7C, a metal layer 115 (plating layer) is formed on the entire surface of the copper foil layer 104 by plating. Subsequently, as shown in FIG. 7D, a resist layer 112 having a predetermined opening pattern is formed on the plane-shaped metal layer 115. Subsequently, as shown in FIG. 7E, the metal layer 115 and the copper foil layer 104 in the opening pattern of the resist layer 112 are removed by, for example, etching. Thereafter, as shown in FIG. 7F, the resist layer 112 is removed. Thereby, the pattern of the conductor circuit 119 comprised from the copper foil layer 104 and the metal layer 115 can be formed. Through the above steps, the printed wiring board 101 of the fourth embodiment is obtained. In the fourth embodiment, the same effect as in the first embodiment can be obtained.

As described above, according to the present embodiment, a fine circuit processing of an ultrathin copper foil with a carrier foil, a fine circuit shape, a method of manufacturing a printed wiring board excellent in insulation reliability, and the printed wiring board It becomes possible to provide.

The printed wiring board manufacturing method of the present embodiment is not only for forming a conductor circuit layer on both sides of a printed wiring board substrate, but also for forming a conductor circuit layer only on one side of the printed wiring board substrate. Can be applied. Further, as shown in FIG. 2 (c), the double-sided printed wiring board can be used as the inner layer circuit board, and the case of the multilayer printed wiring board of the third embodiment can also be applied. Therefore, any of a single-sided printed wiring board, a double-sided printed wiring board, and a multilayer printed wiring board can be produced by the method for producing a printed wiring board of the present embodiment.

Hereinafter, an ultrathin copper foil with a carrier foil according to the present invention and a copper clad laminate using the copper foil will be manufactured, and an embodiment of a method for manufacturing a printed wiring board according to the present invention will be described. Here, the case where an electrolytic copper foil is used as the carrier foil will be mainly described. The present invention will be described in detail based on examples and comparative examples, but the present invention is not limited thereto.
Unless otherwise specified, “parts” described below indicates “parts by weight” and “%” indicates “% by weight”.

1. Production of Ultrathin Copper Foil with Carrier Foil Hereinafter, production of an ultrathin copper foil with a carrier foil will be described.
(Production Example 1)
As a carrier foil (supporting metal foil), a release layer and an ultrathin copper foil layer were sequentially formed on the glossy surface of an electrolytic copper foil having a thickness of 18 μm. The manufacturing conditions are as follows.
First, the carrier foil was immersed in an acid cleaning tank (sulfuric acid: 30 g / L) for 5 seconds to remove surface oil, oxide film, and the like. Next, a release layer formation tank (nickel sulfate hexahydrate: 30 g / L, sodium molybdate dihydrate: 3 g / L, trisodium citrate dihydrate: 30 g / L, liquid temperature: 30 ° C.) Was used for 5 seconds at a current density of 20 A / dm ² to form a release layer on the glossy surface of the carrier foil. Next, a bulk portion (hereinafter referred to as a bulk copper layer) was formed on the release layer. The bulk copper layer was formed as follows. First, electrolytic treatment was performed for 15 seconds at a current density of 2.0 A / dm ² using a plating bath (copper pyrophosphate: 80 g / L, potassium pyrophosphate: 320 g / L, ammonia water: 2 ml / L, liquid temperature: 40 ° C.). A first bulk copper layer was formed on the release layer. Next, plating bath (copper sulfate pentahydrate: 160 g / L, sulfuric acid: 100 g / L, gelatin (manufactured by Nippi, trade name PBH, weight average molecular weight (MW) 5000): 15 ppm, chloride ion: 5 ppm, liquid The second bulk copper layer was formed on the first bulk copper layer by electrolytic treatment at a current density of 3.5 A / dm ² using a temperature of 40 ° C. for 150 seconds. Thereby, a bulk copper layer was formed. Next, using a plating bath (copper sulfate pentahydrate: 150 g / L, sulfuric acid: 100 g / L, liquid temperature: 30 ° C.), the current density was 5 A / dm after electrolytic treatment at a current density of 30 A / dm ² for 3 seconds. ² for 70 seconds to form a roughened foot portion (hereinafter referred to as a roughened copper layer) on the bulk copper layer. Next, electrolytic treatment was performed at a current density of 0.5 A / dm ² for 2.5 seconds using a rust prevention treatment tank (sodium dichromate dihydrate: 3.5 g / L, liquid temperature 28 ° C.) to prevent rust. Processed. Next, it was immersed in an aqueous solution of 1 wt% of N-phenylaminopropyltrimethoxysilane to perform surface treatment. Then, it dried for 10 minutes at 80 degreeC. As a result, an ultrathin copper foil with a carrier foil according to Production Example 1 was formed.

