TWI578871B - The manufacturing method of laminates - Google Patents

Description

Method for manufacturing laminate

The present invention relates to a method for producing a specific laminate, and further relates to a method for producing a circuit board using the obtained laminate.

The circuit forming method of the core material is a method of reducing the excess metal foil portion of the metal foil laminate, and applying the remaining metal foil portion to directly form a circuit, and removing all the metal foil of the metal foil laminate, and The unevenness from the metal foil formed on the insulating layer is used as a anchor to perform electroless plating, and then a semi-additive method of forming a conductor layer by electrolytic plating (Patent Document 1). However, when irregularities are formed on the surface of the insulating layer, it is difficult to remove the metal in the unevenness by etching to remove the conductor layer and the plating shielding layer which are not required for circuit formation, and on the other hand, under conditions which can be sufficiently removed At the time of etching, the dissolution of the necessary portion of the conductor layer becomes remarkable, and there is a problem that the fine wiring is hindered. Further, in Patent Document 1, since the B-stege resin composition sheet is sandwiched, it is disadvantageous for downsizing of the substrate.

Further, a copper foil laminate using a metal foil with an adhesion aid formed on a metal foil with an adhesion aid layer has been developed (Patent Document 2). However, since the adhesive auxiliary layer is provided, it is disadvantageous for the miniaturization of the substrate, and the step of removing the metal foil is required, and after the reliability test, the interface between the plating interface and the adhesive auxiliary layer is expanded, or The expansion of the interface between the adhesion aid layer and the prepreg layer causes a problem that sufficient reliability cannot be ensured.

[Previous Technical Literature]

[Patent Literature]

[Patent Document 1] Japanese Patent Laid-Open Publication No. 2003-332734

[Patent Document 2] Japanese Patent Laid-Open Publication No. 2006-218855

An object of the present invention is to provide a laminate for forming a laminate which can maintain a glass transition temperature and a tensile modulus while maintaining a glass transition temperature and a tensile modulus while forming a conductor layer having a good peeling strength on the surface of a smooth insulating layer without removing the metal foil. method.

The inventors of the present invention have conducted intensive studies to solve the above problems, and as a result, have found that the above problems can be attained by a specific method for producing a laminate.

The features of the present invention are as follows.

[1] A method for producing a laminated board, comprising: (A) disposing one or more prepregs between the supports, and curing the prepreg by heating and pressurizing under reduced pressure; The step of forming an insulating layer,

(B) the step of removing the support,

(C) a step of roughening the surface of the insulating layer, and

(D) a step of forming a metal film layer on the surface of the insulating layer by electroless plating; and containing 40% by mass of the inorganic filler relative to 100% by mass of the nonvolatile matter in the curable resin composition in the prepreg 80% by mass or less; the glass transition temperature of the insulating layer is 150° C. or higher and 270° C. or lower, and the tensile modulus is 10 GPa or more and 35 GPa or less; and the insulating layer after the step of roughening the surface of the insulating layer (C) The arithmetic mean roughness is 0.1 nm or more and 600 nm or less; and the peeling strength of the insulating layer and the metal film layer after the step of forming a metal film layer on the surface of the insulating layer by electroless plating is (0.45) or more. 10kgf/cm or less.

[2] The method for producing a laminate according to the above [1], wherein the support is a release plastic film.

[3] The method for producing a laminate according to the above [1] or [2] wherein the prepreg is composed of a curable resin composition and a sheet-like fibrous base material.

[4] The method for producing a laminate according to the above [3], wherein the sheet-like fibrous base material in the prepreg contains one or more selected from the group consisting of glass fibers, organic fibers, glass nonwoven fabrics, and organic nonwoven fabrics.

[5] The method for producing a laminate according to the above [4], wherein the sheet-like fibrous base material is a glass fiber having a thickness of 1 to 200 μm.

[6] The method for producing a laminate according to the above [1] to [5], wherein the curable resin composition in the prepreg contains an epoxy resin and a curing agent.

[7] The method for producing a laminate according to the above [6], wherein the curable resin composition in the prepreg is a naphthalene type epoxy resin and a naphthol type curing agent.

[8] The method for producing a laminate according to the above [1] to [7], wherein the prepreg is cured at 150 to 250 ° C for 60 to 150 minutes to form an insulating layer.

[9] The method for producing a laminate according to the above [1] to [8], further comprising (E) a step of forming a through hole.

[10] The method for producing a laminate according to the above [9], wherein (E) forming a through hole is performed before the step of (B) removing the support.

[11] The method for producing a laminate according to the above [1] to [10], which further comprises (F) a step of forming a conductor layer by electrolytic plating.

[12] A multilayer printed wiring board using the laminate obtained by the production method of the above [1] to [11].

[13] A semiconductor device using the laminate obtained by the production method of the above [1] to [11].

By the method for producing a specific laminate of the present invention, an unnecessary step of removing the metal foil can be obtained, and the glass transition temperature and the tensile modulus can be maintained while forming the peel strength on the surface of the smooth insulating layer. A laminate of good conductor layers.

Hereinafter, the present invention will be described in detail in accordance with preferred embodiments.

The present invention provides a method for producing a laminate, comprising: (A) disposing one or more prepregs between the supports, and curing the prepreg by heating and pressurizing under reduced pressure; The step of forming an insulating layer,

(B) the step of removing the support,

(C) a step of roughening the surface of the insulating layer, and

(D) a step of forming a metal film layer on the surface of the insulating layer by electroless plating.

[(A) Step]] <prepreg>

The prepreg used in the present invention is preferably composed of a curable resin composition and a sheet-like fibrous base material, and the curable resin composition can be impregnated into a sheet-like fibrous base material and dried by heating. The curable resin composition is not particularly limited and can be used. Among them, a composition containing (a) an epoxy resin is preferable, and a composition containing (a) an epoxy resin, (b) a hardener, and (c) a thermoplastic resin is particularly preferable.

(a) The epoxy resin may, for example, be a bisphenol A type epoxy resin, a biphenyl type epoxy resin, a naphthol type epoxy resin, a naphthalene type epoxy resin, a bisphenol F type epoxy resin, or a phosphorus containing ring. Oxygen resin, bisphenol S type epoxy resin, alicyclic epoxy resin, aliphatic chain epoxy resin, phenol-phenolic epoxy resin, cresol novolac epoxy resin, bisphenol A phenolic epoxy resin An epoxy resin having a butadiene structure, a diglycidyl ether compound of bisphenol, a diglycidyl ether compound of naphthalenediol, a glycidyl ether compound of a phenol, and a diglycidyl ether of an alcohol, and the like An alkyl group, an halide, a hydrogenated product, or the like of an epoxy resin. These may be used alone or in combination of two or more.

Among them, bisphenol A type epoxy resin, naphthol type epoxy resin, naphthalene type epoxy resin, etc. are preferable from the viewpoints of improvement in heat resistance, improvement in insulation reliability, and adhesion to a metal film. A biphenyl type epoxy resin, an epoxy resin having a butadiene structure, and a naphthalene type epoxy resin are particularly preferable. Specifically, for example, liquid bisphenol A type epoxy resin ("Epikote 828EL" manufactured by Mitsubishi Chemical Corporation) and naphthalene type bifunctional epoxy resin (HP4032" and "HP4032D" manufactured by DIC Corporation ), a naphthalene type tetrafunctional epoxy resin ("HP4700" manufactured by DIC Corporation), a naphthol type epoxy resin ("ESN-475V" manufactured by Tohto Kasei Co., Ltd.), and an epoxy resin having a butadiene structure ( "PB-3600" manufactured by Daicel Chemical Industry Co., Ltd.), epoxy resin having a biphenyl structure ("NC3000H" manufactured by Nippon Kayaku Co., Ltd., "NC3000L", "YX4000" manufactured by Mitsubishi Chemical Corporation).

