TW201124264A - Copper clad laminate - Google Patents

Abstract

To provide a copper clad laminate having a copper layer formed with high adhesive strength for an insulating layer although surface roughness of the insulating layer is extremely small. The copper clad laminate is manufactured through the processes of: arranging one or more prepregs between two copper foils each having a copper alloy plating layer formed on a surface by electroplating with copper alloy plating layers on prepreg sides, and bonding the copper foils to the prepregs by thermocompression by heating and pressing them under reduced pressure; removing the copper foils with a copper etchant; and forming copper layers on prepreg surfaces by electroless plating.

Description

201124264 VI. Description of the Invention: [Technical Field of the Invention] The present invention relates to a method for manufacturing a copper-clad laminate and a copper-clad laminate. [Prior Art] It has been known that the rough surface of the copper foil is bonded to the surface of the curable resin composition layer, and the hardenable resin composition layer is cured, and the copper foil is improved by the anchor effect on the uneven surface of the rough surface of the copper foil. A technique in which a copper foil is used as a conductor layer can be used as a sealing force with an insulating layer (curable resin composition layer after curing). In addition, after the copper foil is bonded to the curable resin composition layer and cured, the copper foil is removed, and the rough surface of the copper foil is unevenly transferred into an insulating layer, and the anchor effect of the unevenness of the insulating layer is transferred. The technique of increasing the adhesion to the plated conductor layer formed on the insulating layer is known. However, when the unevenness of the surface of the insulating layer is increased, the peeling strength of the coated conductor layer is increased, and when the circuit is formed on the reverse side, it is difficult to remove the conductive layer of the uneven portion when the conductive layer is removed by etching. When the etching is performed under the condition that the conductive layer of the uneven portion is sufficiently removed, the dissolution of the circuit wiring is remarkable, and the problem of fine wiring is caused. On the other hand, a copper foil which is a copper foil for a plasma display panel and which is to be blackened by a Ni alloy or the like to prevent light reflection is known (Patent Document 1). [PRIOR ART DOCUMENT] [Patent Document] 201124264 [Patent Document 1] International Publication No. 2005/079130 A SUMMARY OF THE INVENTION An object of the present invention is to provide a high-density strength for an insulating layer even if the surface roughness of the insulating layer is extremely small. A method for producing a copper-clad laminate in which a copper layer is formed. As a result of repeating the detailed examination, the inventors have found that the step of thermally pressing the copper alloy plating layer toward the insulating layer under specific conditions, the step of removing the copper foil, and the step of forming a copper layer can solve the above problems. The present invention has been completed. That is, the present invention contains the following forms. [1] A method for producing a copper-clad laminate, comprising the following steps (A) to (C); (A) forming a copper alloy plating layer between two copper foils on a surface by electroplating, One or more prepregs are placed in a copper alloy ore layer to be a prepreg side, and heated and pressurized under reduced pressure to heat the copper box: in the step of _ stomach dip, (B) copper The step of removing the foil by a copper etching solution, and (C) the step of forming a copper layer on the surface of the prepreg by electroless plating. [2] The method for producing a copper-clad laminate according to the above [1], wherein the copper alloy plating layer has a surface roughness (Ra) of 300 nm or less. [3] The surface roughness of the surface of the prepreg of the copper-clad laminate according to the above [1] or [2] (RO is 300 nm or less. 201124264 [4] Any of the above [1] to [3] The method for producing a copper-clad laminate according to the present invention, further comprising the step of removing the copper alloy plating layer according to any one of the above [1] to [4]. The method of producing a copper-clad laminate according to any one of the above-mentioned [1] to [5], further comprising (F) a desmear step. The method for producing a copper-clad laminate according to any one of the above-mentioned, further comprising the step (G) of forming a conductor layer by electroplating. [8] In the above [1] to [7] A method for producing a copper-clad laminate according to any one of the invention, wherein, as the copper foil in the step (A), a copper foil further laminated with an adhesive layer on a surface of the copper alloy plating layer and/or used as a prepreg is used. The method of producing a copper-clad laminate according to any one of the above-mentioned [1] to [8] wherein the copper alloy is selected from the group consisting of Ni-Co-C Any of Ni, Cu, and Co-Cu. [10] A copper-clad laminate, characterized in that the surface roughness (Ra) of the surface of the insulating layer of the prepreg is 5 nm or more and 300 nm or less. A conductor layer is formed on the surface of the insulating layer, and the peeling strength (kgf/cm) of the insulating layer of the conductor layer is 0.50 or more and 10 or less. Under special conditions, the copper alloy plating layer is hot pressed toward the insulating layer. The steps of removing the copper foil and the step of forming the copper layer, even if the surface roughness of the insulating layer is extremely small, can provide a method for producing a copper-clad laminate which forms a copper layer with high adhesion strength to the insulating layer. MODE FOR CARRYING OUT THE INVENTION 201124264 The method for producing a copper-clad laminate according to the present invention includes the following steps as a main feature. (A) A copper alloy plating layer is formed between two copper boxes on the surface by a shovel' One or more prepregs are disposed as a copper alloy plating layer to form a pre-body side, a step of heating and pressurizing under reduced pressure to heat the copper box to the prepreg, and (B) a copper foil as copper. The step of removing the etching solution, and (C) the surface of the prepreg by electroless shovel Step of forming a copper layer [copper foil formed on the surface of a copper alloy plating layer] (copper foil) As the copper foil, for example, an electrolytic copper foil or a rolled copper foil is used. The surface roughness of the surface on which the copper alloy plating layer is formed (Ra The thickness is preferably 150 nm or less, and preferably 1 2 Onm or less. The thickness of the copper foil is not particularly limited, but the upper limit is preferably 70 μm or less from the viewpoint that the handleability is too large when the thickness is too large, and the thickness is 50 μm or less. More preferably, it is more preferably 30 μm or less, and still more preferably 18 μm or less. Further, when the thickness is too thin, the lower limit of the thickness of the copper foil is preferably 9 μm or more. The copper foil is further provided with a carrier to lower the thickness of the copper foil to a lower limit of less than 9 μm. The carrier is a self-supporting film and a sheet-like material, and is not particularly limited, and specific examples thereof include a metal foil such as copper or aluminum, polyethylene terephthalate, and poly 2,6-naphthalenedicarboxylic acid. Plastic film such as ethylene glycol ester. The thickness of the carrier is preferably from 1 2 to 50 μm, and when the thickness is thinner than 12 2 μm, the handleability tends to decrease. Further, a copper foil with a carrier is formed on the carrier to form a release layer made of a chromium-based dissimilar metal or an organic substance such as a nitrogen-containing compound or a sulfur-containing compound, and a thin copper film is formed thereon by electroplating. (Copper alloy plating layer) The "copper alloy plating layer" in the present invention is a layer obtained by performing a plating treatment of a copper alloy on a copper foil. Further, the copper alloy is an alloy formed of a metal other than copper and copper, and is specifically selected from the group consisting of Ni-Co-Cu, Ni-Cu, and Co-Cu. The method for forming the copper alloy plating layer is not particularly limited, and may be carried out by a copper plating method for plating the surface of the copper foil. The surface roughness in the copper alloy plating layer from the viewpoint of the surface roughness of the copper alloy plating layer formed on the copper foil (the surface of the prepreg (the surface of the insulating layer) after the RO is transferred by the hot pressing) The upper limit of (Ra) is preferably 3,000 nm or less, preferably 250 nm or less, more preferably 200 nm or less, and further preferably 150 nm or less. On the other hand, if the surface roughness of the copper alloy plating layer ( When Ra) is too small, the surface roughness (Ra) of the rough surface of the surface of the prepreg (the surface of the insulating layer) after the transfer heating and pressing is too small, and the adhesion of the conductor layer formed on the surface of the insulating layer may occur. From the viewpoint of the reduction, the lower limit of the surface roughness (Ra) in the copper alloy plating layer is preferably 10 nm or more, more preferably 20 nm or more, and even more preferably 30 nm or more. The amount of plating metal on the surface of the copper foil is adjusted to the thickness of the copper alloy. -9- 201124264 The surface roughness of the coating layer. Specifically, in the case of forming a Ni-Co-Cu layer, the amount of plating to Ni + Co is performed (Ni The total adhesion amount with Co is preferably 130 to 1 000 mg/m 2 . If the adhesion amount of Ni + C 少 is less than I30 mg/m 2 , On the surface of the metal foil, there is a tendency that a sufficient copper alloy plating layer cannot be formed. If it exceeds 1000 mg/m2, the surface roughness of the copper alloy plating layer tends to be too large. Further, when the Ni-Cu layer is formed, the ore is formed. When the amount of adhesion to Ni is 200 to 1 000 mg/m 2 , if the amount of adhesion of Ni is less than 200 mg/m 2 , it is difficult to form a sufficient copper alloy plating layer on the surface of the metal foil, and when it exceeds 1,000 mg/m 2 . There is a tendency that the surface roughness of the copper alloy plating layer is too large, and when the Co-Cu layer is formed, the adhesion amount of plating to Co is preferably 300 to 1000 m g/m 2 . If the adhesion amount of Co is 300 m g / When m2 is small, it tends to be difficult to form a sufficient copper alloy plating layer on the surface of the metal foil. When it exceeds 1,000 mg/m2, the surface roughness of the copper alloy plating layer tends to be too large. The following shows formation of Ni-Co-Cu. Preferred plating conditions for the layer, Ni-Cu layer or Co-Cu layer (Cu-Ni-Co plating solution)

Cu : 5 ~ 30g / L

Ni: 5 ~ 30g / L

Co : 5 ~ 3 0g / L pH : 2 ~ 4

Liquid temperature: 20~60°C Current density: 30~60A/dm2 -10- 201124264 (C u - C 0 plating solution)

Cu: 5 to 30 g/L Co: 10 to 30 g/L pH: 2 to 4 Liquid temperature: 20 to 60 ° C Current density: 30 to 50 A/dm 2 (Cu-Ni plating solution)