(Production Example 2)
An ultrathin copper foil with a carrier foil was formed in the same manner as in Production Example 1 except for the production conditions for the bulk copper layer.
In this production example, the bulk copper layer was formed as follows. First, using a plating bath (copper sulfate pentahydrate: 30 g / L, trisodium citrate dihydrate: 40 g / L, liquid temperature: 40 ° C.) at a current density of 2.0 A / dm ² for 15 seconds. Then, a first bulk copper layer was formed on the release layer. Next, plating bath (copper sulfate pentahydrate: 160 g / L, sulfuric acid: 100 g / L, gelatin (manufactured by Nippi, trade name PBF, weight average molecular weight (MW) 3000): 20 ppm, chloride ion: 5 ppm, liquid The second bulk copper layer was formed on the first bulk copper layer by electrolytic treatment at a current density of 3.5 A / dm ² using a temperature of 40 ° C. for 150 seconds. Thereby, a bulk copper layer was formed.

(Production Example 3)
An ultrathin copper foil with a carrier foil was formed in the same manner as in Production Example 1 except for the production conditions for the bulk copper layer.
In this production example, the bulk copper layer was formed as follows. First, using a plating bath (copper sulfate pentahydrate: 30 g / L, trisodium citrate dihydrate: 40 g / L, liquid temperature: 40 ° C.) at a current density of 2.0 A / dm ² for 15 seconds. Then, a first bulk copper layer was formed on the release layer. Next, plating bath (copper sulfate pentahydrate: 160 g / L, sulfuric acid: 100 g / L, gelatin (manufactured by Nippi, trade name PA-10, weight average molecular weight (MW) 1000): 25 ppm, chloride ion: 5 ppm And a liquid temperature of 40 ° C. for 150 seconds at a current density of 3.5 A / dm ² to form a second bulk copper layer on the first bulk copper layer. Thereby, a bulk copper layer was formed.

(Production Example 4)
An ultrathin copper foil with a carrier foil was formed in the same manner as in Production Example 1 except for the production conditions for the bulk copper layer.
In this production example, the bulk copper layer was formed as follows. First, current density using a plating bath (copper sulfate pentahydrate: 30 g / L, nickel sulfate hexahydrate: 5 g / L, trisodium citrate dihydrate: 40 g / L, liquid temperature: 40 ° C.) Electrolytic treatment was carried out at 2.0 A / dm ² for 15 seconds to form a first bulk copper layer on the release layer. Next, plating bath (copper sulfate pentahydrate: 160 g / L, sulfuric acid: 100 g / L, gelatin (manufactured by Nippi, trade name PA-10, weight average molecular weight (MW) 1000): 35 ppm, chloride ion: 5 ppm And a liquid temperature of 40 ° C. for 150 seconds at a current density of 3.5 A / dm ² to form a second bulk copper layer on the first bulk copper layer. Thereby, a bulk copper layer was formed.

(Production Example 5)
An ultrathin copper foil with a carrier foil was formed in the same manner as in Production Example 1 except for the production conditions for the bulk copper layer.
In this production example, the bulk copper layer was formed as follows. First, current density using a plating bath (copper sulfate pentahydrate: 30 g / L, nickel sulfate hexahydrate: 5 g / L, trisodium citrate dihydrate: 40 g / L, liquid temperature: 40 ° C.) Electrolytic treatment was carried out at 2.0 A / dm ² for 15 seconds to form a first bulk copper layer on the release layer. Next, plating bath (copper sulfate pentahydrate: 160 g / L, sulfuric acid: 100 g / L, gelatin (manufactured by Nippi, trade name PBH, weight average molecular weight (MW) 5000): 30 ppm, chloride ion: 5 ppm, liquid The second bulk copper layer was formed on the first bulk copper layer by electrolytic treatment at a current density of 3.5 A / dm ² using a temperature of 40 ° C. for 150 seconds. Thereby, a bulk copper layer was formed.