(b) The curing agent may, for example, be an amine-based curing agent, an oxime-based curing agent, an imidazole-based curing agent, a benzene-based curing agent containing a triazine skeleton, a phenol-based curing agent, or a naphthol-based curing agent containing a triazine skeleton. A naphthol-based curing agent, an acid anhydride-based curing agent, or such an epoxy-addition or microencapsulation, an active ester-based curing agent, a benzoxazine-based curing agent, a cyanate resin, or the like. From the viewpoint of improving the peel strength of plating, the hardener is preferably a nitrogen atom in a molecular structure, and among them, a phenolic hardener containing a triazine skeleton and a naphthol hardener containing a triazine skeleton are preferable. Particularly preferred is a phenol-phenolic resin containing a triazine skeleton. From the viewpoint of improvement in heat resistance, improvement in insulation reliability, and adhesion to a metal film, a naphthol-based curing agent is preferred. These may be used alone or in combination of two or more.

Specific examples of the phenolic curing agent and the naphthol-based curing agent include MEH-7700, MEH-7810, MEH-7851 (made by Megumi Kasei Co., Ltd.), NHN, CBN, and GPH (Nippon Chemical Co., Ltd.) System, SN170, SN180, SN190, SN475, SN485, SN495, SN375, SN395 (made by Dongdu Chemical Co., Ltd.), TD2090 (made by DIC Corporation), etc. Specific examples of the phenolic curing agent containing a triazine skeleton include LA3018 (manufactured by DIC Corporation). Specific examples of the phenol-phenolic curing agent containing a triazine skeleton include LA7052, LA7054, and LA1356 (manufactured by DIC Corporation).

As the active ester-based curing agent, two or more ester groups having high reactivity in one molecule, such as phenol esters, thiophenol esters, N-hydroxylamine esters, and esters of heterocyclic hydroxy compounds, can be suitably used. Compound. The active ester compound is preferably obtained by a condensation reaction of a carboxylic acid compound and/or a sulfuric acid compound with a hydroxy compound and/or a thiol compound. Particularly, from the viewpoint of heat resistance and the like, an active ester compound obtained from a carboxylic acid compound and a phenol compound or a naphthol compound is preferred. Examples of the carboxylic acid compound include benzoic acid, acetic acid, succinic acid, maleic acid, itaconic acid, phthalic acid, isophthalic acid, terephthalic acid, and pyrogolite. Examples of the phenol compound or naphthol compound include hydroquinone, resorcin, bisphenol A, bisphenol F, bisphenol S, phenolphthalein, methylated bisphenol A, methylated bisphenol F, and methyl group. Bisphenol S, phenol, o-cresol, m-cresol, p-cresol, catechol, α-naphthol, β-naphthol, 1,5-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 2 6-dihydroxynaphthalene, dihydroxydiphenyl ketone, trihydroxydiphenyl ketone, tetrahydroxydiphenyl ketone, cadaveric triol, trihydroxybenzene, dicyclopentadiene diol, phenol-phenolic aldehyde, and the like. One or two or more kinds of the active ester compounds can be used. As the active ester compound, an active ester compound disclosed in JP-A-2004-277460 or a commercially available product can be used. For example, EXB-9451, EXB-9460 (manufactured by DIC Corporation), and acetal-phenolic acetal compound can be exemplified by DC808 and phenol. The benzyl hydrazine compound of phenol is YLH1026 (made by Mitsubishi Chemical Corporation).

Specific examples of the benzoxazine-based curing agent include F-a, P-d (manufactured by Shikoku Chemicals Co., Ltd.), HFB2006M (manufactured by Showa Polymer Co., Ltd.), and the like.

(a) When the ratio of the epoxy resin to the curing agent (b) is a phenolic curing agent or a naphthol-based curing agent, the phenolic hydroxyl group of the curing agent when the epoxy group has an epoxy group number of 1 is preferably used. The ratio of the number to the range of 0.4 to 2.0 is particularly preferably a ratio of a range of 0.5 to 1.0. When the ratio of the reactive group is outside this range, the mechanical strength or water resistance of the cured product tends to decrease.

(c) The thermoplastic resin is formulated for the purpose of imparting appropriate flexibility to the cured composition, and examples thereof include a phenoxy resin, a polyvinyl acetal resin, a polyimine resin, and a polyfluorene. Amine amide resin, polyether oxime resin, polyfluorene resin, and the like. These may be used alone or in combination of two or more. When the non-volatile content in the curable resin composition is 100% by mass, the thermoplastic resin is preferably blended at a ratio of 0.5 to 60% by mass, and more preferably in a ratio of 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, so that it is difficult to form a uniform curable resin composition layer. When the content exceeds 60% by mass, the viscosity of the resin composition becomes excessive. When it is high, there is a tendency that it is difficult to manage the wiring pattern on the substrate.

Specific examples of the phenoxy resin include FX280, FX293 manufactured by Tohto Kasei Co., Ltd., YX8100, YL6954, YL6974, YL7213, YL6794, YL7553, and YL7482 manufactured by Mitsubishi Chemical Corporation.

The polyvinyl acetal resin is preferably a polyvinyl butyral resin, and a specific example of the polyvinyl butyral resin is, for example, Denka Butyral 4000-2, 5000-A, 6000-C, 6000 manufactured by Denki Kogyo Co., Ltd. -EP, S-REC BH series, BX series, KS series, BL series, BM series, etc. manufactured by Sekisui Chemical Industry Co., Ltd.

Specific examples of the polyimine resin include polyimine "Liquacoat SN20" and "Liquacoat PN20" manufactured by Nippon Chemical and Chemical Co., Ltd. Further, a linear polyimine obtained by reacting a polybutadiene having a bifunctional hydroxyl ink end, a diisocyanate compound, and a tetraprotic acid anhydride (described in JP-A-2006-37083) contains polyoxyalkylene oxide. A modified polyimine such as a polyimine of the skeleton (described in JP-A-2002-12667, JP-A-2000-319386).

Specific examples of the polyamidoximine resin include polyacrylamide imine "Vylomax HR11NN" and "Vylomax HR16NN" manufactured by Toyobo Co., Ltd. Further, modified polyamidoquinone imines such as polyacrylamide skeletons "KS9100" and "KS9300" manufactured by Hitachi Chemical Co., Ltd., which are made of a polyoxyalkylene skeleton, may be mentioned.

Specific examples of the polyether oxime resin include polyether oxime "PES5003P" manufactured by Sumitomo Chemical Co., Ltd., and the like.

Specific examples of the polybenzazole resin include polyfluorene "P1700" and "P3500" manufactured by Solvay Advanced Polymers Co., Ltd.

The curable resin composition may further contain (d) a curing accelerator from the viewpoint of efficiently curing the epoxy resin and the curing agent. Examples of the hardening accelerator include an imidazole compound, a pyridine compound, and an organic phosphine compound. Specific examples thereof include 2-methylimidazole, 4-dimethylimidazole, and triphenylphosphine. These may be used alone or in combination of two or more. When the (d) hardening accelerator is used, it is preferably used in an amount of 0.1 to 3.0% by mass based on the epoxy resin.

The curable resin composition may further contain (e) an inorganic filler from the viewpoint of lowering the thermal expansion coefficient of the insulating layer. Examples of the inorganic filler include cerium oxide, aluminum oxide, mica, pure mica, cerium silicate, barium sulfate, magnesium hydroxide, titanium oxide, etc., preferably cerium oxide or aluminum oxide, and particularly preferably amorphous. Cerium dioxide, molten cerium oxide, crystalline cerium oxide, synthetic cerium oxide, hollow cerium oxide or the like. The cerium oxide is preferably spherical, and one type or two or more types may be used. From the viewpoint of lowering the dielectric constant, the dielectric tangent, and the coefficient of thermal expansion, it is preferred to use hollow cerium oxide. The hollow ceria is composed of a shell portion and a hollow portion, and the average void ratio is preferably from 30 to 80% by volume.

The upper limit of the average particle diameter of the inorganic filler is preferably 5 μm or less, more preferably 4 μm or less, still more preferably 3 μm or less, still more preferably 2 μm or less, and most preferably 1.5 μm from the viewpoint of improving the insulation reliability. Hereinafter, it is particularly preferably 1 μm or less, and most preferably 0.5 μm or less. On the other hand, the lower limit of the average particle diameter of the inorganic filler is preferably 0.01 μm or more, and more preferably 0.05 μm or more, and more preferably 0.1 μm or more from the viewpoint of improving the dispersibility. The average particle diameter of the inorganic filler can be measured by a laser diffraction scattering method according to the Mie scattering theory. Specifically, the particle size distribution of the inorganic filler can be produced on a volume basis by a laser diffraction type particle size distribution measuring apparatus, and the median diameter can be measured as an average particle diameter. The sample is measured, and the inorganic filler is dispersed in water by ultrasonic waves as appropriate. For the laser diffraction type particle size distribution measuring apparatus, LA-500 manufactured by Horiba, Ltd., etc. can be used.

