Method for manufacturing a printed wiring board

Abstract

To provide a method for manufacturing a printed wiring board, which can suppress occurrence of resin peeling when peeling a protection film, and a temporary applying machine to be used in manufacturing a printed wiring board.SOLUTION: A method for manufacturing a printed wiring board comprises the steps of: preparing a protection film-attached adhesive sheet 1 including an adhesive sheet 4 including a support body 2 and a resin composition layer bonded to the support body 2, and a protection film 5 provided so as to be bonded to the resin composition layer of the adhesive sheet 4; heating the protection film-attached adhesive sheet to peel the protection film; and disposing the adhesive sheet with the resin composition layer exposed so that the resin composition layer is bonded to a circuit board.SELECTED DRAWING: Figure 1

Description

Technical Field

[0001] The present invention relates to a method for manufacturing a printed wiring board and a temporary fixing device.

Background Art

[0002] An adhesive sheet with a protective film used for forming an interlayer insulating layer of a printed wiring board generally has a layer structure of a support / resin composition layer / protective film. As described in, for example, Patent Documents 1 and 2, the insulating layer can be formed by peeling the protective film of the adhesive sheet with a protective film, laminating the resin composition layer on the inner layer circuit board, and then curing the resin composition layer.

Prior Art Documents

Patent Documents

[0003]

Patent Document 1

Patent Document 2

Summary of the Invention

Problems to be Solved by the Invention

[0004] As a method for efficiently forming an insulating layer, a roll-shaped adhesive sheet with a protective film is set in a temporary fixing device (auto cutter device), and while the adhesive sheet with a protective film is being conveyed, the protective film is peeled off during the conveyance. The adhesive sheet from which the protective film has been peeled is temporarily fixed so that the resin composition layer is in contact with the circuit board. The circuit board with the adhesive sheet temporarily fixed is conveyed to a laminating device, and the resin composition layer and the circuit board are laminated. These are generally performed in a constant temperature clean room environment of 20 to 25 ° C to prevent foreign matter from being mixed in.

[0005] However, when the protective film is peeled off by these methods, a phenomenon may occur in which even a part of the resin composition layer is peeled off together with the protective film (hereinafter sometimes referred to as "resin peeling"), which is a factor reducing the yield of printed wiring boards.

[0006] In Patent Document 1, an attempt is made to suppress the occurrence of resin peeling by setting the charge amount on the peeling surface of the protective film to a certain value or less, and in Patent Document 2, by setting the difference in peeling strength between the support and the protective film within a specific range. However, from the viewpoint of versatility, it cannot be said that these are always satisfactory methods, and a simpler and more versatile method has been demanded.

[0007] The present invention has been made in view of the above circumstances, and an object thereof is to provide a method for manufacturing a printed wiring board capable of suppressing the occurrence of resin peeling and a temporary fixing device used for manufacturing a printed wiring board.

Means for Solving the Problems

[0008] As a result of intensive studies on the above problems, the present inventors have found that the occurrence of resin peeling can be suppressed by heating the adhesive sheet with a protective film before peeling the protective film of the adhesive sheet with a protective film, and have completed the present invention.

[0009] That is, the present invention includes the following contents. [1] A step of preparing an adhesive sheet with a protective film including (A) an adhesive sheet composed of a support and a resin composition layer joined to the support, and a protective film provided so as to be joined to the resin composition layer of the adhesive sheet, (B) a step of peeling the protective film, and (C) a step of arranging the adhesive sheet with the resin composition layer exposed so that the resin composition layer is joined to the circuit board, including A method for manufacturing a printed wiring board, wherein the adhesive sheet with a protective film is heated before peeling the protective film in step (B). [2] The method for manufacturing a printed wiring board according to [1], wherein in step (B), the surface temperature of the protective film of the adhesive sheet with the protective film when peeling the protective film is 26°C or higher and 110°C or lower. [3] The method for manufacturing a printed wiring board according to [1] or [2], wherein in step (B), the surface temperature of the protective film of the adhesive sheet with the protective film when peeling the protective film is 80°C or lower. [4] Step (D) of heating and pressing a laminate in which an adhesive sheet is temporarily attached to a circuit board, and laminating the adhesive sheet on the circuit board, and (E) Step of thermosetting the resin composition layer to form an insulating layer, The method for manufacturing a printed wiring board according to any one of [1] to [3]. [5] A temporary attachment device that peels off the protective film of an adhesive sheet with a protective film including a support and an adhesive sheet composed of a resin composition layer joined to the support, and a protective film provided so as to be joined to the resin composition layer of the adhesive sheet, and temporarily attaches the adhesive sheet with the resin composition layer exposed to the circuit board so that the resin composition layer is joined to the circuit board, The temporary attachment device includes a heating means for heating the adhesive sheet with the protective film.