(Production Example 6)
As a carrier foil (supporting metal foil), a release layer and an ultrathin copper foil layer were sequentially formed on the glossy surface of an electrolytic copper foil having a thickness of 18 μm. The manufacturing conditions are as follows.
First, the carrier foil was immersed in an acid cleaning tank (sulfuric acid: 50 g / L) for 15 seconds to remove surface oil, oxide film, and the like. Next, the film was immersed in a release layer formation tank (carboxybenzotriazole solution: reagent, liquid temperature 40 ° C.) for 15 seconds to form a release layer on the glossy surface of the carrier foil. Next, plating bath (copper sulfate pentahydrate: 150 g / L, sulfuric acid: 150 g / L, gelatin (manufactured by Nippi, trade name PBH, weight average molecular weight (MW) 5000): 15 ppm, chloride ion: 5 ppm, Electrolytic treatment was performed at a current density of 10 A / dm ² using a liquid temperature of 40 ° C. for 180 seconds to form a bulk copper layer on the release layer. Next, using a plating bath (copper sulfate pentahydrate: 150 g / L, sulfuric acid: 100 g / L, liquid temperature: 30 ° C.), the current density was 5 A / dm after electrolytic treatment at a current density of 30 A / dm ² for 3 seconds. ² for 70 seconds to form a roughened copper layer on the bulk copper layer. Next, electrolytic treatment was performed at a current density of 0.5 A / dm ² for 2.5 seconds using a rust prevention treatment tank (sodium dichromate dihydrate: 3.5 g / L, liquid temperature 28 ° C.) to prevent rust. Processed. Next, it was immersed in an aqueous solution of 1 wt% of N-phenylaminopropyltrimethoxysilane to perform surface treatment. Then, it dried for 10 minutes at 80 degreeC. As a result, an ultrathin copper foil with a carrier foil according to Production Example 6 was formed.

(Production Example 7)
An ultrathin copper foil with a carrier foil was formed in the same manner as in Production Example 1 except for the production conditions for the bulk copper layer.
In this production example, the bulk copper layer was formed as follows. First, using a plating bath (copper sulfate pentahydrate: 30 g / L, trisodium citrate dihydrate: 40 g / L, liquid temperature: 40 ° C.) at a current density of 2.0 A / dm ² for 15 seconds. Then, a first bulk copper layer was formed on the release layer. Next, using a plating bath (copper sulfate pentahydrate: 160 g / L, sulfuric acid: 100 g / L, chloride ion: 5 ppm, liquid temperature 40 ° C.), electrolytic treatment is performed at a current density of 3.5 A / dm ² for 150 seconds. A second bulk copper layer was formed on the first bulk copper layer. Thereby, a bulk copper layer was formed.

(Production Example 8)
An ultrathin copper foil with a carrier foil was formed in the same manner as in Production Example 1 except for the production conditions for the bulk copper layer.
In this production example, the bulk copper layer was formed as follows. First, using a plating bath (copper sulfate pentahydrate: 30 g / L, trisodium citrate dihydrate: 40 g / L, liquid temperature: 40 ° C.) at a current density of 2.0 A / dm ² for 15 seconds. Then, a first bulk copper layer was formed on the release layer. Subsequently, a plating bath (copper sulfate pentahydrate: 160 g / L, sulfuric acid: 100 g / L, gelatin (manufactured by Nippi, trade name: PBF, weight average molecular weight (MW) 3000): 20 ppm, liquid temperature: 40 ° C.) Electrolytic treatment was performed at a current density of 3.5 A / dm ² for 150 seconds to form a second bulk copper layer on the first bulk copper layer. Thereby, a bulk copper layer was formed.

(Production Example 9)
An ultrathin copper foil with a carrier foil was formed in the same manner as in Production Example 1 except for the production conditions for the bulk copper layer.
In this production example, the bulk copper layer was formed as follows. First, using a plating bath (copper sulfate pentahydrate: 30 g / L, trisodium citrate dihydrate: 40 g / L, liquid temperature: 40 ° C.) at a current density of 2.0 A / dm ² for 15 seconds. Then, a first bulk copper layer was formed on the release layer. Then, plating bath (copper sulfate pentahydrate: 160 g / L, sulfuric acid: 100 g / L, gelatin (manufactured by Nippi, trade name AP, weight average molecular weight (MW) 8000): 30 ppm, chloride ion: 5 ppm, liquid The second bulk copper layer was formed on the first bulk copper layer by electrolytic treatment at a current density of 3.5 A / dm ² using a temperature of 40 ° C. for 150 seconds. Thereby, a bulk copper layer was formed.