The upper limit of the content of the inorganic filler in the curable resin composition is a curable resin composition from the viewpoint of preventing the mechanical strength of the cured product from being lowered, improving the workability, and improving the adhesion of the plating. When the nonvolatile content is 100% by mass, it is preferably 80% by mass or less, more preferably 75% by mass or less, still more preferably 70% by mass or less, and still more preferably 65% by mass or less. On the other hand, the lower limit of the content of the inorganic filler in the curable resin composition is a non-volatile matter in the curable resin composition from the viewpoint of lowering the coefficient of thermal expansion and imparting rigidity to the prepreg. When the amount is 100% by mass, it is preferably 40% by mass or more.

In order to improve moisture resistance, dispersibility, and the like, the inorganic filler is preferably treated by the following surface treatment agents, namely, aminopropyl methoxydecane, amine propyl triethoxy decane, and urea propyl triethoxy decane. An amine decane coupling agent such as N-phenylaminopropyltrimethoxyoxane or N-2(aminoethyl)aminopropyltrimethoxy decane; glycidoxypropyltrimethoxy decane, glycidoxy Epoxy decane such as propyl triethoxy decane, glycidoxypropyl methyl diethoxy decane, glycidyl butyl trimethoxy decane or (3,4-epoxycyclohexyl)ethyltrimethoxy decane a coupling agent; a mercapto decane coupling agent such as propyl propyl trimethoxane or propyl propyl triethoxy decane; methyl trimethoxy decane, octadecyl trimethoxy decane, phenyl trimethoxy decane, methacryloxy a decane coupling agent such as propyltrimethoxyoxane, imidazolium or triazine decane; hexamethyldiazepine, hexaphenyldioxane, dimethylaminotrimethoxynonane, triazane, Organic sulfonium compound such as cyclotriazane, 1,1,3,3,5,5-hexamethylcyclotriazane; butyl titanate dimer , octyl methacrylate, bis(triethanolamine) diisopropylate titanate, dihydroxy ester of dilactic acid titanate, di(urmonium lactate) dihydroxy ester of titanate, bis(dioctylpyrophosphate) titanate Ester, bis(dioctylpyrophosphate) titanate oxyacetate, tri-n-butoxide monostearate, tetra-n-butyl titanate, tetrakis(2-hexylhexyl) titanate, bis ( Dioctylphosphite) tetraisopropyl titanate, bis(di(dodecyl)phosphinic acid) tetraoctyl titanate, bis(ditridecyl)phosphinic acid titanate 2,2-diallyloxymethyl-1-butyl)ester, isopropyl trioctanyl titanate, isopropyl triisopropylphenyl phenyl titanate, isopropyl triisopropoxide Stearic acid ester, isopropyl isostearyl phthalate diacrylate, isostearyl isopropyl dimethacrylate, isopropyl tris(dioctylphosphinate) titanate, Isopropyltris(dodecyl)benzenesulfonate titanate, isopropyltris(dioctylpyrophosphate) titanate, isopropyltris(N-decylamineethyl/amineethyl) An ester titanate coupling agent or the like. These may be used alone or in combination of two or more.

In the curable resin composition, a bismaleimide-triazine resin, an acrylic resin, a maleimide compound, or a bisallylylene may be blended in a range in which the effects of the present invention are exerted as necessary. A thermosetting resin other than an epoxy resin such as a quinone imine compound, a vinyl benzyl resin, a vinyl benzyl ether resin, or a blocked isocyanate compound. These may be used alone or in combination of two or more. Examples of the maleimide include BMI1000, BMI2000, BMI3000, BMI4000, BMI5000 (made by Daiwa Kasei Kogyo Co., Ltd.), BMI, BMI-70, BMI-80 (made by KI Chemical Co., Ltd.), and ANILIX-MI (Mitsui). The product of the bisallyl naphthyl imide compound is BANI-M, BANI-X (made by Maruzen Petrochemical Co., Ltd.), and the vinyl benzyl resin is V5000 (Showa high). The vinyl benzyl ether resin may, for example, be V1000X or V1100X (manufactured by Showa Polymer Co., Ltd.).

In the curable resin composition, a flame retardant may be contained in a range in which the effects of the present invention are exerted as necessary. Examples of the flame retardant include an organic phosphorus-based flame retardant, an organic nitrogen-containing phosphorus compound, a nitrogen compound, a polyoxyalkylene-based flame retardant, and a metal hydroxide. Examples of the organic phosphorus-based flame retardant include a phosphine compound such as HCA, HCA-HQ, and HCA-NQ manufactured by Sanko Co., Ltd.; and a phosphorus-containing benzoxazine compound such as HFB-2006M manufactured by Showa Polymer Co., Ltd. AFRinomoto Fine Techno Co., Ltd. REOFOS 30, 50, 65, 90, 110, TPP, RPD, BAPP, CPD, TCP, TXP, TBP, TOP, KP140, TIBP, PPQ, manufactured by Behind Chemical Industry Co., Ltd. Phosphate compound such as OP930 manufactured by Clariant Co., Ltd. and PX200 manufactured by Daeba Chemical Co., Ltd.; phosphorus-containing epoxy compound such as FX289 and FX310 manufactured by Tohto Kasei Co., Ltd.; ERF001 manufactured by Dongdu Chemical Co., Ltd. Such as phosphorus-containing phenoxy resin and the like. Examples of the nitrogen-containing phosphorus compound of the organic system include phosphate phthalamide compounds such as SP670 and SP703 manufactured by Shikoku Chemicals Co., Ltd.; and phosphazene compounds such as SPB100 and SPE100 manufactured by Otsuka Chemical Co., Ltd. Examples of the metal hydroxy compound include magnesium hydroxide such as UD65, UD650, and UD653 manufactured by Ube Materials Co., Ltd., and B-30, B-325, B-315, B-308, and B-303 manufactured by Ba Industrial Co., Ltd. , such as UFH-20 and other aluminum hydroxide. These may be used alone or in combination of two or more.

In the curable resin composition, solid rubber particles may be contained for the purpose of improving the mechanical strength of the cured product, the stress relieving effect, and the like, within the range in which the effects of the present invention are exerted. The solid rubber particles are preferably organic solvents which are not dissolved in the preparation of the resin composition, and are not compatible with the components in the resin composition such as epoxy resin, and are dispersed in the varnish of the resin composition. Exist. The rubber particles are generally prepared by increasing the molecular weight of the rubber component to such an extent that it does not dissolve in an organic solvent or resin and is formed into a particulate form. Examples of the rubber particles include core-shell type rubber particles, crosslinked acrylonitrile 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 examples thereof include a two-layer structure in which a shell layer of an outer layer is a glassy polymer, and a core layer of an inner layer is a rubbery polymer. The outer layer is composed of a glassy polymer, the intermediate layer is a rubbery polymer, and the core layer is a three-layer structure composed of a glassy polymer. The glassy polymer is composed of, for example, a polymer of methyl methacrylate or the like, and the rubbery polymer is composed of, for example, a butyl methacrylate polymer (butyl rubber). Specific examples of the core-shell type rubber particles include Stafiloid AC3822, AC3816N (trade name of Ganz Chemical Co., Ltd.), and Metablen KW-4426 (trade name of Mitsubishi Rayon Co., Ltd.). Specific examples of the acrylonitrile butadiene rubber (NBR) particles include specific examples of styrene butadiene rubber (SBR) particles such as XER-91 (average particle diameter: 0.5 μm) and JSR Co., Ltd. XSK-500 (average particle diameter 0.5 μm, manufactured by JSR Co., Ltd.) is listed. Specific examples of the acrylic rubber particles include Metablen W300A (average particle diameter: 0.1 μm), W450A (average particle diameter: 0.5 μm) (manufactured by Mitsubishi Rayon Co., Ltd.), and the like.