Cu: 5 to 30 g/L Ni: 1 〇 to 30 g/L pH: 2 to 4 Liquid temperature: 20 to 55 ° C Current density: 30 to 55 A/dm 2 (rust-proof treatment layer) Copper alloy plating layer of the present invention The copper foil formed on the surface is preferably further subjected to rust-preventing treatment on the copper alloy plating layer from the viewpoint of suppressing oxidation of copper. In the anti-rust treatment, inorganic rust inhibitors such as zinc (Zn), chromate, zinc alloy (specifically Zn-Ni, Zn-Ni-P, etc.) may be used, and the rust inhibitor may be used alone or in combination. 2 or more types. Further, the method of preventing rust treatment using the rust preventive agent is not particularly limited, and an electroplating method, an electroless plating method, a sputtering method, or the like can be used. Among them, Ζη·chromate treatment is preferred, and as the plating conditions by electroplating, the following conditions can be specifically exemplified. (Ζ η, chromate treatment solution) -11 - 201124264 K2Cr207 : 2 〜1 〇g/L Zn : 0· 1 ～0.5g/L Na2S〇4 : 5 〜20g/L pH : 3.5 ～5.0 Liquid temperature: 20~60°C Current density: 〇. 1~3 .OA/dm2 Plating time: 1~3 seconds and even if it is treated by anti-rust, there is no substantial change in the copper dad, and the copper alloy after the anti-rust treatment ( The upper limit of Ra) is preferably 300 nm or less, more preferably 200 nm or less, and 150 nm is preferably 10 nm or more, preferably 20 nm or more. <Adhesive layer> The copper alloy plating layer of the present invention is formed in the game. The adhesive layer can be laminated in the step of adhesion to the prepreg during heat pressing. The copper alloy shovel layer is laminated on the rustproof surface. The thickness of the same adhesive layer of the curable resin composition to be specifically used on the adhesive layer is not particularly limited, and the upper limit of the thickness of the adhesive layer is specifically determined from the viewpoint of the thermal expansion coefficient in the copper-clad laminate. 5 μιη or less is preferable, and the surface roughness of the plating layer is preferably 1 ο μηι or less and the surface roughness of the surface of the coating layer is preferably 250 nm or less, and the step is more preferable. Further, in the copper foil having a better surface of 30 nm or more, in order to improve the copper alloy plating layer, a prepreg resin composition to be described later can be used for the rust-preventing body. The thinner the better the tendency. The suppression of the rise or the reduction in rigidity is preferably 20 μm or less, preferably 5 μιη or less. -12- 201124264 One step is better. Further, from the viewpoint of excellent stability in production, the lower limit of the thickness of the adhesive layer is preferably 0. 5 μm or more, and more preferably 1 μm or more. The adhesive layer can be obtained by forming a layer of a curable resin on the copper alloy plating layer. The method of forming the adhesive layer is not particularly limited, and a known method can be used. Specifically, the resin varnish can be prepared by dissolving the resin composition in an organic solvent, applying the resin varnish to a copper alloy plating layer by a die coating or the like, and drying the organic solvent by heating or hot air blowing. The organic solvent is not particularly limited as long as it dissolves the resin composition, and specific examples thereof include ketones such as acetone, methyl ethyl ketone and cyclohexanone, ethyl acetate, butyl acetate, and sirolimus acetate. Acetate such as propylene glycol monomethyl ether acetate or carbitol acetate, carbitol such as 赛路苏, butyl carbitol, aromatic hydrocarbons such as toluene and xylene, and dimethyl ketone Indoleamine, dimethylacetamide, N-methylpyrrolidone, and the like. The organic solvent may be used alone or in combination of two or more. The drying condition is not particularly limited as long as the content of the organic solvent in the resin composition can be reduced, and the content of the organic solvent in the resin composition layer is preferably 1% by mass or less, and 5% by mass or less. good. Depending on the amount of the organic solvent in the varnish, the boiling point of the organic solvent, etc., specifically, the varnish containing 30 to 60% by mass of the organic solvent is dried at 50 to 150 ° C for 3 to 10 minutes to form an adhesive. Floor. The adhesive layer is different from the copper foil, and the adhesive film of the curable resin composition layer is formed on the support, and the curable resin composition layer is brought into contact with the copper alloy plating layer on the surface of the copper foil to adhere thereto. The film can be formed by bonding a film to a copper foil under heating. -13- 201124264 The so-called adhesive film support is a self-supporting film or sheet, and a plastic film or the like can be used, and is particularly suitable for a plastic film. Examples of the plastic film include polyethylene terephthalate, polyethylene-2,6-naphthalate, polyimine, polyamidimide, polyamine, and polytetrafluoroethylene. From the viewpoint of cost efficiency, a film such as polycarbonate is preferably a polyethylene terephthalate film or a polyethylene 2,6-naphthalate film, and is preferably polyethylene terephthalate. good. Further, from the viewpoint of easily peeling off the support itself, it is preferred to apply a surface treatment (corona treatment or the like) to the surface of the support or to form a release layer on the surface of the support. A support for a vending product may also be used, and specifically, T6 0 (a polyethylene terephthalate film made by Toray) and A4100 (a polyethylene terephthalate film made by Toyobo Co., Ltd.) may be mentioned. Q83 (polyethylene 2,6-naphthalate film made by Teijindupontfilm Co., Ltd.), polyethylene terephthalate with alkyd type release agent (AL-5) made by Lintec Co., Ltd. Film, Dia foil B100 (polyethylene terephthalate film made by Mitsubishi Chemical Polyester Film Co., Ltd.). The adhesion between the adhesive film and the copper foil is such that the adhesive film is superposed on the copper foil so that the curable resin composition layer faces the copper foil, and is subjected to hot pressing, a hot roll or the like. The heating temperature at this time is preferably selected from the range of 60 to 140 ° C, more preferably from 80 to 120 ° C. The pressing pressure is better! ～ llkgf/cm 2 ( 9·8 χ 104 ～ 107.9 gt; &lt; 104 N/m 2 ), preferably selected from the range of 2 to 7 kgf/cm 2 (19.6×10 4 to 68.6×10 4 N/m 2 ), and the time is in the range of 5 seconds to 3 minutes. Preferably, it is preferably in the range of 15 seconds to 1 minute. Further, it is preferred to carry out lamination under a reduced pressure of 20 mmHg (26_7 hPa) or less. Further, heating, pressing, and the like in the bonding of the adhesive film and the copper foil are carried out until the hardening resin composition layer is stopped in the intermediate stage (stage B) of the hardening reaction. Further, in the present invention, a "copper alloy plating layer formed on the surface of a copper foil" can be used as a retail product. Specifically, "HLPFN" manufactured by Nippon Minerals Co., Ltd. (copper alloy plating layer: Ni-Co-Cu, rust-preventing treatment: Zn' chromate treatment, surface roughness (Ra): about 205 nm ) "BHY-HA" made of Nippon Mining Metal Co., Ltd. (copper alloy plating layer: Ni-Co-Cu, rust-proof treatment: Zn 'chromate treatment, surface roughness (Ra) · about 300 nm) . [Prepreg] The prepreg system of the present invention can be obtained by impregnating a flaky fiber substrate with a hardenable resin composition and drying it by heating. The curable resin composition is not particularly limited as long as the cured product has sufficient hardness and insulation. Specifically, it is used for epoxy resin, cyanate resin, phenol resin, and bismaleimide. A composition in which at least a curing agent is added to a curable resin such as a triazine resin, a polyimine resin, an acrylic resin or a vinyl benzyl resin. In particular, a composition containing an epoxy resin and a curing agent is preferable, and a composition containing an epoxy resin and a curing agent together with a thermoplastic resin is preferable. The epoxy resin is not particularly limited as long as it has curability, and specific examples thereof include a bisphenol A type epoxy resin, a biphenyl type epoxy resin, a naphthol type epoxy resin, and a naphthalene type ring. Oxygen resin, bisphenol F type epoxy resin, phosphorus-containing epoxy resin, bisphenol S-type epoxy resin, alicyclic epoxy resin, aliphatic chain epoxy resin, phenolic phenolic phenolic resin Type epoxy tree-15- 201124264 phenolic epoxy resin for phenolic phenolic paint, phenolic epoxy resin for bisphenol ray paint, epoxy resin with butyl dibasic structure, bisphenol epoxy a propyl etherate, a diepoxypropyl etherate of naphthalenediol, a phenolic propyl ether etherate of a phenol, and a diepoxypropyl etherate of an alcohol, and an alkyl substitution of the epoxy resin Body, halides and hydrides. One type or two or more types of epoxy resins may be used in combination. From the viewpoints of heat resistance, insulation reliability, and adhesion to a metal film, bisphenol A type epoxy resin, naphthol type epoxy resin, naphthalene type epoxy resin, biphenyl type ring An oxy resin or an epoxy resin having a butyl diene structure, a liquid bisphenol A type epoxy resin ("jER828EL" manufactured by Nippon Epoxy Co., Ltd.), and a naphthalene type 2-functional epoxy resin ( DIC (product) "HP4032", "HP4032D", etc.), naphthalene type 4-functional epoxy resin ("HP4700" manufactured by DIC Co., Ltd.), and naphthol type epoxy resin (ESN manufactured by Tohto Kasei Co., Ltd.) -4 75V", "ESN-185V"), 蒽醌-type epoxy resin (YX8 8 00, manufactured by Nippon Epoxy Resin Co., Ltd.), epoxy resin with dibutyl structure (Daicel Chemical Industry Co., Ltd.) ) "PB-3 600"), epoxy resin with biphenyl structure ("NC3 000H", "NC3 000L", "NC3100", "NC3000", Nippon Epoxy resin manufactured by Nippon Kayaku Co., Ltd. It is preferable to use "γχ4〇〇〇" and "GK3 207" manufactured by Toto Chemicals Co., Ltd.) as a curing agent. The ability to harden is not particularly limited, and specific examples thereof include an amine curing agent, an lanthanum curing agent, an imidazole curing agent, a phenolic curing agent containing a triazine skeleton, a phenolic curing agent, and a naphthalene cool containing a triazine skeleton. a hardener, a naphthoquinone-based hardener, an acid anhydride-based hardener or a ring thereof - 16 to 201124264 oxy-adduct or microencapsulated, an active ester-based hardener, a benzoxazine-based hardener, cyanic acid An ester resin, etc. These may be used singly or in combination of two or more kinds. From the viewpoint of improving the peel strength of plating, it is preferred that the curing agent has a nitrogen atom in the molecular structure, and a phenol containing a triazine skeleton. A hardening agent, a naphthol-based curing agent containing a triazine skeleton, and a phenol novolak resin containing a triazine skeleton are more preferable. The phenolic curing agent and the naphthol-based curing agent are not particularly limited, and specifically Examples include MEH-7700, MEH-7810, MEH-7851 (Mingwa Chemical Co., Ltd.), NHN, CBN, GPH (Nippon Chemical Co., Ltd.), SN170, SN180, SN190, SN47 5, SN4 8 5, SN49 5 ' SN375 , SN 3 9 5 (Dongdu Huacheng Co., Ltd.), T D2 090 (manufactured by DIC). The phenolic curing agent containing a triazine skeleton is not particularly limited, and specific examples thereof include LA3018, LA7052 'LA7054 &gt; LA1356 (manufactured by DIC). The agent is not particularly limited as long as it has a function as a curing agent for the epoxy resin, but specifically has two or more phenolic esters, thiophenolic esters, and N-hydroxylamine esters in one molecule. A compound having a highly reactive ester group such as an ester of a heterocyclic hydroxy compound is preferred. The active ester-based hardener is preferably obtained by a condensation reaction of a carboxylate and/or a sulfuric acid compound with a hydroxy compound and/or a thiol compound. From the viewpoint of heat resistance and the like, it is more preferable to use an active ester-based curing agent obtained from a carboxylate compound and a phenol compound or a naphthol compound. Specific examples of the carboxylate include benzoic acid, acetic acid, succinic acid, maleic acid, itaconic acid, phthalic acid, isophthalic acid, terephthalic acid, and pyromellitic acid. Examples of the phenol compound or naphthol compound -17-201124264 include hydroquinone, resorcin, bisphenol A, bisphenol F, bisphenol S, phenolphthalein, methylated bisphenol A, and methylated bisphenol. F, methylated bisphenol S, phenol, hydrazine-cresol, m-cresol, p-cresol, catechol, α-naphthol, /3-naphthol, 1,5-dihydroxynaphthalene, 1 ,6-dihydroxynaphthalene' 2,6-dihydroxynaphthalene, dihydroxybenzophenone, trihydroxybenzophenone, tetrahydroxybenzophenone, phloroglucinol, benzenetriol, dicyclopentadiene Diphenols, phenolic paints, etc. Two or more kinds of active ester-based curing agents may be used alone or in combination. Further, as the active ester-based curing agent, an active ester-based curing agent disclosed in JP-A-2004-42 776 1 may be used, and it may be used as a seller. Specific examples of the commercially available active ester-based curing agent include EXB-945 1 and EXB-9460 (manufactured by DIC Co., Ltd.) containing a dicyclopentadiene diphenol structure, and an acetamino group as a phenolic phenolic aldehyde. Illustrative examples of the compound include DC 8 08 (manufactured by Nippon Epoxy Resin Co., Ltd.), and benzyl hydrazine phenolate for phenol paint, and YLH 1 02 6 (manufactured by Nippon Epoxy Co., Ltd.). Specific examples of the benzoxazine-based curing agent include F-a, P-d (manufactured by Shikoku Chemical Co., Ltd.), and HFB2 006M (manufactured by Showa Polymer Co., Ltd.). Specific examples of the cyanate resin include a phenolic type for a paint (a phenol type for a phenol paint, a phenol type for an alkyl phenol paint), a cyanate resin, and a bisphenol type (bisphenol A type, bisphenol F type, and bisphenol S). Type, etc.) cyanate resin and a part of the triazine-based prepolymer. Specific examples of the preferred cyanate resin include bisphenol A dicyanate and polyphenol cyanate (oligo(3-methyl-1,5-phenylene), 4,4' - Methyl bis(2,6-dimethylphenyl cyanate), 4,4'-ethylene diphenyl dicyanate, hexafluorobisphenol A dicyanate, 2,2- Bis(4-cyanate) phenylpropane, 1,1-bis(4-cyanate phenylmethane), bis(4-cyanate-18- 201124264 ester-3, 5-dimethylphenyl) Methane, 1,3-bis(4-cyanate phenyl-1-(methylethylidene))benzene, bis(4-cyanate phenyl) sulfide, bis(4-cyanate phenyl) a bifunctional cyanate resin such as ether, a phenolic phenolic phenol, a polyfunctional cyanate resin derived from phenolic phenolic or the like, a partially-triazine-based prepolymer of these cyanate resins, and the like. Examples of the commercially available cyanate resin include PT30 (phenolic polyfunctional cyanate resin for phenol paint, cyanate equivalent 124) manufactured by Lonza Japan Co., Ltd., and BA23 0 manufactured by Lonza Japan Co., Ltd. ( Part or all of bisphenol A dicyanate is triazineized to a prepolymer of a terpolymer, cyanate equivalent 232), Lonza Japan ( DT4000 (dicyclopentadiene type polyfunctional cyanate resin, cyanate ester amount of 140%) manufactured by the company. The blending ratio of the epoxy resin and the curing agent is not particularly limited as long as it exhibits a resin, and is specifically a phenolic curing agent containing a triazine skeleton, a phenolic curing agent, and a naphthol-based hardening containing a triazine skeleton. In the case of a solvent or a naphthol-based curing agent, the ratio of the phenolic hydroxyl equivalent of the curing agent to the range of 0·4 to 2·0 is preferably 5% of the epoxy equivalent of the epoxy resin. The ratio of the range of 4 to 1.0 is preferably 0.5 to 〖. The ratio of the range of 〇 is more preferable. When the reaction group equivalent ratio is outside the range, the mechanical strength or water resistance of the cured product tends to decrease.