(Production Example 10)
An ultrathin copper foil with a carrier foil was formed in the same manner as in Production Example 1 except for the production conditions for the bulk copper layer.
In this production example, the bulk copper layer was formed as follows. First, using a plating bath (copper sulfate pentahydrate: 30 g / L, trisodium citrate dihydrate: 40 g / L, liquid temperature: 40 ° C.) at a current density of 2.0 A / dm ² for 15 seconds. Then, a first bulk copper layer was formed on the release layer. Next, plating bath (copper sulfate pentahydrate: 160 g / L, sulfuric acid: 100 g / L, gelatin (manufactured by Nippi, trade name PBF, weight average molecular weight (MW) 3000): 5 ppm, chloride ion: 5 ppm, liquid The second bulk copper layer was formed on the first bulk copper layer by electrolytic treatment at a current density of 3.5 A / dm ² using a temperature of 40 ° C. for 150 seconds. Thereby, a bulk copper layer was formed.

2. Manufacture of resin varnish 20 parts by weight of naphthylene ether type epoxy resin (manufactured by DIC, HP-6000), 5 parts by weight of naphthalene type epoxy resin (manufactured by DIC, HP 4032D), cyanate resin (manufactured by Lonza Japan, PT- 30) 17 parts by weight, bismaleimide resin (manufactured by Keiai Chemical Industry Co., Ltd., BMI-70) 7.5% by weight, silica particles (NSS-5N manufactured by Tokuyama Co., Ltd., average particle size 70 nm), 7 parts by weight, spherical silica (ad Matex Corporation SO-25R, average particle size 0.5 μm) 35.5 parts by weight, silicone particles (manufactured by Shin-Etsu Chemical Co., Ltd., KMP600, average particle size 5 μm) 7.5 parts by weight, zinc octylate 0.01 Part by weight and 0.5 part by weight of epoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., KBM-403E) were dissolved and mixed in methyl ethyl ketone. Subsequently, it stirred using the high-speed stirring apparatus and adjusted so that it might become 70 weight% of non volatile matters, and the resin varnish was prepared.

3. Manufacture of prepreg Glass woven fabric (manufactured by Nitto Boseki Co., Ltd., T glass woven fabric, WTX-1078, basis weight 48 g / m ² , thickness 45 μm) is used as a fiber base material, and the resin varnish prepared above is impregnated and applied. And dried in a heating furnace at 180 ° C. for 2 minutes to obtain a prepreg having a thickness of 0.05 mm.

4). Production of copper-clad laminate Four prepregs obtained as described above are stacked, and an ultrathin copper foil (2 μm) with a carrier foil is stacked on both sides, and the pressure is 3 MPa and the temperature is 200 ° C. for 60 minutes (after reaching 200 ° C. , Heated for 60 minutes) A copper-clad laminate having copper foil on both sides was obtained by heat and pressure molding. In addition, the ultrathin copper foil with a carrier foil used in each Example and Comparative Example is as described in Table 1 and Table 2.

5. Evaluation The following evaluation was performed using the ultra-thin copper foil with a carrier obtained by each Example and the comparative example. The evaluation items are shown together with the contents, and the obtained results are shown in Tables 1 and 2.

(1) Measurement of Vickers Hardness Vickers hardness was measured at 23 ° C. using a micro hardness tester (model number MVK-2H) manufactured by Akashi Corporation according to JIS Z 2244 according to the following procedure. As a normal sample, an ultrathin copper foil with a carrier immediately after forming a bulk copper layer was used. As the sample after the heat treatment, a sample after leaving the ultrathin copper foil with a carrier formed up to the bulk copper layer in an oven (nitrogen atmosphere) heated to 230 ° C. for 1 hour was used. The measurement conditions were as follows: an indentation was made on a cut sample under conditions of a load speed of 3 μm / second, a test load of 5 gf, and a holding time of 15 seconds, Vickers hardness was calculated from the measurement result of the indentation, and an average of five arbitrary Vickers hardnesses measured The value was the value of the condition.