In the curable resin composition, other components may be blended as necessary. Examples of the other components include a filler such as polysiloxane powder, nylon powder, and fluorine powder; a tackifier such as organic bentonite or bentonite; and a polyoxyalkylene-based, fluorine-based or polymer-based antifoaming agent. Or a tackifier such as a flattening agent, an imidazole-based, a thiazole-based, a triazole-based or a decane-based coupling agent; a coloring agent such as phthalocyanine blue, phthalocyanine green, iodine green, disazo yellow or carbon black; .

One type or two or more types selected from the group consisting of glass fibers, organic fibers, glass nonwoven fabrics, and organic nonwoven fabrics can be used for the sheet-like fibrous base material used in the prepreg. A sheet-like fibrous base material such as a glass woven fabric, a guanamine nonwoven fabric, a liquid crystal polymer nonwoven fabric or the like can be preferably used, and a glass woven fabric is particularly preferable. The thickness of the sheet-like fibrous base material is preferably from 1 to 200 μm, more preferably from 5 to 175 μm, still more preferably from 10 to 150 μm, still more preferably from 20 to 125 μm, and most preferably from 30 to 100 μm. Specific examples of the sheet-like fibrous base material include Style 1027MS manufactured by Asahi Schwebel Co., Ltd. (75 linear density/25 mm, weft density 75/25 mm, cloth weight 20 g/m ² , thickness 19 μm). Style 1037MS manufactured by Asahi Schwebel Co., Ltd. (elastic density 70 pieces/25 mm, weft density 73 pieces/25 mm, cloth weight 24 g/m ² , thickness 28 μm), 1078 (manufactured by Yoshizawa Seisakusho Co., Ltd.) /25mm, weft density: 54/25mm, cloth weight: 48g/m ² , thickness: 43μm), 2116 made by Yoshizawa Seisakusho Co., Ltd. (warp density 50 pieces / 25mm, weft density 58 pieces / 25mm, cloth weight 103.8g / m ² , thickness 94 μm), and the like. In addition, the liquid crystal polymer is not woven, and Vecls (weight per unit area: 6 to 15 g/m ² ) of a non-woven fabric manufactured by a polyarylate-based liquid crystal polymer manufactured by Kuraray Co., Ltd. or Kuraray Co., Ltd. The manufactured Vectoron is used as a non-woven fabric of fiber raw materials.

The method for producing the prepreg used in the present invention is not particularly limited, and the following method is preferred.

The prepreg can be produced by a commonly known hot melt method, solvent method, or the like. The hot-melt method does not require the resin composition to be dissolved in an organic solvent, and is first applied to a release paper having good peelability from the resin composition, and then laminated or directly coated by a die coating. A method of producing a prepreg from a sheet-like fibrous base material or the like. Further, the solvent method is a method in which a flaky fiber substrate is immersed in a resin composition varnish in which a resin composition is dissolved in an organic solvent, and a resin composition varnish is impregnated into a flaky fiber substrate, followed by drying. . Further, the adhesive film composed of the curable resin composition laminated on the support may be thermally laminated from both sides of the sheet-like reinforcing substrate under heating and pressing conditions to be prepared.

Examples of the organic solvent in the preparation of the varnish include ketones such as acetone, methyl ethyl ketone, and cyclohexanone; ethyl acetate, butyl acetate, cellosolve acetate, propylene glycol monomethyl ether acetate, and carbitol. Acetate such as acetate; cellulolytic agent, carbitol such as butyl carbitol; aromatic hydrocarbon such as toluene or xylene; dimethylformamide, dimethylacetamide, N-methylpyrrolidone and the like. These may be used alone or in combination of two or more.

The drying conditions of the varnish are not particularly limited, and in the molding step, the curable resin composition must have fluidity and adhesion. On the other hand, when a large amount of organic solvent remains in the prepreg, it causes swelling after hardening. Therefore, the content ratio of the organic solvent to the curable resin composition is preferably 5% by mass or less, and particularly preferably 2% by mass or less. The specific drying conditions vary depending on the curability of the curable resin composition or the amount of the organic solvent in the varnish. However, in the varnish containing 30 to 60% by mass of the organic solvent, it is preferably 80 to 180 ° C. Dry for 3 to 13 minutes. The preferred drying conditions can be appropriately set by simple experimentation.

The thickness of the prepreg is preferably in the range of 20 to 250 μm, particularly preferably in the range of 40 to 180 μm, more preferably 60, from the viewpoint of the cost of the sheet-like fibrous substrate and the desired rigidity of the prepreg. ~150μm range. The thickness of the prepreg can be controlled by adjusting the impregnation amount of the curable resin composition. In addition, since the prepreg must have a fluidity which can be laminated without causing a gap under molding, the curable resin composition in the prepreg preferably has a minimum melt viscosity in the range of 200 to 30000 poise, in particular Good for the range of 1000~20000poise.

<support>

In the method of the present invention, since the support is used instead of the metal foil and the prepreg is hardened, the unnecessary step of removing the metal foil is not required, and the productivity of the laminate is good, and the waste liquid can be reduced in terms of the environmental surface. The advantages are further advantageous in that it is low cost and easy to remove compared to metal foil. The support used in the present invention is a self-supporting film, and a plastic film can be suitably used. The plastic film may, for example, be polyethylene terephthalate, polyethylene naphthalate, polyimide, polyamidimide, polyamine, polytetrafluoroethylene, polycarbonate, etc., preferably The polyethylene terephthalate film or the polyethylene naphthalate film is particularly preferably a polyethylene terephthalate film from the viewpoint of being inexpensive. In addition, for the purpose of improving the releasability after hardening, the plastic film is preferably a release plastic film subjected to surface treatment such as rough treatment or corona treatment, or a polyoxyalkylene resin is present on the surface of the support. A release plastic film of another release layer such as an alkyd resin or a fluororesin. In addition, the surface of the support may be subjected to a surface treatment. The arithmetic mean roughness (Ra value) is preferably 50 nm or less, and particularly preferably 40 nm, from the viewpoint of smoothly maintaining the surface of the prepreg when the prepreg is in contact with the prepreg. Hereinafter, it is more preferably 35 nm or less, still more preferably 30 nm or less, and most preferably 25 nm or less. The lower limit of the arithmetic mean roughness (Ra value) is not particularly limited, and is preferably 0.1 nm or more, and particularly preferably 0.5 nm or more from the viewpoint of practicality of the support. The measurement of the arithmetic mean roughness (Ra value) can be carried out by a generally known method, and can be measured, for example, using a device such as a non-contact surface roughness meter (for example, WYKO NT3300 manufactured by Veeco Instruments Co., Ltd.). Commercially available products can be used as the support, and examples thereof include T60 (manufactured by Toray Co., Ltd., polyethylene terephthalate film), and A4100 (manufactured by Toyobo Co., Ltd., polyethylene terephthalate film). ), Q83 (made by Teijin DuPont Co., Ltd., polyethylene naphthalate film), and polyethylene terephthalate film made of Lintec Co., Ltd. with an alkyd type release agent (AL-5) , Diafoil B1000 (polyethylene terephthalate film manufactured by Mitsubishi Chemical Polyester Film Co., Ltd.) and the like.

The thickness of the support is preferably from 10 to 70 μm, particularly preferably from 15 to 70 μm. When the thickness is too small, the handleability tends to deteriorate or the peelability of the support layer tends to decrease. In addition, when the thickness is too large, the cost-effectiveness tends to deteriorate.

<Etherating the prepreg to form an insulating layer>

In the step (A), one or more prepregs are placed between the supports, and the prepreg is cured by heating and pressurizing under reduced pressure to form an insulating layer. When two or more prepregs are used, the same prepreg or different prepregs can be used. When a different prepreg is used, one or all of the composition of the curable resin composition, the material of the sheet-like fibrous base material, and the thickness of the sheet-like fibrous base material may be different from each other. The insulating layer of the present invention can be directly used in the production of a laminate without providing an adhesive layer.