In the thermosetting resin composition of the present invention, a hardener is added, and a hardening accelerator may be further added. The hardening accelerator is not particularly limited as long as it has a hardening-promoting action, and examples thereof include an imidazole compound, a diazabicyclo compound, an organic phosphine, and a scaly compound. Specifically, 2MZ (2-methylidene D sitting), C11Z -19- 201124264 (2-undecylimidazole), (: 17Z (2 -heptadecyl), manufactured by Shikoku Chemical Co., Ltd. Imidazole), 1.2DMZ (1,2-dimethylimidazole), 2E4MZ (2-ethyl-4-methylimidazole), 2ΡΖ(2·phenylimidazole), 2Ρ4ΜΖ(2-phenyl-4-methyl) Imidazole), 1Β2ΜΖ (1-Benzyl-2-methylimidazole), 1Β2ΡΖ (1-Benzyl-2-phenylimidazole), 2MZ-CN(1-cyanoethyl-2-methylimidazole) , C11Z-CN (1-cyanoethyl-2-undecylimidazole), 2E4MZ-CN (1-cyanoethyl-2-ethyl-4-methylimidazole), 2PZ-CN ( 1- Cyanoethyl-2-phenylimidazole), C11-CNS (1. cyanoethyl-2·undecylimidazole trimellitic acid), 2PZCNS-PW (1-cyanoethyl-2-benzene) Benzimidazole trimellitic acid), 2MZ-A (2,4-diamino-6-[2'-methylimidazolyl-(1,)]-ethyl-s-triazine, C11Z-A (2 , 4-diamino-6-[2'-undecylimidazolyl-(1,)]-ethyl-s-triazine), 2E4MZ-A (2,4-diamino-6-[ 2,-Ethyl_4'-methylimidazolyl-(1,)]-ethyl-s-triazine), 2MA-OK (2,4-diamino-6'[2'-methyl Imidazolyl-(1,)]-ethyl-s-triazine iso-cyanurate addenda), 2?1^-?^(2-phenyl-4,5-dihydroxymethylimidazole), 2P4MHZ-PW (2-phenyl-4-methyl-5-hydroxymethylimidazole), hydrazine (2,3-dihydro-1 Η-pyrrolo[l,2-a]benzimidazole, SFZ ( 1- Imidazole compound such as dodecyl-2-methyl-3-benzylimidazolium chloride, Ρ·0505 (epoxy-imidazole adduct), U-CAT SA1 manufactured by San-apro Co., Ltd. (DBU-phenolate), U-CATSA102 (DBU-octyl acid salt), U-CAT SA 506 (DBU-p-toluenesulfonate), U-CAT SA 603 (DBU-formate), U- CAT SA 810 (DBU-phthalate, U-CAT SA 831, 841, 851, U-CAT 881 (DBU-phenolic resin phenolic resin salt), U-CAT 5002 (N-benzyl DBU-) Tetraphenylborate) -20- 201124264 and other diazabicyclo compounds, TPP-S (triphenylphosphine triphenylborane), TPP-K (tetraphenyl iron tetra) manufactured by Beixing Chemical Industry Co., Ltd. An organic phosphine/iron compound such as phenylborate or TBP-DA (tetrabutyl citrate). When the curing accelerator is used, the amount used is not particularly limited, but it is preferably used in the range of 0.1 to 3.0% by mass based on the epoxy resin. In the thermosetting resin composition of the present invention, a thermoplastic resin may be added for the purpose of imparting appropriate flexibility to the composition after curing. Specific examples of the thermoplastic resin include a phenoxy resin, a polyvinyl acetal resin, a polyimine, a polyamidimide, a polyether oxime, and a polyfluorene. These may be used alone or in combination of two or more. When the non-volatile content of the thermosetting resin composition is 100% by mass, the thermoplastic resin is preferably added in a ratio of 0.5 to 60% by mass, preferably 3 to 50% by mass. When the blending ratio of the thermoplastic resin is less than 0.5% by mass, the viscosity of the resin composition is lowered, and it is difficult to form a uniform thermosetting resin composition layer. When the content exceeds 60% by mass, the viscosity of the resin composition may pass. High, there is a resin that cannot flow between the gaps between the glass cloths, and there is a tendency to easily leave voids in the glass cloth. The phenoxy resin is not particularly limited, and specific examples thereof include FX2 80, FX293 manufactured by Tohto Kasei Co., Ltd., γχ8100, YL6954, YL6974, YL7213, YL6794, YL74 82, and YL75 5 3 manufactured by Nippon Epoxy Resin Co., Ltd. YL7290 and so on. The polyvinyl acetal resin is preferably a polyvinyl butyral resin, and the polyvinyl acetal resin is specifically an electrochemical Butyral 4000-2, 5 000-A, 6000-C manufactured by the Electrochemical Industry Co., Ltd. 6000-ΕΡ, Sekisui Chemical Industry Co., Ltd. s-recl BH series, BX series 'KS system 歹[J, BL series-21 - 201124264 column, BM series, etc. Specific examples of the polyimine are Polyimine amide "Liquacoat SN20" and "Liquacoat PN20" manufactured by Shin-Nihon Chemical Co., Ltd. Further, a linear polyimine obtained by reacting a bifunctional hydroxyl-terminated polybutylene dichloride, a diisocyanate compound, and a tetrabasic acid anhydride (described in JP-A-2006-3 807), and Denatured polyimine, such as a polyfluorene skeleton of the polyoxyalkylene skeleton (described in JP-A-2002-12667, JP-A-2000-319386, etc.). Specific examples of the polyamidoximine are the polyanilide oxime "VylomaxHRl 1NN" manufactured by Toyobo Co., Ltd., "