(2) Etching rate (V1, V2)
1. The board | substrate which laminated | stacked the ultrathin copper foil from which carrier foil was removed on both surfaces is cut | judged to 40 mm x 80 mm, and a sample piece is obtained. Read the sample piece with a caliper to 2 digits after the decimal point, and calculate the area of the sample piece.
2. In the horizontal drying line, the sample piece is dried at 80 ° C. for 1 minute × 3 times.
3. The initial weight W0 of the sample piece is measured (however, including the substrate weight).
4). Adjust the etchant.
4-1: Weigh 60 g of 95% sulfuric acid (special grade, manufactured by Wako Pure Chemical Industries, Ltd.) and place in a 1 L beaker.
4-2: Put pure water into the beaker used in 4-1 to make a total of 1000 cc.
4-3: Stir for 3 minutes at 30 ° C. ± 1 ° C. using a magnetic stirrer.
4-4: Weigh 20 cc of 34.5% hydrogen peroxide water (Kanto Chemical Co., Ltd., deer grade 1), put it in the beaker used in 4-1, make a total of 1020 cc, then 3 minutes at 30 ° C ± 1 ° C Stir. As a result, an etching solution containing 55.9 g / L of sulfuric acid and 19.6 cc / L of 34.5% hydrogen peroxide water is obtained.
5. The sample piece is immersed in the etching solution (liquid temperature 30 ° C. ± 1 ° C., stirring condition: magnetic stirrer, 250 rpm).
6). The weight W1 of the sample piece is measured every 30 seconds (including the substrate weight) until the ultrathin copper foil bulk layer is completely etched.
7). The etching weight (W0-W1) / (area of both surfaces immersed = m ² ) is calculated, and the etching time (seconds) is plotted on the X axis and the etching mass (g / m ² ) is plotted on the Y axis. From the slope K1 calculated using the method of least squares for 0 to 150 seconds, the etching rate V1 (μm / min) of the bulk copper layer = K1 (g / sec · m ² ) ÷ 8.92 (copper specific gravity) g / cm ³ ) × 60 (sec / min) is calculated.
8). Thereafter, the weight W2 of the sample piece is measured every 10 seconds (however, including the substrate weight) until the rough copper layer of the ultrathin copper foil is completely etched.
9. The etching weight (W0−W2) / (both surface area immersed = m ² ) is calculated, and the etching time (seconds) is plotted on the X axis and the etching mass (g / m ² ) is plotted on the Y axis. From the slope K2 calculated using the least square method for 0 to 30 seconds, the etching rate V2 (μm / min) of the roughened copper layer = K2 (g / sec · m ² ) ÷ 8.92 (copper Specific gravity g / cm ³ ) × 60 (sec / min) is calculated.

(3) Concavity and convexity evaluation method Using the SEM image (2000 times) obtained by observing the printed wiring board obtained in (4), which will be described later, from the top, binarize the copper residue between the wirings (Media Cybernetics) Residual copper degree was calculated by using image processing software (Image Pro Plus ver. 5.1) manufactured by the company.

Each code | symbol in Table 1 and Table 2 is as follows.
◎: 2 or less ○: 10 or less above 2 ×: 10 or more

(4) Insulation between thin wires The surface of the substrate on which the ultrathin copper foil from which the carrier foil has been removed is laminated on both sides is soft-etched with a chemical polishing liquid (Mitsubishi Gas Chemical Co., Ltd., product name: CPB-60) for 5 seconds at 23 ° C. Copper was removed. Next, an ultraviolet-sensitive dry film having a thickness of 25 μm (manufactured by Asahi Kasei Co., Ltd., Sunfort UFG-255) was bonded onto the substrate by a hot roll laminator. Next, alignment of a glass mask (manufactured by Topic) on which a pattern having a minimum line width / line spacing of 20/20 μm was drawn was performed. Next, the dry film was exposed with an exposure apparatus (Ono Sokki EV-0800) using the glass mask, and developed with an aqueous sodium carbonate solution. Thereby, a resist mask was formed.
2. Next, electrolytic copper plating (81-HL manufactured by Okuno Pharmaceutical Co., Ltd.) was performed at 3 A / dm ² for 25 minutes using the ultrathin copper foil layer as a power supply layer electrode to form a copper wiring pattern having a thickness of about 20 μm. Next, the resist mask was peeled off with a monoethanolamine solution (R-100, manufactured by Mitsubishi Gas Chemical Company) using a peeling machine.
3. Then, the ultrathin copper foil layer as the power feeding layer was removed by flash etching (the same solution as the etching rate) to form a pattern of L / S = 20/20 μm (patterned etching). Thereby, a printed wiring board was obtained.
4). As a test sample, an insulating resin sheet (manufactured by Sumitomo Bakelite Co., Ltd., BLA-3700GS) is laminated instead of a solder resist, and a sample cured at a temperature of 220 ° C. is used. Conditions of a temperature of 130 ° C., a humidity of 85%, and an applied voltage of 10V The continuous wet insulation resistance was evaluated. A resistance value of 10 ⁶ Ω or less was regarded as a failure.
The symbols are as follows.
◎: No failure for 300 hours or more ○: Failure in 150 to less than 300 hours ×: Failure in less than 150 hours