Further, from the viewpoint of workability, a prepreg with a support attached to the surface of the support to which the prepreg is applied may be used. The bonding of the support to the prepreg can be carried out by heating and pressing by means of a molding, a batch type laminator, a roll laminator or the like. The heating temperature is preferably from 60 to 140 ° C, particularly preferably from 70 to 130 ° C, from the viewpoint of adhesion between the support and the prepreg. The pressing pressure is preferably in the range of 1 to 11 kgf/cm ² (9.8×10 ⁴ to 107.9×10 ⁴ N/m ² ), particularly preferably 2 to 7 kgf/cm, when using a batch type laminating machine. ² (19.6 × 10 ⁴ ~ 68.6 × 10 ⁴ N / m ² ). The pressing time is preferably in the range of 5 seconds to 3 minutes. When a roll laminator is used, the line pressure is preferably in the range of 1 to 15 kgf/cm, and more preferably in the range of 1 to 10 kgf/cm. When the pressure is too small, the fluidity of the resin composition is insufficient, and the adhesion to the support tends to be lowered. When the pressure is too large, it tends to be difficult to maintain the film thickness due to the bleeding of the resin. A vacuum laminating machine can use a commercially available vacuum laminating machine. For example, a vacuum laminating machine MVLP-500 manufactured by Nippon Seisakusho Co., Ltd., a vacuum wet film coater manufactured by Nichigo Morton Co., Ltd., and Hitachi Industries Co., Ltd. A roll dry coater made by the company, a vacuum laminator made by Hitachi AIC Co., Ltd., and the like.

When the prepreg with the support is used, the layers of the prepreg are overlapped relative to each other, or the other one or more prepregs are placed between the two prepreg layers of the prepreg with the support and overlap. Thereafter, heating and pressurization are performed under reduced pressure to harden the prepreg to form an insulating layer. As described above, the prepreg to be inserted may be the same as or different from the prepreg used as the prepreg layer of the prepreg to which the support is attached.

The step of forming the insulating layer by curing the prepreg by heating and pressurizing under reduced pressure can be carried out using a vacuum hot press. For example, it can be performed by molding from a metal plate such as a SUS plate heated to the side of the support body.

The molding conditions are preferably carried out under reduced pressure of 1 × 10 ^-2 MPa or less. Heating and pressurization can be carried out in one stage. From the viewpoint of controlling the bleeding of the resin, it is preferred to carry out the conditions in two or more stages. The molding of the first stage is preferably carried out at a temperature of 70 ° C to 150 ° C, a pressure of 1 to 15 kgf / cm ² , and a time of 15 to 45 minutes. The molding of the second stage is preferably carried out at a temperature of 150 ° C to 250 ° C, a pressure of 1 to 140 kgf / cm ² , and a time of 60 to 150 minutes, and more preferably at a temperature of 160 ° C to 240 ° C. The pressure is in the range of 1 to 40 kgf/cm ² and the time is in the range of 75 to 130 minutes.

For example, MNPC-V-750-5-200 (made by Nippon Seisakusho Co., Ltd.), VH1-1603 (made by Kitagawa Seiki Co., Ltd.), etc. are mentioned.

The lower limit of the glass transition temperature of the insulating layer prevents cracking at the end of the through hole, improves the adhesion reliability between the resin composition and the conductor layer, and reduces warpage at a high temperature to improve the structure of the wafer. From the viewpoint, it is preferably 150 ° C or higher, and particularly preferably 155 ° C or higher. Further, the upper limit of the glass transition temperature of the insulating layer is preferably 175 ° C or less, more preferably 180 ° C or less, still more preferably 190 ° C or less, and still more preferably 200 ° C or less. It is preferably 230 ° C or less, particularly preferably 250 ° C or less, and most preferably 270 ° C or less.

The tensile modulus of the insulating layer is preferably 10 GPa or more, and particularly preferably 15 GPa or more, from the viewpoint of ensuring rigidity during mounting of the electronic component, and low warpage and impact resistance of the product. Further, the tensile modulus of the insulating layer is preferably 25 GPa or less, more preferably 30 GPa or less, and still more preferably 35 GPa or less from the viewpoint of higher and better.

[(B) Steps]

(B) The step of removing the support is generally carried out by mechanical peeling by means of a manual or automatic peeling device. The support is preferably peeled off after the prepreg is cured to form an insulating layer. When the step of forming the through hole (E) is described later, the step of forming the through hole (E) may be performed before or after the step of (B) removing the support, and from the viewpoint of protecting the insulating layer when the through hole is formed, It is preferable to carry out (E) the step of forming the through hole before the step of (B) removing the support.

[(C) Steps]

The (C) step can be carried out by a dry method such as plasma or a wet method such as an aqueous oxidizing agent such as an alkaline permanganic acid solution. In particular, it is preferable from the viewpoint of the roughening of the surface of the insulating layer and the improvement of the plating adhesion strength in accordance with the degreasing performed by the oxidizing agent. When the step (C) is carried out by an oxidizing agent, it is preferred to carry out the swelling treatment according to the swelling liquid, the roughening treatment according to the oxidizing agent, and the neutralization treatment according to the neutralizing agent in this order. The swelling liquid is not particularly limited, and examples thereof include an alkali solution and a surfactant solution, and an alkali solution is preferred. The alkali solution is preferably a sodium hydroxide solution or a potassium hydroxide solution. For example, Swelling Dip Securiganth P, Swelling Dip Securiganth SBU manufactured by Atotech Japan Co., Ltd., and the like are exemplified. The swelling treatment of the swelling liquid is not particularly limited, and specifically, the swelling liquid at 30 to 90 ° C may be allowed to adhere for 1 minute to 15 minutes. From the viewpoint of workability and the fact that the resin is not excessively swollen, a method of immersing the swelling liquid at 40 to 80 ° C for 5 seconds to 10 minutes is preferred. The oxidizing agent is not particularly limited, and examples thereof include an alkaline permanganic acid solution in which potassium permanganate or sodium permanganate is dissolved in an aqueous sodium hydroxide solution. The roughening treatment by an oxidizing agent such as an alkaline permanganic acid solution is preferably carried out by immersing in an oxidizing agent solution heated to 60 to 80 ° C for 10 minutes to 30 minutes. Further, the concentration of the neutral permanganate in the alkaline permanganic acid solution is preferably 5 to 10% by mass. The commercially available oxidizing agent may, for example, be an alkaline permanganic acid solution such as Concentrate Compact CP or Dosing Solution Securiganth P manufactured by Atotech Japan Co., Ltd. Further, the neutralizing agent is preferably an acidic aqueous solution, and a commercially available product is Reduction Solution Securiganth P (neutralizing solution) manufactured by Atotech Japan Co., Ltd. According to the neutralization treatment of the neutralizing agent, a method of allowing the neutralizing liquid of 30 to 80 ° C to adhere to the treated surface after the roughening treatment according to the oxidizing agent solution may be used for 5 minutes to 30 minutes. From the viewpoint of workability and the like, it is preferred to immerse the object after the roughening treatment with the oxidizing agent solution in a neutralizing solution at 40 to 70 ° C for 5 minutes to 20 minutes. In the step (C), the wall residue generated by the step of forming the through hole by (E) can be removed, and from the viewpoint of roughening the wall surface, it is preferable to carry out the step of (E) forming the through hole. .

The upper limit of the arithmetic mean roughness (Ra value) of the insulating layer after the step (C) is preferably 600 nm or less, and particularly preferably 570 nm from the viewpoint of forming finer wiring under high smoothness. Hereinafter, it is more preferably 540 nm or less, still more preferably 510 nm or less, and most preferably 480 nm or less, and particularly preferably 450 nm or less. On the other hand, the lower limit of the arithmetic mean roughness (Ra value) of the insulating layer is preferably 0.1 nm or more, and more preferably 0.5 nm or more, and more preferably 1 nm or more from the viewpoint of obtaining high peel strength. More preferably, it is 10 nm or more, and it is excellently 50 nm or more, and particularly preferably 100 nm or more.