VylomaxHR16NN". Further, a modified polyamidoquinone imine such as "polyacrylamide"-containing polyamine amidoxime "KS9100" or "KS 93 00" manufactured by Hitachi Chemical Co., Ltd. can be cited. Specific examples of the polyether oxime include polyether oxime "PES5003 P" manufactured by Sumitomo Chemical Co., Ltd., and the like. As a specific example of the polyfluorene, a polyfluorene "P1700" manufactured by Solvay Advanced Polymers Co., Ltd. is exemplified. , "P3500" and so on. In the thermosetting resin composition of the present invention, an inorganic enamel filler which is intended to reduce the thermal expansion of the hardened composition may be contained. Specific examples of the inorganic cerium filling material include cerium oxide, aluminum oxide, mica, mica, ceric acid salt, barium sulfate, magnesium hydroxide, titanium oxide, etc., preferably cerium oxide or aluminum oxide, and particularly preferably no. Forming cerium oxide, molten cerium oxide, crystalline cerium oxide, and synthetic cerium oxide such as cerium oxide. It is preferred that the cerium oxide is spherical. Further, the inorganic chelating agent is preferably one having an average particle diameter of 22 to 201124264 of 3 μm or less, and preferably having an average particle diameter of not more than 5 μη1 from the viewpoint of insulation reliability. The average particle diameter of the inorganic cerium can be measured by a laser diffraction/scattering method according to the Mi e scattering theory. Specifically, the particle size distribution of the inorganic cerium filling material can be prepared by volume measurement based on the laser diffraction type particle size distribution measuring device, and the same diameter is measured as the average particle diameter. The measurement sample is preferably used. It is preferred that the inorganic cerium filling material is dispersed in water by ultrasonic waves. As the laser diffraction type particle size distribution measuring apparatus, LA-500 or the like manufactured by Horiba, Ltd. can be used. The inorganic ruthenium filler is preferably subjected to surface treatment by the following surface treatment agent in order to improve moisture resistance, dispersibility, and the like. Examples of the surface treatment agent include aminopropyl methoxy decane, aminopropyl triethoxy decane, ureidopropyl triethoxy decane, and N-phenylaminopropyl trimethoxy decane. An amine decane-based coupling agent such as n-2 (aminoethyl)aminopropyltrimethoxydecane; glycidoxypropyltrimethoxydecane, glycidoxypropyltriethoxydecane, Epoxy propoxypropylmethyldiethoxydecane, epoxypropylbutyltrimethoxydecane, (3,4-epoxycyclohexyl)ethyltrimethoxy sand courtyard, etc. An affinity agent; a thiosulfanyl couplant such as a thiopropylpropyltrimethoxylate or a thiopropylpropyltriethoxy decane; a methyltrimethoxy sulphate or an octadecyltrimethoxydecane , phenyl trimethoxy decane, methacryloxypropyl trimethoxy decane, imidazolium, triazine decane, etc.; hexamethyldidecylamine, hexaphenyldioxanylamine, Organic sand nitrogen compound compounds such as dimethylaminotrimethylnonane, triazane, cyclotriazane, anthracene, anthracene, 3,3,5,5-hexamethylcyclotricarbaea Butyl phthalate dimer, chinosin glycolate diisopropoxy bis (ammonium triacetate), dihydroxy-23- 201124264 base titanium dilactate, dihydroxy bis(ammonium lactate) Titanium, bis(dioctyl pyrophosphate) extended ethyl titanate, bis(dioctylpyrophosphate)oxyacetate titanate, tri-n-butoxytitanium monostearate, Tetra-n-butyl titanate, tetrakis(2-ethylhexyl) titanate, tetraisopropylbis(dioctyl phosphate) titanate, tetraoctyl bis(ditridecyl phosphate) Titanate, tetrakis(2,2-diallyloxymethyl-1-butyl)bis(ditridecyl)phosphate titanate, isopropyl trioctadecyl titanate, isopropyl Trisyl phenyl phenyl titanate, isopropyl triisostearyl strontium titanate, isopropyl isostearyl decyl dipropenyl titanate, isopropyl dimethyl propylene isostearyl Mercapto titanate, isopropyl tris(dioctyl phosphate) titanate, isopropyl dodecyl benzene sulfonate titanate, isopropyl ginseng (dioctyl pyrophosphate) titanium Acid salt, isopropyl tris(indole-nonylaminoethylaminoethyl) titanate A titanate-based coupling agent or the like. These may be used alone or in combination of two or more. The content of the inorganic chelating agent in the curable resin composition is not particularly limited as long as the effect of the present invention is not inhibited, and the nonvolatile content of the curable resin composition is 100% by mass. 20 to 80% by mass is preferable, preferably 20 to 70% by mass, more preferably 20 to 60% by mass, still more preferably 20 to 5% by mass. When the content of the inorganic chelating agent is less than 20% by mass, the effect of lowering the coefficient of thermal expansion may not be sufficiently exhibited. When the content of the inorganic chelating agent exceeds 80% by mass, the mechanical strength of the cured product is lowered. tendency. Further, the curable resin composition may contain solid rubber particles for the purpose of improving the mechanical strength of the cured product, the stress relieving effect, and the like. The rubber particles are not dissolved in the organic solvent in the preparation of the resin composition, and are not compatible with the components in the resin composition such as the epoxy group-24-201124264 resin, and are dispersed in the varnish of the resin composition. The survivor is better. Such rubber particles are generally prepared in a particulate form by increasing the molecular weight of the rubber component to a level that is insoluble in an organic solvent or resin. Specific examples of the rubber particles include core-shell type rubber particles, crosslinked nitrile butadiene rubber particles, crosslinked styrene butadiene rubber particles, and acrylic rubber particles. The core-shell type rubber particles are rubber particles having a core layer and a shell layer, and specifically, the shell layer of the outer layer is a glassy polymer, and the core layer of the inner layer is a two-layer structure or outer layer composed of a rubbery polymer. The shell layer is a glassy polymer, and the intermediate layer is a rubber-like polymer, and the core layer is a three-layer structure composed of a glassy polymer. The glassy polymer layer is specifically composed of a polymer of methacrylic acid methyl group or the like, and the rubbery polymer layer is specifically composed of a butyl acrylate polymer (butyl rubber) or the like. Specific examples of the core-shell type rubber particles include Staphyloid AC3822 and AC3 8 1 6N (product name of ganz chemical product)