(5) Wiring shape (or circuit linearity)
1. As the sample, the printed wiring board obtained in the above (4) was used.
2. Using a microscope, the contour of the circuit bottom when the circuit after etching was observed from directly above was evaluated. Moreover, the wiring shape at the time of observing the cross section of the circuit after an etching using the microscope was evaluated.
The code is as follows.
A: When observed from directly above, the outline of the circuit bottom portion looks straight. Moreover, there is no bottom hem expansion in the cross section.
○: When observed from directly above, the outline of the circuit bottom portion looks straight. In addition, the bottom hem is small in the cross section.
X: When observed from directly above, there is a portion where the outline of the circuit bottom portion looks like a curve. Moreover, the bottom hem is large in the cross section.

(6) Grain boundary diameter (μm)
The grain boundary diameter was measured according to JIS H 0501. The procedure is as follows.
1. After processing the board | substrate which laminated | stacked the ultra-thin copper foil which removed the carrier foil on both surfaces using a FIB (focused ion beam) processing apparatus, a SIM (Scanning Ion Microscope) observation photograph is image | photographed.
2. The crystal grain size of the cross section of the photograph taken is calculated from the standard photograph of the comparative method specified in JIS H 0501. In addition, since the attached drawing of this standard shows only the crystal grain size of 0.010 mm observed at 75 times, it was calculated considering the most similar figure and the magnification at the time of observation.

Of course, the embodiment and the plurality of modifications described above can be combined within a range in which the contents do not conflict with each other. Further, in the above-described embodiments and modifications, the structure of each part has been specifically described, but the structure and the like can be changed in various ways within a range that satisfies the present invention.

This application claims priority based on Japanese Patent Application No. 2012-059742 filed on Mar. 16, 2012, the entire disclosure of which is incorporated herein.

Claims

A laminated plate used for an element mounting substrate, comprising an insulating layer and a copper foil located on at least one surface of the insulating layer, and obtained by forming a conductor circuit by etching the copper foil,
The laminate was placed in a sulfuric acid / hydrogen peroxide etching solution comprising 55.9 g / L of sulfuric acid and 19.6 cc / L of 34.5% hydrogen peroxide solution and having a liquid temperature of 30 ° C. ± 1 ° C. The laminated board whose etching rate of the said copper foil on the conditions made to immerse is 0.68 micrometer / min or more and 1.25 micrometers / min or less.
The laminate according to claim 1,
The laminated board whose difference of the Vickers hardness of the said copper foil is 0 Hv or more and 50 Hv or less before and after the heat processing of the following conditions.
Conditions: The heating temperature is 230 ° C. and the heating time is 1 hour.
In the laminated board of Claim 1 or 2,
The laminated board whose film thickness of the said copper foil is 0.1 micrometer or more and 5 micrometers or less.
In the laminated board of any one of Claim 1 to 3,
The laminated board whose Vickers hardness of the said copper foil is 230 Hv or more and 240 Hv or less after heat processing at 230 degreeC for 1 hour.
In the laminated board of any one of Claim 1 to 4,
The laminated board whose cross-sectional grain size of the said copper foil after 230 degreeC and 1 hour heat processing is 2.0 micrometers or less.
Preparing a laminate comprising an insulating layer and a copper foil located on at least one surface of the insulating layer;
Forming a conductor circuit by selectively removing the copper foil,
The manufacturing method of the printed wiring board whose said laminated board is a laminated board of any one of Claim 1 to 5.