[(D) Steps]

(D) The step of forming a metal film layer on the surface of the insulating layer by electroless plating can be carried out by a generally known method, for example, by treating the surface of the insulating layer with a surfactant or the like to impart a plating contact of palladium or the like. The medium is impregnated with an electroless plating solution to form a metal film. Copper, nickel, gold, palladium, etc. are mentioned, and among them, copper is preferable. The thickness of the metal film layer is preferably 0.1 to 5.0 μm, more preferably 0.2 to 2.5 μm, still more preferably 0.2 to 1.5 μm from the viewpoint of sufficiently covering the surface of the resin and cost-effectiveness. The metal film layer can also be formed by a direct electroplating method using electroless plating.

The upper limit of the peeling strength of the insulating layer and the metal film layer after the step (D) is preferably 0.8 kgf/cm or less, and particularly preferably 1 kgf/cm or less, more preferably from the viewpoint of higher and better. It is 3 kgf/cm or less, more preferably 5 kgf/cm or less, and most preferably 10 kgf/cm or less. On the other hand, the lower limit of the peeling strength of the insulating layer and the metal film layer is preferably 0.45 kgf/cm or more from the viewpoint of maintaining insulation reliability.

[(E) Step]

In the method of the present invention, the step of forming a through hole (E) can be further performed. The step (E) is not particularly limited as long as it can reach the intended purpose, and a through hole can be formed by a generally known method, and a mechanical drill or a laser such as a carbon dioxide gas laser or a YAG laser can be used.

(E) The step of forming the through hole is preferably performed before the step of (B) removing the support from the viewpoint of protecting the surface of the insulating layer when the through hole is formed. Further, from the viewpoint of preventing the surface of the insulating layer from being roughened, it is preferably carried out after (D) a step of forming a metal film layer on the surface of the insulating layer by electroless plating. When the through hole is formed from the support by the laser, the laser absorbing property can be contained in the support in order to improve the laser workability. Examples of the laser absorptive component include metal compound powder, carbon powder, metal powder, and black dye. The blending amount of the laser energy absorbing component is preferably from 0.05 to 40% by mass, particularly preferably from 0.1 to 20% by mass, and more preferably from 1 to 10% by mass, based on all the components constituting the layer containing the component. Examples of the carbon powder include carbon black powder such as furnace black, channel black, acetylene black, hot black, and black, graphite powder, or a mixture of these. Examples of the metal compound powder include titanium oxide such as titanium oxide, magnesia such as magnesium oxide, iron oxide such as iron oxide, nickel oxide such as nickel oxide, zinc oxide such as manganese dioxide or zinc oxide, and the like. Cobalt oxide such as cerium oxide, aluminum oxide, rare earth oxide or cobalt oxide, tin oxide such as tin oxide, tungsten oxide such as tungsten oxide, tantalum carbide, tungsten carbide, boron nitride, tantalum nitride, Titanium nitride, aluminum nitride, barium sulfate, rare earth sulfur oxides, or a mixture of such a powder. Examples of the metal powder include powders of silver, aluminum, lanthanum, cobalt, copper, iron, magnesium, manganese, molybdenum, nickel, palladium, iridium, ruthenium, tin, titanium, vanadium, tungsten, zinc, or alloys or mixtures thereof. Wait. Examples of the black dye include azo (monoazo, disazo) dyes, azo-methine dyes, anthraquinone dyes, quinoline dyes, ketimine dyes, fluorone dyes, nitro dyes, and oxa dyes. Scallion dye, anthraquinone dye, quinoline yellow dye, aminoketone dye, methine dye, anthraquinone dye, coumarin dye, anthrone dye, triphenyl dye, triallyylene dye, phthalocyanine dye, inklophenol dye , diazonine dye, or a mixture of these, and the like. The black dye is preferably a solvent-soluble black dye in order to enhance the dispersibility in the water-soluble resin. These may be used alone or in combination of two or more. The laser energy absorbing component is preferably carbon powder, and particularly preferably carbon black, from the viewpoints of conversion efficiency or versatility of laser energy to heat energy.

[(F) Step]

In the method of the present invention, (F) a step of forming a conductor layer by electrolytic plating may be further performed. Preferably, after (D) a step of forming a metal film layer on the surface of the insulating layer by electroless plating, the metal film layer is applied to perform (F) a step of forming a conductor layer by electrolytic plating. The formation of the conductor layer can be carried out by a generally known method such as a semi-additive method. For example, an electroplated resist layer is formed, and the metal film layer formed in the step (D) is used as a plating mask layer, and then a conductor layer is formed by electrolytic plating. The conductor layer formed by electrolytic plating is preferably copper. Although the thickness varies depending on the design of the desired circuit board, it is preferably 3 to 35 μm, and more preferably 5 to 30 μm. After electrolytic plating, the plating resist is removed by plating a resist stripping solution such as an alkaline aqueous solution, and then the plating mask layer is removed to form a wiring pattern. For the method of removing the plating mask layer, an etching solution can be used. For example, in the case of copper, an acidic etching solution such as an aqueous solution of ferric chloride, an aqueous solution of sodium peroxodisulfate and sulfuric acid, or a CF-6000 manufactured by Mec Co., Ltd., Meltex can be used. An alkaline etching solution such as E-Process-WL manufactured by the company. In the case of nickel, an etching solution containing nitric acid/sulfuric acid as a main component can be used. Commercially available products include NH-1865 manufactured by Mec Co., Ltd., and Melstrip N-950 manufactured by Meltex Co., Ltd., and the like. After the formation of the conductor layer, by annealing at 150 to 200 ° C for 20 to 90 minutes, the peel strength of the conductor layer can be further increased to achieve stability.

(F) a step of forming a conductor layer by electrolytic plating, preferably after (E) forming a through-hole, preferably (E) forming a through-hole, and (C) performing a surface of the insulating layer After the step of roughening treatment, it is more preferably a step of forming a through hole in (E), (C) a step of roughening the surface of the insulating layer, and (D) forming a metal on the surface of the insulating layer by electroless plating. The step of the film layer is carried out.

When the step of (E) forming the through hole is performed on the prepreg having a small thickness, the inside of the through hole may be filled by electroplating while (E) is performed by electrolytic plating to form a conductor layer. This is referred to as through-hole filling plating, whereby it has the advantage of shortening the process of the circuit substrate.

[Multilayer Printed Wiring Substrate]

Next, a method of manufacturing the multilayer printed wiring board of the present invention using the laminate of the present invention will be described. Preferably, the curable resin composition layer of the adhesive film formed on the support by layering the curable resin composition is preferably laminated on the single side of the laminate or directly in contact with the laminate. Double sided. The adhesive film was then laminated to the laminate under reduced pressure by vacuum lamination. The lamination method can be batch or roll continuous. In addition, before the lamination, the adhesive film and the laminate may be preheated (preheated) as necessary.

For the lamination condition, the temperature is preferably set to 70 to 140 ° C, the pressure is preferably set to 1 to 11 kgf / cm ² (9.8 × 10 ⁴ ~ 107.9 × 10 ⁴ N / m ² ), and the air pressure is preferably set to 20 mmHg (26.7 hPa) below. Vacuum lamination can be carried out using a commercially available vacuum laminator. A commercially available vacuum laminating machine, for example, a vacuum wet film coater manufactured by Nichigo Morton Co., Ltd., a vacuum pressurizing laminator manufactured by Nippon Seisakusho Co., Ltd., and a roll manufactured by Hitachi Industries Co., Ltd. Dry coater, vacuum laminator made by Hitachi AIC Co., Ltd., etc.

After the adhesive film is laminated on the laminate in this manner, peeling and thermal curing are performed when the support film is peeled off, whereby the insulating layer can be formed on the laminate. The conditions for heat curing can be selected from 150 ° C to 220 ° C for 20 minutes to 180 minutes, preferably 160 ° C to 200 ° C for 30 minutes to 120 minutes. After the insulating layer is formed, when the support film is not peeled off before curing, it can be peeled off here. The insulating layer is then opened to form via holes. The opening can be carried out by a generally known method such as a drill, a laser, or a plasma. Then, the surface of the insulating layer is roughened by the same method as the above method using an oxidizing agent, and the surface of the insulating layer of the anchor having irregularities is formed by roughening, by combining electroless plating and electrolytic plating. To form a conductor layer. As a method of patterning the conductor layer to form a circuit, for example, a subtractive method, a semi-additive method, or the like which is well known to those skilled in the art can be used.