, Metablen KW-4426 ( MITSUBISHI RAYON (share) trade name). Specific examples of the acrylonitrile butyl rubber (NBR) particles include XER-91 (average particle diameter 〇.5μηι, manufactured by JSR). Specific examples of the styrene butyl rubber (SBR) particles include XSK-500 (average particle diameter 〇5 μΐΏ, manufactured by JSR Co., Ltd.). Specific examples of the acrylic rubber particles include Metablen W300A (average particle diameter Ο.ίμιη), W450A (average particle diameter 〇_5μηι) (manufactured by MITSUBISHI RAYON Co., Ltd.), and the like. The average particle diameter of the rubber particles in the present invention can be measured by a dynamic light scattering method. Specifically, in a suitable organic solvent, rubber particles are uniformly dispersed by ultrasonic waves or the like, and FPRA_ 1 000 (large bismuth electrons are prepared by using a particle size distribution of rubber particles as a mass basis and a diameter as an average particle diameter. The rubber particles to be added are preferably in the range of 0.005 to 1 μm, and the content of the rubber particles in the range of 0.2 to 6.6 μηη is 1 to 10% by mass in terms of the resin composition of 100% by mass. The range of % is preferably in the range of a good amount of %. Further, the curable resin composition may be added to the range of the present invention, and may be added with a maleimide compound, a bisallylndiimide compound, or a benzene. A thermosetting resin other than the epoxy resin, such as a base resin-based ether resin. The resin may be used alone or in combination of two or more. Examples of the amine resin include BMI1000, BMI2000, BMI3000, and BMI5100 (Daiwa Chemical Industry Co., Ltd.) )), BMI BMI-80 (Aikei Chemicals Co., Ltd.) 'ANILIX-MI Fine (share) system), as diennene bisallylnadiimide) compounds can be cited BANI-M, j (Nine good stone Chemical Industry Co., Ltd.) Benzene Benzene V5 000 (manufactured by Showa Polymer Co., Ltd.), and vinyl benzene, V10 00X, V1100X (Showa Polymer Co., Ltd.), and a curable resin composition. Further, it is difficult to provide a flame retardant. Specific examples of the flame retardant include a solvent, an organic nitrogen-containing phosphorus compound, a nitrogen compound, a sand, a metal hydroxide, etc. As an organic phosphorus-based flame retardant, The average particle size of the equivalent amount may be preferably. It is non-volatile, with a 2~5 quality effect of diimine (, ethylene styrene is so hard-hardened as Malayan BMI4000, BMI-70' (Mitsui Chemical yttrium (F is BANI-X) The resin may be a methyl ether resin. i) A flammable target phosphorus-based flame retardant oxygen-based flame retardant is a phosphine compound such as HCA, HCA-HQ or HCA-NQ manufactured by Sanguang (-26-201124264). A benzoxazine compound containing phosphorus such as HFB-2〇06M manufactured by Showa Polymer Co., Ltd., and Reofos 30, 50, 65, 90, 1 10, TPP, and RPD 'B APP' manufactured by Ajinomoto Fine-Techno Co., Ltd. CPD, TCP, TXP, TBP, TOP, KP140, TIBP, PPQ made by Beixing Chemical Industry Co., Ltd., OP930 made by Clariant, PX200 made by Da Ba Chemical Co., Ltd., Dongdu Huacheng Phosphorus-containing epoxy resin such as FX289 or FX310, and phosphorus-containing phenoxy resin such as ERF 001 manufactured by Tosho Kasei Co., Ltd., etc. As an organic nitrogen-containing phosphorus compound, the Shikoku Chemical Industry Co., Ltd. Phosphate imine compounds such as SP6 70 and SP703, and SPB100 and SPE100 manufactured by Otsuka Chemical Co., Ltd. Examples of the metal hydroxides include magnesium hydroxide such as UD65, UD650, and UD653 manufactured by Ube Materials Co., Ltd., and B-30, B-325, B-3, and B-made by Ba-Industry Co., Ltd. 308, such as aluminum hydroxide, such as B-303 and UFH-20, etc. These flame retardants can be used singly or in combination of two or more. Further, the curable resin composition does not block the effects of the present invention. In addition, it is preferable to contain any other various resin additives other than the above. Specific examples of the resin additive include organic ruthenium powders such as polyfluorene oxide powder, nylon powder, and fluorine powder, tackifiers such as orbene and benton, and polyoxyl oxide. It is a non-foaming agent such as a fluorine-based or polymer-based antifoaming agent or a leveling agent, a decane coupling agent, a triazole compound, a thiazole compound, a triazine compound, or a porphyrin compound, phthalonitrile blue, phthalonitrile green, A coloring agent such as iodine green, bisazo yellow, carbon black, etc. The flaky fibrous base material is not particularly limited, and can be specifically used as a prepreg, such as Bolivia -27-201124264 cloth, polyarsenide non-woven fabric, liquid crystal polymer non-woven fabric, etc. It is commonly used as a substrate for impregnation. Specifically, ASAH can be mentioned. I SCHWEBEL (Style) Style 1 02 7MS (75 warp density / 25mm, weft density 75 / 25mm, cloth quality 20g / m2, thickness 19μηι), ASAHI SCHWEBEL (Style) Stylel 03 7MS (warp density 70 / 25mm, weft density 73/25mm, cloth quality 24g/m2, thickness 28μιη), (stock) Aozawa Manufacturing Co., Ltd. 1 07 8 (warp density 54 pieces / 25mm, weft density 54 pieces / 25mm, cloth quality 48g / m2, thickness 43μπι ), (share) A glass cloth substrate such as 21 16 (warp density 50 pieces / 25mm, weft density 58 pieces / 25mm, cloth quality 103.8g / m2, thickness 94μηι) made by Ozawa Seisakusho Co., Ltd.; The family polyester is made of Beckles (unit amount: 6 to 15 g/m2) manufactured by Melt-Blow method or Vectran made of Kuraray as non-woven fabric of fiber material. The sheet-like fibrous base material is preferably a thickness of 10 to 150 μm, and preferably 10 to ΙΟΟ μηη. The prepreg can be produced by a known hot melt method, a solvent method, or the like. The hot melt method is a method in which the resin composition is not required to be dissolved in an organic solvent, and once applied to a release paper having good releasability to a resin composition, the laminate is applied to a sheet-like fibrous substrate or directly coated by a mold. A method of producing a prepreg by coating or the like. In addition, the solvent method is a method in which a resinous composition varnish is impregnated with a sheet-like fibrous base material by dissolving a sheet-like fibrous base material in a resin composition varnish in which a resin composition is dissolved in an organic solvent, and then the resin composition varnish is impregnated into a sheet-like fibrous base material. In addition, the adhesive film formed of the curable resin composition laminated on the support can be continuously thermally laminated by heating and pressurizing both sides of the sheet-like reinforcing substrate. -28- 201124264 The organic solvent in the preparation of the varnish is not particularly limited as long as it can dissolve the resin composition, and specific examples thereof include ketones such as acetone, methyl ethyl ketone, and cyclohexanone, and ethyl acetate and acetic acid. Aromatic esters such as butyl acrylate, sirolimus acetate vinegar, propylene glycol monomethyl ether acetate, carbitol acetate, carbaryl, butyl carbitol, etc., toluene, xylene, etc. The hydrocarbons are dimethylformamide, dimethylacetamide, N-methylpyrrolidone and the like. The organic solvent may be used alone or in combination of two or more. The drying conditions are not particularly limited, but the curable resin composition must have fluidity and adhesion at the temperature in the hot pressing step. Therefore, it is important to prevent the hardening of the curable resin composition as much as possible during drying. On the other hand, when a large amount of the organic solvent remains in the prepreg, the amount of the organic solvent in the curable resin composition at the end of the drying is preferably 5% by mass or less. 2% by mass or less is preferred. The specific drying conditions vary depending on the curability of the curable resin composition or the amount of the organic solvent in the varnish, but for example, for a varnish containing 30 to 60% by mass of an organic solvent, it can be used at 80 to 180 ° C. Dry for 3 to 13 minutes. The trader can set suitable and suitable drying conditions by simple implementation. Further, when the copper foil of the adhesive layer is further laminated on the surface of the copper alloy plating layer, the prepreg may be pressurized and heated under reduced pressure in advance. The prepreg is pressurized and heated under reduced pressure in advance, and specifically, the metal foil of the commercially available metallized laminate can be removed, and the prepreg is pressed under reduced pressure using the prepreg. The copper foil of the copper-clad laminate prepared by heat-pressing the copper foil into the prepreg -29-201124264 body can be prepared, and the prepreg is sandwiched between the plastic film treated with the release agent. After pressurization and heating under reduced pressure, the film can be produced by peeling off the release-treated plastic film. The hot pressing step of pressurizing and heating under reduced pressure can be carried out using a general vacuum heat press. Specifically, it is possible to press a metal plate such as a heated SUS plate by pressing both sides of a support or a copper foil. The pressurization condition is such that the degree of pressure reduction is set to lxl (T2 MPa or less, preferably lxl (under a reduced pressure of T3 MPa or less. Pressurization and heating can also be performed by one step, from the viewpoint of controlling the leakage of the resin) It is preferable to carry out the conditions of two stages or more. Specifically, the pressure of the first stage is in the range of 70 to 150 ° C, the pressure is 1 to 15 kgf / cm 2 , and the time is 10 to 60 minutes. The pressurization of the second stage is preferably carried out at a temperature of 1 50 to 250 ° C, a pressure of 1 to 40 kgf/cm 2 , and a time of 60 to 120 minutes. In the present invention, the prepreg is not limited to the above. For the above, the prepreg can be used. Specifically, "GEA-679FG" manufactured by Hitachi Chemical Co., Ltd., "CCL-HL8 32NX Type A" manufactured by Mitsubishi Gas Chemical Co., Ltd., and "CCL-HL" can be used. 8 3 2 NB", etc. The thickness of the prepreg is not particularly limited. From the viewpoint of the cost of the glass cloth and the rigidity expected as the prepreg, it is preferably 20 to 2 50 μm, and 20 to 180 μm. Preferably, it is preferably 20 to 150 μm, and the thickness of the prepreg can be adjusted by impregnation of the curable resin composition. It is easy to control. In addition, the prepreg must have a fluidity that can be laminated without void under pressure. The minimum melt viscosity is preferably in the range of 200 to 30000 poise, and is in the range of 1 000 to -30 to 201124264 20000 poiSe. Further, as described above, the adhesive layer formed on the copper alloy plating layer may be formed on the surface of the prepreg. In this case, the prepreg is specifically made in the resin varnish of the resin composition dissolved in the organic solvent. The body is impregnated or the resin varnish is applied to the prepreg. Further, after drying the organic solvent to form a resin composition layer by heating or hot air blowing, an adhesive layer can be formed on the surface of the prepreg. Organic solvent and drying conditions. The same as the above. [Manufacturing method of copper-clad laminate] The method for producing a copper-clad laminate according to the present invention is at least subjected to the following steps (A), (B) and (C). (A) Copper alloy by electroplating The mineral deposit is formed between two copper foils on the surface. 'One or more prepregs are placed on the copper alloy plating layer to be the prepreg side, and heated and pressed under reduced pressure to heat the copper foil. In the prepreg step, (B) will a step of removing the foil with a copper etching solution, (C) a step of forming a copper layer by electroless plating on the surface of the prepreg, in step (A), heating and pressing under reduced pressure, and hot pressing the copper foil The operation of the prepreg can be carried out by using a general vacuum heat press. Specifically, the metal plate such as a heated SUS plate can be pressed by both the support and the copper foil. The pressurization condition is that the pressure is reduced. The degree is set to 1 x l 〇 2 MPa or less, preferably set to lxl (under a pressure reduction of T3 MPa or less. Heating and pressurization can be performed in one step, but from the viewpoint of controlling leakage of the resin, it can be divided into 2 - 31 - 201124264 It is better to perform under the conditions above the stage. It is better to divide the condition into two or more stages. Specifically, the pressurization of the first stage is performed at a temperature of 70 to 150 ° C, a pressure of 1 to 15 kg f /cm 2 , and a time of 10 to 60 minutes. It is preferably carried out at a temperature of 250 ° C for a pressure of 1 to 40 kgf/cm 2 and a time of 60 to 120 minutes. Specific examples of the commercially available vacuum heat presses include MNPC-V-750-5-200 (manufactured by Nippon Seiki Co., Ltd.), VH 1 - 1 603 (manufactured by Kitagawa Seiki Co., Ltd.), and the like. When two or more prepregs are used, a different prepreg can be used. Specifically, the same or the same may be used as the composition of the curable resin composition constituting the prepreg or the material or thickness of the sheet-like fibrous base material. Further, when the copper foil is further laminated to the copper alloy ore layer, or the prepreg is formed on the surface, the adhesive layer is placed between the copper foil and the prepreg, and One or more prepregs were placed between the copper foils, and a copper-clad laminate precursor of the prepreg and the copper foil was produced in the same manner. Further, from the viewpoint of workability, a copper foil prepreg in which a prepreg is bonded to a copper foil in advance may be used. In this case, two copper-clad prepregs are stacked on the side of the prepreg, or one or more other prepregs are placed between the prepregs of the two copper foil prepregs, and then overlapped. The film was heated and pressed under pressure to prepare a copper-clad laminate precursor of the prepreg and the copper foil. The copper alloy and the prepreg are laminated to form a copper alloy plating layer and a prepreg, which can be laminated by hot pressing, batch lamination, roll lamination, or the like. The heating temperature was 60 from the viewpoint of adhesion between the copper foil-attached film and the prepreg. (: It is better to use -32-201124264. Also, when the temperature is too high, the prepreg will be hardened, and the fluidity of the resin tends to decrease, so it is preferable to be less than 1 7 ° C. The pressure in the case of batch lamination is preferably in the range of 1 to 1 Ugf/cm 2 ( 9.8 χ 104 to 107.9 x 10 4 N/m 2 ), and is 2 to 7 kgf/cm 2 (19.6×10 4 to 6 8 · 6 X 1 ). The range of 04 N/m 2 ) is particularly preferable. The lamination time is preferably in the range of 5 seconds to 3 minutes. In the case of roll lamination, the linear pressure is 1 to 15 kgf/cm, preferably 1 to 1 Okgf/cm. When the pressure is too small, the fluidity of the resin composition is insufficient, and the adhesion to the metal film layer tends to be lowered. When the pressure is too large, there is a tendency that the thickness of the resin is maintained due to the leakage of the resin. When the prepreg is pressurized and heated under reduced pressure in advance, a copper foil having an adhesive layer is laminated on the surface of the prepreg and heated or heated under reduced pressure to be hot pressed. When the prepreg and the copper foil are attached to the copper laminate precursor, the prepreg is preliminarily pressed under reduced pressure and formed on the surface of the heater. When the layer is laminated on the upper surface of the copper foil and heated, or heated and pressed under reduced pressure to perform hot pressing, the intended copper-clad laminate precursor can be produced. Lamination, pressure pressing, etc., wherein lamination is carried out under reduced pressure by vacuum lamination. Further, the lamination method may be batchwise or continuous by a roll. The heating temperature at the time of lamination is preferably from 60 to 140 ° C, preferably from 80 to 120 ° C. The pressure is preferably in the range of from 1 to llkgf/cm 2 ( 9.8 χ 104 to 107.9 x 10 4 N/m 2 ). The range of 2 to 7 kgf/cm 2 (19_6×10 4 to 68.6×10 4 N/m 2 ) is particularly preferable. The time is preferably in the range of 5 seconds to 3 minutes, and preferably in the range of 15 seconds to 33 to 201124264 to 1 minute. The pressure is preferably carried out under a reduced pressure of 20 mm Hg (26.7 hPa) or less. The vacuum lamination can be carried out using a vacuum laminator sold. As a vacuum laminator for sale, a machine manufacturer can be specifically mentioned. Batch-type vacuum pressure laminator MVLP-500, Nichigo-Morton (manufactured) vacuum nozzle, (share) Hitachi Plant Technologies roller Dry coating machine, vacuum laminate for Hitachi AIC (share), etc. The curing conditions after lamination differ depending on the type of curable resin, etc., but generally the curing temperature is 120 to 200 ° C, and the hardening time is 15~ It is preferably carried out at 90 minutes, and it is preferably from the viewpoint of preventing wrinkles on the surface of the formed insulating layer by performing stepwise hardening from a relatively low curing temperature to a high hardening temperature or hardening while rising. . In the present invention, "one or more prepreg-forming copper alloy plating layers may be placed between the two copper foils on the surface of the copper alloy plating layer to form a prepreg side". When the prepreg and the copper foil having a copper alloy plating layer formed on the surface are disposed in a relative relationship, when the copper foil prepreg is used, the copper foil prepreg is attached to the copper alloy by the copper alloy plating layer. On the side of the prepreg, two