Advantages of the Invention

[0010] According to the present invention, it is possible to provide a method for manufacturing a printed wiring board capable of suppressing the occurrence of resin peeling, and a temporary attachment device used for manufacturing a printed wiring board.

Brief Description of the Drawings

[0011]

Figure 1

Figure 2

Embodiments for Carrying Out the Invention

[0012] Hereinafter, embodiments of the present invention will be described with reference to the drawings. It should be noted that each drawing only schematically shows the shape, size, and arrangement of the components to the extent that the invention can be understood. The present invention is not limited by the following description, and each component can be changed as appropriate. In the drawings used in the following description, the same components are denoted by the same reference numerals, and redundant descriptions may be omitted. Also, the configuration according to the embodiment of the present invention is not necessarily manufactured or used in the arrangement shown in the drawings.

[0013] Before explaining in detail the method for manufacturing a printed wiring board of the present invention, an adhesive sheet with a protective film used in the method for manufacturing a printed wiring board of the present invention will be described.

[0014] [Adhesive Sheet with Protective Film] The adhesive sheet with a protective film includes an adhesive sheet composed of a support and a resin composition layer joined to the support, and a protective film provided so as to be joined to the resin composition layer of the adhesive sheet.

[0015] Fig. 1 shows a schematic end view showing an example of an adhesive sheet with a protective film. The adhesive sheet with a protective film 1 includes an adhesive sheet 4 composed of a support 2 and a resin composition layer 3 joined to the support, and a protective film 5 provided so as to be joined to the resin composition layer of the adhesive sheet. Hereinafter, the support, resin composition layer, and protective film in the adhesive sheet with a protective film will be described.

[0016] [Support] The adhesive sheet with a protective film includes a support. Examples of the support include a film made of a plastic material, a metal foil, and a release paper, and a film made of a plastic material and a metal foil are preferable.

[0017] When using a film made of a plastic material as the support, examples of the plastic material include polyesters such as polyethylene terephthalate (hereinafter sometimes abbreviated as "PET"), polyethylene naphthalate (hereinafter sometimes abbreviated as "PEN"), etc., polycarbonate (hereinafter sometimes abbreviated as "PC"), acrylics such as polymethyl methacrylate (PMMA), cyclic polyolefin, triacetyl cellulose (TAC), polyethersulfide (PES), polyether ketone, polyimide, etc. Among them, polyethylene terephthalate and polyethylene naphthalate are preferred, and inexpensive polyethylene terephthalate is particularly preferred.

[0018] When using a metal foil as the support, examples of the metal foil include copper foil, aluminum foil, etc., and copper foil is preferred. As the copper foil, a foil made of single metal copper may be used, or a foil made of an alloy of copper and other metals (for example, tin, chromium, silver, magnesium, nickel, zirconium, silicon, titanium, etc.) may be used.

[0019] The support may be subjected to mat treatment, corona treatment, or antistatic treatment on the surface that joins the resin composition layer.

[0020] In addition, as the support, a support with a release layer having a release layer on the surface on the side joined to the resin composition layer may be used. Examples of the release agent used for the release layer of the support with a release layer include one or more release agents selected from the group consisting of alkyd resin, polyolefin resin, urethane resin, and silicone resin. Among them, it is preferable to contain one or more release agents selected from the group consisting of alkyd resin, polyolefin resin, and urethane resin. As the support with a release layer, commercially available products may be used. For example, a PET film having a release layer mainly composed of an alkyd resin-based release agent such as "SK-1", "AL-5", "AL-7" manufactured by Lintec Corporation, "Lumirror T60" manufactured by Toray Industries, Inc., "Purex" manufactured by Teijin Limited, "Unipile" manufactured by Unitika Ltd., etc.; "U2-NR1" manufactured by DuPont Films; etc.

[0021] The thickness of the support is not particularly limited, but a range of 5 μm to 75 μm is preferable, and a range of 10 μm to 60 μm is more preferable. When using a support with a release layer, it is preferable that the total thickness of the support with the release layer is within the above range.

[0022] <Resin composition layer> The adhesive sheet with a protective film includes a resin composition layer made of a resin composition. The resin composition layer is joined to the support to form an adhesive sheet. When manufacturing a printed wiring board, the resin composition layer is laminated on a circuit board and an insulating layer is formed by thermosetting. The resin composition for forming the resin composition layer is not particularly limited, as long as its cured product has sufficient hardness and insulating properties. Examples of such a resin composition include a composition containing (a) a curable resin and (b) an inorganic filler. As the curable resin, a conventionally known curable resin used when forming an insulating layer of a printed wiring board can be used, and an epoxy resin and a curing agent are preferable. The resin composition may further contain (c) a curing accelerator, (d) a thermoplastic resin, and (e) other additives, if necessary.