[semiconductor device]

Furthermore, the semiconductor device of the present invention can be manufactured by using the multilayer printed wiring substrate of the present invention. A semiconductor device is manufactured by bonding a semiconductor element to a connection electrode portion on a multilayer printed wiring board. The method of loading the semiconductor element is not particularly limited, and examples thereof include a wire bonding structure, a flip chip mounting structure, an assembly according to an anisotropic conductive film (ACF), and a structure according to a non-conductive film (NCF).

[Examples]

The present invention will be more specifically described by the following examples, but the present invention is not limited to the following examples. The "parts" in the following description means "parts by mass".

First, the measurement method and evaluation method of the physical property evaluation in the present specification will be described.

<Measurement of Peel Strength (Peel Strength) of Conductor Layer>

The peel strength of the conductor layer was measured in accordance with JIS C6481. Specifically, the circuit board obtained in the examples and the comparative examples was cut into small pieces of 150 mm × 30 mm. A notch having a width of 10 mm and a length of 100 mm was cut into a copper foil portion of the small piece by a cutter, and one end of the copper foil was peeled off and clamped by a holder, and an Instron universal testing machine was used at a rate of 50 mm/min at room temperature. 35 mm was pulled in the vertical direction, and the load at this time was measured as the peeling strength. The thickness of the conductor layer was set to approximately 30 μm.

<Measurement of arithmetic mean roughness (Ra value) of insulating layer>

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 NT3300 manufactured by Veeco Instruments Co., Ltd.) was used in the VSI contact mode by a 50-fold lens. The surface of the insulating layer was measured with a measurement range of 121 μm × 92 μm to obtain an arithmetic mean roughness (Ra value). The Ra value is a measurement site where 10 points are randomly set, and the average value of these is used.

<Measurement of glass transition temperature (Tg)>

The insulating layer produced in the examples and the comparative examples was cut into a test piece having a width of about 5 mm and a length of about 15 mm, and was subjected to a tensile weighting method using a thermomechanical analyzer (Thermo Plus TMA8310) manufactured by Rigaku Co., Ltd. Thermomechanical analysis. After the test piece was placed in the above apparatus, the test piece was continuously measured twice under the measurement conditions of a load of 1 g and a temperature increase rate of 5 ° C /min. The glass transition temperature (° C.) was calculated from the point where the change in the slope of the dimensional change signal in the second measurement was changed.

<Measurement of Tensile Elasticity>

The insulating layer produced in the examples and the comparative examples was subjected to a tensile test using a Tensilon universal testing machine (manufactured by A and D Co., Ltd.) in accordance with Japanese Industrial Standards (JIS K7127), and the tensile modulus was measured.

<Evaluation of the presence or absence of the metal foil removal step>

In the laminates produced in the examples and the comparative examples, the step of removing the metal foil was "○", and the step of removing the metal foil was "x".

(Example 1) <Production of prepreg >

28 parts of liquid bisphenol A type epoxy resin (epoxy equivalent weight 180, "Epikote 828EL" by Mitsubishi Chemical Corporation), naphthalene type tetrafunctional epoxy resin (epoxy equivalent 163, DIC Corporation "HP4700" "28 parts, phenoxy resin ("XX6954BH30" manufactured by Mitsubishi Chemical Corporation, a solution of 30% by mass of MEK and cyclohexanone 1:1), and a mixture of 15 parts of MEK and 15 parts of cyclohexanone The solvent was heated and dissolved while stirring. Then, a triazine-containing phenol-phenolic resin (hydroxyl equivalent of 125, DIC Co., Ltd. "LA7054", solid content of 60% by mass of MEK solution) of 27 parts, and a naphthol-based curing agent (hydroxyl equivalent 215, Dongdu Huacheng Co., Ltd.) 27 parts of MEK solution with 50% solid content and 0.1 part of hardening catalyst ("2E4MZ" manufactured by Shikoku Chemicals Co., Ltd.) and spherical cerium oxide (average particle size 0.5 μm, Admatechs) 70 parts of "SOC2" manufactured by Co., Ltd.), polyvinyl butyral resin ("KS-1" manufactured by Sekisui Chemical Co., Ltd.), dissolved in a mixed solvent of ethanol and toluene at a mass ratio of 1:1 to produce a solid A 15% solution was prepared, and 30 parts of this solution was mixed with the above-mentioned solution after heating and dissolving, and uniformly dispersed by a high-speed rotary blender to prepare a varnish of a curable resin composition. The varnish was impregnated with a 2116 glass fabric (thickness: 94 μm) manufactured by Azawa Seisakusho 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 is 0.1 to 1% by weight in the curable resin composition containing no glass fabric, and the thickness of the prepreg is 120 μm.

<Formation of insulating layer>

The prepreg produced above was cut into a size of 340 mm × 500 mm by a cutter. Then, two prepregs were placed between two PTFE membranes ("Aflex" 50 μm, manufactured by Asahi Glass Co., Ltd.), and a vacuum molding machine (MNPC-V-750-) manufactured by Nagoya Co., Ltd. after 5-200), the degree of reduced pressure to 1 × 10 ^-3 MPa, at a pressure of 10kgf / cm ^2, heating rate 3 ℃ / min, from room temperature to 130. deg.] C and held for 30 minutes, a pressure of 30 kgf/cm ^{2 was} heated to 190 ° C at a temperature increase rate of 3 ° C / min for 90 minutes, thereby forming an insulating layer.

<Production of circuit board>

The tetrafluoroethylene film was peeled off, and the surface of the insulating layer was subjected to a swelling treatment at 60 ° C for 5 minutes by Swelling Dip Securiganth P manufactured by Atotech Japan Co., Ltd. After washing with water, a thickening treatment was carried out at 80 ° C for 20 minutes by Concentrate Compact CP (alkaline permanganic acid solution) manufactured by Atotech Japan Co., Ltd. After washing with water, a neutralization treatment was carried out at 40 ° C for 5 minutes by Reduction Solution Securiganth P (neutralization solution) manufactured by Atotech Japan Co., Ltd. Then, electroless copper plating (using a chemical solution manufactured by Atotech Japan Co., Ltd. as described in detail below and electroless copper plating) was used to produce a laminate. The film thickness of electroless copper plating was 1 μm. Then, electrolytic copper plating was performed to form a conductor layer having a total thickness of 30 μm to obtain a circuit board.

<Process of electroless copper plating using a chemical solution manufactured by Atotech Japan Co., Ltd.>

1. Alkali washing (resin surface cleaning and charge adjustment)

Product Name: Cleaning cleaner Securiganth 902

Condition: 5 minutes at 60 ° C

2. Soft etching

Acidic aqueous solution of sulfuric acid peroxodisulfate

Condition: 1 minute at 30 ° C

3. Pre-dip (for the purpose of adjusting the surface charge in order to give Pd in the next step)

Product Name: Pre. Dip Neoganth B

Condition: 1 minute at room temperature

4. Activation (Pd is imparted to the surface of the resin)

Product name: Activator Neoganth 834

Condition: 5 minutes at 35 ° C

5. Reduction (reducing Pd attached to the resin)

Product Name:Reducer Neoganth WA:Reducer Acceralator 810 mod.