sheets of the copper foil prepreg are placed on the prepreg side, or one or more prepregs are further disposed between the two copper foil prepregs on the prepreg side. This step (A) is carried out by heating and pressurizing under reduced pressure. By this step (A), the curable resin composition in the prepreg is hardened to the C stage of the final stage of hardening to form an insulating layer of the prepreg. The removal of the copper foil in the step (B) can be achieved if it is achieved, and there is no particular limitation of -34-201124264 'specifically by chlorinating the second iron aqueous solution, chlorinating the second copper aqueous solution, sodium peroxodisulfate and sulfuric acid. A copper etching solution such as an aqueous solution is used. As the copper etching liquid to be sold, an alkaline etching liquid such as CF_6000 manufactured by MEC Co., Ltd. or E-process-WL manufactured by Meltex Co., Ltd. may be mentioned. The thickness of the copper foil differs depending on the thickness of the copper foil, etc., but the removal of the copper foil is generally carried out by immersing the copper foil in a saturated liquid (2 Torr to 60 ° C) for about 10 to 60 minutes. Further, a method of etching the etching liquid into a prepreg and a copper foil-clad laminate precursor may be carried out as a spray. The conditions are the same as the dipping method. The copper foil is removed by the copper etching solution, and the surface roughness (Ra) of the copper foil having the copper alloy plating layer transferred to the surface of the prepreg exposed after the copper foil removal treatment is 300 nm or less. The fine rough surface. The upper limit of the surface roughness (Ra) of the prepreg exposed after the copper box is removed is preferably 300 nm or less, preferably 250 nm or less, more preferably 200 nm or less, and further preferably 150 nm or less. The copper alloy ore layer formed on the surface of the copper foil can be almost removed simultaneously with the copper foil by the removal of the copper foil, but a portion remains on the surface of the prepreg. The residual amount of the copper alloy plating layer can be measured by X-ray photoelectron spectroscopy (X P S ), and the measurement 値 is 1.0% or more. Further, even if the residual amount of the copper alloy plating layer is different, the surface roughness (Ra) of the prepreg is constant. Moreover, the surface of the copper alloy plating layer is often subjected to rustproof treatment. The residual amount of the so-called copper alloy plating layer is 'the surface of the copper alloy plating layer is rustproofed, the copper alloy plating layer and the rustproofing The total amount of the film is treated. Further, there is no particular problem even if the rust-preventing film remains. It is preferred to carry out step (B) after step (A). In the method for producing a copper-clad laminate according to the present invention, the step of removing the copper alloy plating layer by further including -35-201124264 (D) can remove the copper alloy plating layer which is a cause of high-frequency noise. The copper-plated gold plating remaining on the surface of the insulating layer can reduce the electrical characteristics at high frequency. Moreover, since a bump is formed on the copper land after the formation of the loop, when Au-Ni electroless plating is performed on the copper sheet, the micro copper can be avoided even on the surface of the resin which is not deposited by the electroless plating. The occurrence of poor plating, such as plating of a core, is caused by gold plating. Step (D) can be carried out by treatment with an oxidizing agent solution, although there is no particular limitation. 'The oxidizing agent solution is specifically treated by (a) swelling treatment by swelling liquid, (b) roughening treatment by oxidizing agent solution, and (c) borrowing It is preferred that the neutralization liquid is neutralized in the order of treatment. The swelling solution is not particularly limited, and examples thereof include an alkali solution and an interfacial activator solution. The alkali solution is preferred, and a sodium hydroxide solution or a potassium hydroxide solution is preferred. Further, a swelling liquid sold by Atotech Japan Co., Ltd., Swelling Dip Se curi ganth P, Swelling Dip Securiganth SBU, or the like can also be used. The swelling treatment by the swelling liquid is not particularly limited, and specifically, a method of applying a swelling liquid of 20 to 50 ° C to a treatment surface for removing the copper foil for 1 to 2 minutes. From the viewpoint of workability and the fact that the resin does not excessively swell, it is preferable to use a target for removing the copper foil in a immersion liquid of 20 to 5 (TC for 1 sec to 1 minute). There is no particular limitation, and specifically, an alkaline permanganic acid solution in which potassium permanganate or sodium permanganate is dissolved in an aqueous solution of sodium hydroxide is used. The concentration of permanganate in the alkaline permanganic acid solution is 5~ 10% by mass -36- 201124264 is preferred. Alternatively, the oxidant solution sold may be used. As the veneer solution, an alkaline permanganic acid solution such as Atotech japan (CON)RATE CONPRATE CP, Dosing s SecuriganthP, etc. may be mentioned. The treatment with the oxidizing agent solution is not particularly limited. For example, the oxidizing agent solution having a temperature of 20 to 60 ° C can be applied to the surface of the swelling treatment by a swelling solution for 1 sec to 2 minutes. In the case of excessively roughening, it is preferred that the object to be swelled is immersed in an oxidizing agent solution at 20 to 50 ° C for 1 minute. The neutralizing liquid is not particularly limited, and specific examples thereof include Acidic. Again, as a sale A liquid of the product Atotech Japan (Secure GanttP) can be used. The treatment with the neutralizing solution is not particularly limited, and for example, the surface treated by the oxygen solution may be roughened by 2 0 to 6 0. (: The method of applying 10 seconds to 2 minutes is carried out. From the viewpoint of ensuring efficiency, the coarsening treatment by the oxidizing agent solution is neutralized to 20 to 50 ° C The method of immersing in the liquid for 10 seconds to 1 minute is better. By the treatment with the above oxidizing agent solution, the almost completely alloy plating layer is present in the surface of the prepreg after the treatment with the oxidizing agent solution, or even There is a measurement of XPA of 0.5% atomic% or less. Further, step (D) is preferably in step (c). For the method for manufacturing the copper-clad laminate of the present invention, the surface of the prepreg on the step is used by The step of forming a copper layer by electroless plating is not performed, and the side of the roughening of the oxidized ο 1 uti ο η is carried out for 10 seconds~ the aqueous solution reductive solvent dissolves the neutralizing liquid working object to remove The exposed giant cymbal of copper is carried out for the first time ^ (C) Special limit -37- 201124264 Specifically, the surface of the prepreg is treated with an interface activator or the like, and after a shovel coating agent such as palladium is applied, a copper layer can be formed by immersing in an electroless plating solution. The thickness of the copper layer is 0.1 to 5· Ομιη is preferable, preferably 0.2 to 2·5 μηι, more preferably 0.2 to 1.5 μηι, and the copper layer can be formed by a direct printing method of electroless plating. Step (C) is It is preferred to carry out the surface of the prepreg exposed through the step (Β), and it is preferably carried out on the surface of the prepreg exposed through the step (D). The method for producing a copper-clad laminate according to the present invention may further comprise the step of forming a through hole in the step (?). The step (Ε) can be achieved, and is not particularly limited, and can be specifically performed by a mechanical drill, a carbon dioxide laser, a YAG laser or the like. The step (Ε) may preferably be carried out after the step (Α) or the step (Β) or the step (D). The viewpoint of preventing damage to the surface of the resin during the drilling process, or the roughening of the surface of the insulating layer by the degreasing liquid after the formation of the via hole, the step of fine wiring, the step (Ε) in the step (Β) It is better to do it before. The method for producing a copper-clad laminate according to the present invention may further comprise the desmear step of the step (F), whereby the residue of the wall surface formed by the formation of the through-holes is removed, and the wall surface can be roughened. The step (F) is not particularly limited and can be carried out by a known method. Specifically, it is preferably treated by a drying method such as plasma or an oxidizing agent solution such as an alkaline permanganic acid solution (humidification method). The wall surface is sm e a r and the wall surface is roughened with an oxidizing agent, and it is preferable to treat it with an oxidizing agent solution from the viewpoint of enhancing the adhesion strength of the mineral coating. The oxidizing agent solution in the step (F) is not particularly limited, and is (a) swelled by a swelling liquid, (b) roughened by an oxidizing agent solution - 38 - 201124264, and (C) by a neutralizing liquid The order of the neutralization process is preferably performed. The swelling solution is not particularly limited, and examples thereof include an alkali solution, an interfacial activator solution, etc., and an alkali solution is preferred. A sodium hydroxide solution or a potassium hydroxide solution is preferred. Further, a swellable liquid such as Swelling Dip Securiganth P or Swelling Dip Securiganth SBU manufactured by Atotech JaPan Co., Ltd. may be used. The swelling treatment by the swelling liquid is not particularly limited, and specifically, the swelling liquid at 30 to 90 ° C is allowed to be applied for 1 minute to 15 minutes. From the viewpoint of workability and the resin does not excessively swell, it is preferred to immerse the swelling liquid at 40 to 80 ° C for 5 seconds to 1 minute. The oxidizing agent solution is not particularly limited, and specific examples thereof include an alkaline permanganic acid solution in which potassium permanganate or sodium permanganate is dissolved in an aqueous solution of sodium hydroxide. The concentration of the permanganate in the alkaline permanganic acid solution is preferably 5 to 10% by mass. Further, an oxidizer solution such as CONCENTRATE • COMPACT CP or Dosing solution Securiganth P manufactured by Atotech Japan Co., Ltd. can be used. The roughening treatment by the oxidizing agent solution is not particularly limited, and a method of applying an oxidizing agent solution of 50 to 90 ° C for 1 Torr to 4 Torr for a treatment surface which is swelled by a swelling liquid can be used. From the viewpoint of workability and the fact that the resin is not excessively coarsened, it is preferred to immerse the object to be immersed in an oxidizing agent solution at 60 to 85 ° C for 20 minutes to 30 minutes. The neutralizing liquid is not particularly limited, and an acidic aqueous solution is preferred. A neutralizing solution such as a reducing solution manufactured by Atotech Japan Co., Ltd., Secure GanttP, etc. can be used. By the treatment of the neutralizing solution, a method of imparting a neutralizing solution of 30 to 80 ° C for 5 minutes to 30 minutes on the treated surface by the roughening treatment of the oxidizing agent solution can be used. From the viewpoint of workability and the like, it is preferred that the object to be roughened by the oxidizing agent solution -39 - 201124264 is immersed in the liquid at 40 to 70 ° C for 5 minutes to 20 minutes. It is preferred to carry out step (F) after step (E). It is preferable to carry out the step (F) and the step (C) before the electroless plating is performed and the connection reliability of the via hole is improved. In the step (B), the smear of the bottom of the pore-bottomed copper layer on the surface of the via-bottom can be more completely removed, from the viewpoint of further preventing the surface of the insulating layer from being roughened. Step (F) is preferably carried out before step (B). The method for producing a multilayer printed wiring board of the present invention may further comprise (G) a step of forming a conductor layer by electroplating. The method of forming the conductor layer in the step (G) is not particularly limited, and it can be carried out by a known method such as a semi-additive method. Specifically, in order to form a plating resist, it is preferable to form a conductor layer by electroplating using the copper layer formed in the above step (C) as a plating seed layer. Copper is preferably used as the conductor layer to be plated. The thickness of the conductor layer is preferably 3 to 35 μm, and preferably 5 to 30 μm, depending on the design of the circuit substrate. It is preferred to carry out step (G) after step (C). The method of the present invention is such that a conductor layer of high adhesion strength can be formed on the surface of the insulating layer having a very low surface roughness (Ra). Namely, the surface roughness (Ra) of the insulating layer by the prepreg is extremely low, but a conductor layer of high adhesion strength can be formed on the surface of the insulating layer. The lower limit of the surface roughness (Ra) of the insulating layer is preferably 5 nm or more, more preferably 10 nm or more, and 15 nm or more, from the viewpoint of good adhesion between the insulating layer and the copper plating layer (conductor layer). Better. On the other hand, from the viewpoint of the workability of the etching of the unnecessary conductor layer by the formation of the loop and the fine wiring formation property, the upper limit of the surface of the insulating layer - 40, 201124264 (Ra) is 300 nm. The following is preferable, preferably 25 Å or less, more preferably 200 nm or less, and still more preferably 150 nm or less. The lower limit of the peel strength (kgf/cm) of the conductor layer is preferably 0.50 or more, and preferably 0.55 or more, from the viewpoint of forming a circuit having high reliability in which the adhesion stability to the insulating layer is excellent. It is more preferably 0.60 or more, and further preferably 0.65 or more. On the other hand, the higher the peel strength of the conductor layer is, the more preferable, and the upper limit 値 is not particularly limited, and the upper limit of the peel strength (kgf/cm) is preferably 2 or less, and 5 or less, from the viewpoint of sufficient performance. Preferably, it is better to use 10 or less, and further preferably less than 100. In the present invention, the reason why a conductor layer having a high peeling strength can be formed on the surface of the insulating layer having such high smoothness (that is, the surface roughness is extremely small) can be considered as 'applied to the surface of the resin after the copper foil is removed. One of the reasons is the very dense rough surface of the copper plating layer. The copper-clad laminate of the present invention can be used under mild conditions by removing the plating layer by etching, and can suppress the dissolution of the wiring pattern. Therefore, the copper-clad laminate can be used for a circuit substrate requiring fine wiring formation, and can also be used for carrying Their computers, mobile phones, digital cameras, televisions, and other electrical products, or electric bicycles, automobiles, trams, ships, aircraft, and other means of transportation. [Embodiment] [Examples] The present invention will be more specifically described by the following examples, but the present invention is not limited by the following examples. Further, the "parts" in the following description means "parts by mass". -41 - 201124264 First, the measurement method of the physical property evaluation in the present specification will be described. &lt;Peel strength of the conductor layer&gt; The peel strength of the conductor layer is measured in accordance with JIS C 648 1 by the following method. The copper clad laminates obtained in the following examples and comparative examples were cut into small pieces of 150 mm x 30 mm. The copper box of the small piece was cut into a width of 10 mm and a length of 100 mm by a cutter, and one end of the copper box was peeled off and bundled with a bundle, and measured at a temperature of 50 mm/min in a vertical direction using an Instron universal testing machine at room temperature. The load at the peeling of 3 5 mm was pulled apart as the peel strength. The thickness of the conductor layer is about 30 μm. &lt;Insulation Layer Surface Thickness&gt; The electroless copper plating layer and the electrolytic copper plating layer on the circuit substrate were removed by a copper etching solution, and a non-contact surface roughness meter (WYKO NT3 3 00 by Veeco Instruments) was used. The measurement range of the VSI contact type and the 50-fold lens was set to 121 μm Χ 92 μϊη, and the surface of the prepreg after removing the copper foil or removing the copper alloy plating layer was measured to obtain the surface roughness (Ra 値). Further, R a 値 was set to 3 in a random manner, and the average enthalpy of the measurement was measured at three places. [Determination method of residual amount of copper and gold plating in the surface of prepreg] &lt;Measurement device&gt; -42- 201124264 Device type: QUANTERA SXM (automatic scanning type 光-line photoelectron spectroscopy analyzer) Reaching degree of vacuum: 7 .〇χ 1 (T1QTorr X-ray source: Monochromator Α1 Κα (1 486.6eV) Spectroscope: Electrostatic concentric hemispheric analyzer Detector: Multi-channel Detector Neutralization gun setting electron: 1_ 〇ν(20μΑ), ion: 10.0V (7mA) &lt;Measurement conditions&gt;&lt;Measurementspectrum&gt; X Beam diameter: 100μηιΦ (ΗΡ model, 100.6W, 20kV) Measurement area: 1400μηιχ100μηι Signal reading angle: 45.0 °

Pass capacity: 280.0eV

[Example 1] &lt;Preparation of prepreg&gt; 25 parts of a phenolic epoxy resin (epoxy equivalent weight 180, "N740" manufactured by DIC), and a phenol type for bisphenol A paint Epoxy resin (epoxy equivalent 208, "157S70B75" manufactured by Nippon Epoxy Co., Ltd., and cyclohexanone solution of solid content of 7.5 mass%) 25 parts, naphthalene type 4-functional epoxy resin (epoxy 3 parts of base equivalent of 170, DIC (EXA4710), and phenoxy resin (YX6 954BH30, manufactured by Nippon Epoxy Co., Ltd.), MEK with 30% by mass of solid component, and 1 of cyclohexanone. -43- 201124264 1 solution) 25 parts, and the mixture of 15 parts of MEK and 15 parts of cyclohexanone was heated and dissolved while stirring. In this case, 30 parts of a phenol resin for phenol paint containing a triazine (hydroxyl equivalent: 125, "LA7054" manufactured by DIC Co., Ltd., and a MEK solution of 60% by mass of a solid component), and a naphthol-based hardener (hydroxy equivalent 215, Dongdu) were mixed. 20 parts of MEK solution of 60% by mass of solid component ("SN-485"), "2E4MZ" manufactured by Shikoku Chemicals Co., Ltd., 0.1 parts of spherical cerium oxide (average granules) 60 parts of diameter 0·5μιη, ("2" made by Admatechs), 25 parts of organic phosphorus-based flame retardant ("HCA-HQ" made by Sanguang Co., Ltd.), polyvinyl butyral resin (Shuishui Chemical Industry Co., Ltd.) "KS-1" is a solution of 10% by mass of a solid component of a mixed solvent of ethanol and toluene in a mass ratio of 1:1, and is uniformly dispersed in a high-speed rotary mixer to prepare a curable resin. Varnish of the object. The varnish was impregnated with 2116 glass cloth (thickness 94 μm) manufactured by Tosawa Manufacturing Co., Ltd., and dried in a vertical drying oven at 140 ° C for 5 minutes to prepare a prepreg. The amount of the residual solvent of the prepreg was 0.8% by mass in the curable resin composition containing no glass cloth, and the thickness of the prepreg was 120 μm. &lt;Preparation of copper-clad laminate precursor&gt; A copper alloy plating layer having Ni-Co-Cu plated on the surface is subjected to rust treatment of Zn and chromate on the surface, and the Ra値 is A copper foil of 250 nm (electrolyzed copper foil having a thickness of 18 μm) ("HLPFN" manufactured by Nippon Mining Co., Ltd.) and a prepreg were cut into a size of 340 mm x 500 mm by a cutter. Then, two prepregs were placed between two copper foils, and the vacuum press machine (MNPC-V-75 0-750-5 -2 00) was produced by the machine. - 201124264 The pressure is set to lxl (T3MPa, the pressure is l〇kgf/cm2, and the temperature is raised from 3 °C/min to 130 °C for 30 minutes. After 30 minutes, the pressure is set to 30kgf/cm2. The temperature was raised to 190 ° C at a temperature rising rate of 3 ° C /min and held for 90 minutes to prepare a copper-clad laminate precursor. &lt;Removal of copper foil&gt; The copper-clad laminate precursor was in a second aqueous solution of chlorinated iron. The copper foil was removed by immersing for 2 minutes at 5 ° C for 20 minutes. The copper alloy plating layer of 1.0% or more was left on the exposed surface of the copper foil. <Preparation of copper-clad laminate and formation of conductor layer> The exposed surface of the copper foil was removed by the above treatment, and electroless copper plating was performed using an electroless copper plating process using the following Atotech Japan pharmaceutical liquid to form a copper plating layer having a film thickness of 1 μm, thereby producing a sticker. Copper laminate. Thereafter, electrolytic copper plating is performed to form a conductor layer having a total thickness of 30 μm to obtain a circuit substrate. Ch Japan (stock) pharmaceutical liquid electroless copper plating process> 1. Alkali cleaning (resin surface cleaning and charge adjustment) Trade name: Cleaning cleaner Securiganth 902 Condition: 5 minutes under 6 (TC for 2 minutes · Soft Uranium engraving (via-b 〇11 〇m), copper cleaning of the conductor) Acidic acid peroxodisulfate aqueous solution conditions: 1 minute at 30 °C -45- 201124264 3. Pre-dip (use For the purpose of adjustment of the surface charge imparted by Pd in the next step. Trade name: Pre. Dip Neoganth B Condition: 1 minute at room temperature 4. Activator (giving the P d of the resin surface) Trade name: Activator Neoganth 834 Condition: 5 minutes at 35t 5. Reduction (reduction of Pd with resin)

Product Name: Reducer Neoganth WA :Reducer Acceralator 810 mod. Mixture Condition: 5 minutes at 30 ° C