6. Electroless copper plating (precipitating Cu out of the resin surface (Pd surface))

Product Name: Basic Solution Printganth MSK-DK: Copper Solution Printganth MSK: Stabilizer Printganth MSK-DK: Reducer Cu Mixture

Condition: 20 minutes at 35 ° C

(Example 2) <Production of prepreg >

13 parts of a liquid bisphenol A type epoxy resin (epoxy equivalent weight 180, "Epikote 828EL" by Mitsubishi Chemical Corporation), and a naphthalene type 4-functional epoxy resin (epoxy equivalent 163, DIC Corporation "HP4700" ") 6 parts, biphenyl aralkyl type epoxy resin (epoxy equivalent 275, "Nippon Chemical Co., Ltd." "NC3000L") 18 parts, biphenyl type epoxy resin (epoxy equivalent 180, Mitsubishi Chemical Corporation) 10 parts of "YX4000H"), 10 parts of phenoxy resin ("XX6954BH30" manufactured by Mitsubishi Chemical Corporation, a solution of 30% by mass of MEK and cyclohexanone 1:1), and 15 parts of MEK and cyclohexanone 15 The mixture was heated and dissolved while stirring in a mixed solvent. Then, a triazine-containing phenol-phenolic resin (hydroxyl equivalent of 125, DIC Co., Ltd. "LA7054", solid content of 60% by mass of MEK solution) of 15 parts, and a naphthol-based curing agent (hydroxyl equivalent 215, Dongdu Huacheng Co., Ltd.) 15 parts of MEK solution with 60% solid content of the company's "SN-485", 0.1 part of hardening catalyst ("E2MZ" manufactured by Shikoku Chemicals Co., Ltd.), spherical cerium oxide (average particle size 0.5 μm, Admatechs) 135 parts of the company's "SOC2"), phenanthrene-based phosphorus compound ("HCA-HQ" manufactured by Sanko Co., Ltd., average particle size 2 μm), 6 parts, and polyvinyl butyral resin (made by Sekisui Chemical Co., Ltd.) "KS-1"), which is dissolved in a mixed solvent of ethanol and toluene in a mass ratio of 1:1 to prepare a solution having a solid content of 15%, and 15 parts of the solution is mixed with the solution prepared by heating and dissolving, and rotated at a high speed. The blender was uniformly dispersed to prepare a varnish of a curable resin composition. The varnish was impregnated with a 2116 glass fabric (thickness: 94 μm) manufactured by Azawa Seisakusho 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 is 0.1 to 1% by weight in the curable resin composition containing no glass fabric, and the thickness of the prepreg is 120 μm.

Then, in the same manner as in Example 1, an insulating layer was formed and a circuit board was produced.

(Comparative Example 1) <Production of prepreg >

30 parts of a cresol novolac type epoxy resin (epoxy equivalent 215, "N-680" manufactured by DIC Corporation), 75% solid solution of MEK, cresol novolac resin (hydroxy equivalent 119, manufactured by DIC Corporation) "KA-1165") 60% of MEK solution, 16.5 parts, hardening catalyst (manufactured by Shikoku Chemicals Co., Ltd., "2E4MZ"), 0.05 parts, aluminum hydroxide (average particle size: 3.0 μm, manufactured by Ba Industrial Co., Ltd.) "UFE-20") 30 parts and 40 parts of MEK were mixed, and uniformly dispersed by a high-speed rotary blender to prepare a varnish of a curable resin composition. The varnish was impregnated with a 2116 glass fabric (thickness: 94 μm) manufactured by Azawa Seisakusho 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 is 0.1 to 1% by weight in the curable resin composition containing no glass fabric, and the thickness of the prepreg is 120 μm.

Then, in the same manner as in the first embodiment, an insulating layer was formed and a circuit board was produced. However, a plating layer could not be formed on the insulating layer, and the peel strength could not be measured. In the first table, it is indicated as "x".

(Comparative Example 2)

The prepreg prepared in Example 1 was used, and two sheets of electrolytic copper foil ("JTC foil" manufactured by Nikko Materials Co., Ltd., 18 μm) were used instead of the two tetrafluoroethylene films of Example 1, and the others were used. The insulating layer was formed in the same manner as in the first embodiment. Then, it was immersed in an aqueous solution of FeCl _{3 for} 30 minutes to remove the copper foil, and the circuit board was formed in the same manner as in Example 1.

The measurement results are shown in the table below.

It can be seen from Examples 1 and 2 that, according to the method of the present invention, the glass transition temperature and the tensile modulus can be maintained while maintaining the glass transition temperature and the tensile elastic layer without unnecessary steps of removing the metal foil. A laminate of a conductor layer having a good peel strength is formed on the surface. In Comparative Example 1, it was found that the peel strength was not obtained at all because the prepreg of the present invention was not used. Further, in Comparative Example 2, the method of the present invention was not used, and a copper foil was used, so the control of the arithmetic mean roughness was extremely difficult, and an unnecessary step of removing the metal foil was required. Actually, when a copper foil is used, the arithmetic mean roughness of the laminate is increased by the influence of the unevenness of the copper foil, and it is difficult to form fine wiring.

Industrial availability:

According to the present invention, it is possible to produce a laminate which can maintain a glass transition temperature and a tensile modulus while maintaining a glass transition temperature and a tensile modulus while forming a conductor layer having a good peeling strength on the surface of the smooth insulating layer without unnecessary steps of removing the metal foil. This laminate can remove the plating mask layer by etching under mild conditions and suppress the dissolution of the wiring pattern. Therefore, it is particularly suitable for the production of a circuit board in which fine wiring is required. Furthermore, it is also possible to provide a multilayer printed wiring board, a semiconductor device, a computer, a mobile phone, a digital camera, a television, etc., which are loaded with such laminates, or to be used for motorcycles, automobiles, electric cars, ships, airplanes, and the like. machine.

Claims (18)

A method for producing a laminate comprising: (A) arranging one or more prepregs between plastic films and overlapping them, and curing the prepreg by heating and pressurizing under reduced pressure The step of insulating the layer, except that the inner layer circuit substrate is not included between the plastic films, (B) the step of removing the plastic film, (C) the step of roughening the surface of the insulating layer, and (D) by electroless plating a step of forming a metal film layer on the surface of the insulating layer; and containing the inorganic filler 40% by mass or more and 80% by mass or less with respect to 100% by mass of the nonvolatile matter in the curable resin composition in the prepreg; The glass transition temperature of the insulating layer is 150° C. or more and 270° C. or less, and the tensile modulus is 10 GPa or more and 35 GPa or less; and the arithmetic mean roughness of the insulating layer after the step of roughening the surface of the insulating layer (C) is 0.1. The above-mentioned (D) is a step of forming a metal film layer on the surface of the insulating layer by electroless plating, and the peeling strength of the insulating layer and the metal film layer is 0.45 kgf/cm or more and 10 kgf/cm or less. The method for producing a laminate according to the first aspect of the invention, wherein the content of the organic solvent in the curable resin composition of the prepreg is 0.1 to 1% by mass. The method for manufacturing a laminate according to the first aspect of the invention, wherein the plastic film has a thickness of 10 to 70 μm . The method for producing a laminate according to the first aspect of the invention, wherein the surface roughness (Ra) of the surface of the plastic film is 50 nm or less. The method for manufacturing a laminate according to claim 1, wherein the plastic film is a release plastic film. The method for manufacturing a laminate according to claim 1, wherein the step (A) is to superimpose two layers of prepreg with a plastic film prepreg or two prepregs with a plastic film. After one or more other prepregs are placed between the prepreg layers of the material and stacked, the prepreg is cured by heating and pressurization under reduced pressure to form an insulating layer. The method for producing a laminate according to the first aspect of the invention, wherein the prepreg is composed of a curable resin composition and a sheet-like fibrous substrate. The method for producing a laminate according to the seventh aspect of the invention, wherein the sheet-like fibrous base material in the prepreg contains one or more selected from the group consisting of glass fibers, organic fibers, glass nonwoven fabrics, and organic nonwoven fabrics. The method for producing a laminate according to the eighth aspect of the invention, wherein the sheet-like fibrous substrate is a glass fiber having a thickness of from 1 to 200 μm. The method for producing a laminate according to the first aspect of the invention, wherein the curable resin composition in the prepreg contains an epoxy resin and a curing agent. The method for producing a laminate according to claim 10, wherein the curable resin composition in the prepreg contains a naphthalene type epoxy resin and a naphthol type curing agent. The method for producing a laminate according to claim 1, wherein the prepreg is cured at 150 to 250 ° C for 60 to 150 minutes to form an insulating layer. The method for producing a laminate according to claim 1, further comprising (E) a step of forming a through hole. The method for producing a laminate according to claim 13, wherein (E) forming a through hole is performed before the step of (B) removing the plastic film. The method for producing a laminate according to claim 1, further comprising (F) a step of forming a conductor layer by electrolytic plating. A laminate obtained by the production method according to any one of claims 1 to 15. A multilayer printed wiring board using a laminate obtained by the production method of claim 16 of the patent application. A semiconductor device using a laminate obtained by the production method of claim 16 of the patent application.