6. Electroless copper plating (precipitating Cu on the surface of the resin (Pd surface)) Trade name: Basic Solution Printganth MSK-DK : Copper solution Printganth MSK : Stabilizer Printganth MSK-DK : Reducer Cu mixture condition: at 35 ° C 20 minutes was carried out. [Example 2] A circuit board was produced in the same manner as in Example 1 except that a copper foil prepreg was used. The method for producing a copper foil prepreg and the method for producing the circuit substrate are shown below. &lt;Preparation of Prepreg&gt; -46- 201124264 The varnish of the curable resin composition prepared in Example 1 was impregnated with 2116 glass cloth (thickness 94 μη〇, in a vertical drying oven at 144). 〇t was dried for 5 minutes, continuing on one side of the prepreg, continuously laminating a polypropylene film having a thickness of 15 μm, and continuously laminating a polyethylene film having a thickness of 12 μm on the other surface and rolling into a roll. Prepreg The amount of the residual solvent is 1 to 0.1% by mass in the curable resin composition containing no glass cloth, and the thickness of the prepreg layer is 120 μm. &lt;Preparation of copper foil prepreg&gt; Using roll lamination Generally, the polyethylene film of the above-mentioned roll-shaped prepreg is peeled off, and the rust-preventing layer of the same copper foil as in Example 1 is brought into contact with the prepreg at a roll temperature of 100 ° C and a line pressure of 5 kg/cm. The lamination speed was 6 m/min, and the obtained copper foil prepreg was wound into a roll. <Preparation of a copper-clad laminate precursor> A roll-shaped copper foil prepreg was cut by a cutter It is 340mmx 5 00mm in size. No wrinkles or anti-warping is observed on the copper foil prepreg. Two pieces of polypropylene film with copper foil prepreg cut through the cutting, so that the surface of the prepreg is opposite and overlapped, and the vacuum press machine (MNP CV-750-750-5-) is made by the machine. 200), the pressure reduction degree is set to 1x10-3 MPa, the pressure is 10 kgf/cm2, and the temperature rise rate is increased from room temperature to 130 ° C at a temperature increase rate of 3 ° C / minute. After holding for 30 minutes, the pressure is set to 30 kgf / cm 2 to raise the temperature. The temperature was raised to 190 ° C at a rate of 3 ° C / min and held for 90 minutes to prepare a copper-clad laminate precursor. Thereafter, a copper-clad laminate and a ΰ -47 - 201124264 circuit were produced in the same manner as in Example 1. A copper alloy plating layer having a thickness of 1.0% or more was left on the exposed surface of the copper foil. [Example 3] A copper foil was used in the same manner as in Example 1, and a copper box with an adhesive layer was produced as follows. &lt;Preparation of varnish of curable resin composition&gt; 28 parts of liquid bisphenol A type epoxy resin (epoxy equivalent weight 180, "EPIKOTE 82 8EL" made from sakamoto epoxy resin), naphthalene Type 4 functional epoxy resin (epoxy equivalent 163, DIC ("HP4700") made of 28 parts and phenoxy resin (Japan) 20 parts of "YX6954BH30" made of epoxy resin (strand) and 1:1 by weight of Μ EK and cyclohexanone in a solid content of 30 parts, heated in a mixture of 25 parts and 25 parts of cyclohexanone while stirring. This is a mixture of 27 parts of a phenolic resin for phenol paint (a hydroxyl equivalent of 125, a "LA7054" manufactured by DIC (60% by mass) and a 60% by mass of a solid component), and a naphthol-based hardener (hydroxy equivalent 215). 27 parts of a solid content of 50% by mass of a SN-485 of the Tosho Chemical Co., Ltd., and 0.1 part of a curing catalyst ("4Ε4ΜΖ" manufactured by Shikoku Chemicals Co., Ltd.), spherical cerium oxide ( 70 parts of an average particle diameter of 5.5μηι, ("2" made by Admatechs), and a polyvinyl butyral resin ("KS-1" by Sekisui Chemical Co., Ltd.) dissolved in a mass ratio of ethanol to toluene of 1:1 30 parts by weight of a solid solvent 15% by mass of a mixed solvent, and uniformly dispersed by a high-speed rotating mixer to produce a curable resin composition -48-201124264

&lt;Preparation of copper foil with adhesive layer&gt; The varnish was applied by a die coating on a copper box, and the solvent was removed by a hot air drying oven. The thickness of the curable resin composition layer was 5 μm. Layer copper box. &lt;Preparation of copper-clad laminates&gt; The copper foil with the adhesive layer and the commercially available prepreg (GEA-679FG manufactured by Hitachi Chemical Co., Ltd.) and the thickness: 0·1 μπ〇 were cut into a cutting machine. 3 4 0mm X 5 00mm size. Then, two prepregs are placed between the two copper foil films, and the vacuum press machine (MNPC-V-750-750-5) is manufactured by the machine. -200), the decompression degree was set to lxl (T3MPa, the pressure was lOkgf/cm2, and the temperature was raised from room temperature to 130 °C at a temperature increase rate of 3 ° C / min. After holding for 30 minutes, the pressure was set to 30 kgf / cm 2 , The temperature was raised to 190 t at a temperature increase rate of 3 ° C /min and held for 90 minutes to prepare a copper-clad laminate precursor, and then a copper-clad laminate and a circuit substrate were produced in the same manner as in Example 1. [Example 4] The copper-clad laminate precursor produced in Example 1 was drilled and formed with a hole diameter of 1 〇 5 μm. The drilling process was performed using "ND-1V212" manufactured by Via Mechanics. This was carried out. The desmear treatment was carried out as shown below. Then, the copper foil was removed in the same manner as in Example 1 to carry out no electricity.

C -49- 201124264 Deplating copper and performing electrolytic copper plating to obtain a circuit substrate in which a conductor layer (copper layer) having a total thickness of 30 μm was formed. &lt;Degrease treatment&gt; Swelling Dip Securiganth(R) manufactured by Atotech Japan Co., Ltd. was swelled at 6 (TC for 5 minutes), and then washed with water and then CONCENTRATE manufactured by Atotech Japan Co., Ltd. COMP ACT CP (alkaline permanganic acid solution), roughened at 80 ° C for 10 minutes, washed with Atotech Japan (stock) reduction solution. Secure GanttP (neutralizer) The neutralization treatment was carried out under the conditions of 5 minutes at 40 ° C. [Example 5] After the removal treatment of the copper foil, the following method of removing the copper alloy plating layer was further carried out, in the same manner as in Example 1. A copper-clad laminate and a circuit board were produced. The copper alloy plating layer and the rust-preventing residue were not present on the exposed surface after removal of the copper alloy plating layer. &lt;Removal of copper alloy plating layer&gt; Swelling was carried out by Swelling Dip Securiganth P manufactured by Atotech Japan Co., Ltd. under the conditions of 1 minute at 40 ° C. Thereafter, it was washed with water, and C ON CENTRATE · COMPACT CP (alkaline) manufactured by Atotech Japan Co., Ltd. Permanganic acid solution), The roughening treatment was carried out under the conditions of 1 minute at 40 ° C. After washing with water, it was neutralized by Resolvent -50 - 201124264 Liquid · Secure G an 11P (neutralizing solution) manufactured by Atotech Japan Co., Ltd. [Comparative Example 1] In place of the copper foil used in Example 1, electrolytic copper foil (JTC foil manufactured by Nippon Mining Materials Co., Ltd., thickness: 18 μm, rough surface (arithmetic mean roughness): I 2 was used. 00 nm), a prepreg is placed between two copper foils for a rough prepreg of copper foil, and a copper-clad laminate precursor is produced by other methods. Then, a copper laminate is attached as in the first embodiment. A copper foil of a precursor was prepared by electroless copper plating, and a copper substrate was prepared in the same manner as in Example 1. [Comparative Example 2] Instead of the copper foil used in Example 1, use Electrolytic copper foil ("JTC-LP foil" made of bismuth ore material, thickness: 18μηι, hair Ra 値 (arithmetic mean thickness): 305 nm), intended to be used in copper foil prepreg, in 2 A prepreg is placed between the copper foils, and other copper-positive laminate precursors are produced in the same manner as the real S. Thereafter, Example 1 to remove the copper foil attached to a precursor of the laminate, prepared by electroless copper plating copper layer to prepare a copper-laminated plate, further a circuit board fabricated by the method of Example 1. Table 1 below shows the evaluation results of the panels produced in Examples 1 to 5 and Comparative Examples 1 and 2. The Rab surface contact ij 1 of the 40t feed (strand) is similarly removed from the copper layer to make the back surface of the light surface. The same circuit base is formed in the same way as the same process. -51 - 201124264 [Table 1] 1 Example 2 Example 3 Example 4 Example 5 Ra (nm) 10 5 10 5 110 110 110 Peel strength (kgf/cm) 0.8 5 0.8 5 0. 70 0. 90 0. 80 Comparative Example 1 Example 2 Ra (nm) 1 2 0Q 3 5 0 Peel strength (kgf/cm) 1. 20 Expansion It is known from Table 1 that the surface of the insulating layer having a small surface roughness (Ra 値) is produced in Examples 1 to 5 A circuit substrate of a conductor layer of high peel strength. On the other hand, in Comparative Example 1 in which a copper-clad laminate and a circuit substrate were produced by laminating a rough surface of an electrode copper foil which was not treated on the surface to a prepreg, the peel strength was about 1.20 kgf/cm. The sorghum, the surface roughness (Ra 値) of the insulating layer is a maximum of 100 Å or more. In addition, in Comparative Example 2 in which a copper-clad laminate and a circuit board were produced by laminating a light-emitting surface of an electrolytic copper foil which was not treated on the surface to a copper-clad laminate of a prepreg, electroless copper plating and resin were not obtained. The adhesion is made, and electroless copper plating is floated on the interface to expand the industrial availability. The step of hot-pressing the copper alloy plating layer toward the insulating layer under specific conditions, removing the copper foil, and forming copper In the step of the layer, even if the surface roughness of the insulating layer is extremely small, a copper clad laminate in which a copper layer is laminated under high adhesion strength to the insulating layer can be obtained. In the copper-clad laminate, the removal of the plating layer by etching is performed under mild conditions, and the solution pattern of the wiring pattern can be suppressed. Therefore, it is suitable as a material for manufacturing a circuit board in which fine wiring is required. The application is based on Japanese Patent Application No. 2009-165913, the entire disclosure of which is incorporated herein. -53-

Claims (1)

201124264 VII. Patent Application Range: 1. A method for manufacturing a copper-clad laminate, comprising the following steps (A) to (C); (A) forming a copper alloy plating layer on a surface by electroplating Between two copper foils, a step of disposing one or more prepregs into a copper alloy plating layer to form a prepreg side, heating and pressurizing under reduced pressure to heat the copper foil to the prepreg, (B) a step of removing the copper box with a copper etching solution, (C) a step of forming a copper layer by electroless mineral coating on the surface of the prepreg 〇2 _ Manufacture of a copper-clad laminate as claimed in claim 1 The method, wherein the copper alloy plating layer has a surface roughness (Ra) of 300 nm or less. 3. The method for manufacturing a copper-clad laminate according to claim 1 or 2, wherein the surface roughness of the surface of the prepreg is (Ra) is 300 nm or less. 4. The method of producing a copper clad laminate according to claim 1 or 2, further comprising (D) a step of removing the copper alloy plating layer. 5. The method of producing a copper clad laminate according to claim 1 or 2, further comprising (E) a step of forming a through hole. 6. The method for producing a copper clad laminate according to claim 1 or 2, further comprising (F) a desmear step. 7. The method of manufacturing a copper-clad laminate according to claim 1 or 2, further comprising (G) a step of forming a conductor layer by electroplating. 如8, as in claim 1 or 2 Manufacture of copper-clad laminates - 54- 201124264 Method 'Where as the copper foil in the step (A), using a copper foil further laminated on the surface of the copper alloy plating layer, and/or as a prepreg A prepreg forming an adhesive layer on the surface. 9. The method for manufacturing a copper-clad laminate according to the scope of claim 2 or 2, wherein the copper alloy is selected from the group consisting of Ni-Co-Cu, Ni-Cu, and Co-Cu. The copper laminate is characterized in that the surface roughness (Ra) of the surface of the insulating layer of the prepreg is 5 nm or more and 300 nm or less, and a conductor layer is formed on the surface of the insulating layer, and the peeling strength of the conductor layer to the insulating layer (kgf) /cm) is 0.50 or more and 10 or less. -55- 201124264 IV Designation of representative drawings: (1) The representative representative of the case is: None (2) Simple description of the symbol of the representative figure 201124264 5. If there is a chemical formula in this case, please disclose the chemical formula that best shows the characteristics of the invention: none