[0023] <(a) Curable resin> The resin composition contains a curable resin as component (a). Examples of the (a) curable resin include thermosetting resins and photocurable resins, but a thermosetting resin that can be used when forming an insulating layer of a printed wiring board is preferable.

[0024] Examples of the thermosetting resin include, for example, epoxy resins, phenolic resins, naphthol resins, benzoxazine resins, active ester resins, cyanate ester resins, carbodiimide resins, amine resins, acid anhydride resins, and the like. Component (a) may be used alone or in combination of two or more in any ratio. Hereinafter, resins that can react with epoxy resins to cure the resin composition, such as phenolic resins, naphthol resins, benzoxazine resins, active ester resins, cyanate ester resins, carbodiimide resins, amine resins, and acid anhydride resins, may be collectively referred to as "curing agents". From the viewpoint of forming an insulating layer, the resin composition preferably contains an epoxy resin and a curing agent as component (a) and contains any one of an epoxy resin, a naphthol resin, and an active ester resin.

[0025] Examples of the epoxy resin as component (a) include, for example, bixylenol type epoxy resin, bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, bisphenol AF type epoxy resin, dicyclopentadiene type epoxy resin, trisphenol type epoxy resin, naphthol novolak type epoxy resin, phenol novolak type epoxy resin, tert-butyl-catechol type epoxy resin, naphthalene type epoxy resin, naphthol type epoxy resin, anthracene type epoxy resin, glycidylamine type epoxy resin, glycidyl ester type epoxy resin, cresol novolak type epoxy resin, biphenyl type epoxy resin, linear aliphatic epoxy resin, epoxy resin having a butadiene structure, alicyclic epoxy resin, heterocyclic epoxy resin, spiro ring-containing epoxy resin, cyclohexane type epoxy resin, cyclohexanedimethanol type epoxy resin, naphthylene ether type epoxy resin, trimethylol type epoxy resin, tetraphenylethane type epoxy resin, and the like. The epoxy resin may be used alone or in combination of two or more.

[0026] The resin composition preferably contains, as component (a), an epoxy resin having two or more epoxy groups in one molecule. From the viewpoint of significantly obtaining the desired effects of the present invention, the proportion of the epoxy resin having two or more epoxy groups in one molecule is preferably 50% by mass or more, more preferably 60% by mass or more, and particularly preferably 70% by mass or more, based on 100% by mass of the non-volatile components of component (a).

[0027] Epoxy resins include epoxy resins that are liquid at 20°C (hereinafter sometimes referred to as "liquid epoxy resins") and epoxy resins that are solid at 20°C (hereinafter sometimes referred to as "solid epoxy resins"). The resin composition may contain only a liquid epoxy resin or only a solid epoxy resin as component (a), but from the viewpoint of significantly obtaining the effects of the present invention, it is preferable to contain a combination of a liquid epoxy resin and a solid epoxy resin.

[0028] As the liquid epoxy resin, a liquid epoxy resin having two or more epoxy groups in one molecule is preferable.

[0029] Preferred liquid epoxy resins include bisphenol A type epoxy resins, bisphenol F type epoxy resins, bisphenol AF type epoxy resins, naphthalene type epoxy resins, glycidyl ester type epoxy resins, glycidyl amine type epoxy resins, phenol novolac type epoxy resins, alicyclic epoxy resins having an ester skeleton, cyclohexane type epoxy resins, cyclohexanedimethanol type epoxy resins, glycidyl amine type epoxy resins, and epoxy resins having a butadiene structure. More preferred are bisphenol A type epoxy resins and naphthalene type epoxy resins.

[0030] Specific examples of the liquid epoxy resin include "HP4032", "HP4032D", "HP4032SS", "EXA4032SS", "EXA-7311G4S" (naphthalene-type epoxy resin) manufactured by DIC Corporation; "828US", "jER828EL", "825", "Epicoat 828EL" (bisphenol A-type epoxy resin) manufactured by Mitsubishi Chemical Corporation; "jER807", "1750" (bisphenol F-type epoxy resin) manufactured by Mitsubishi Chemical Corporation; "jER152" (phenol novolac-type epoxy resin) manufactured by Mitsubishi Chemical Corporation; "630", "630LSD" (glycidylamine-type epoxy resin) manufactured by Mitsubishi Chemical Corporation; "ZX1059" (a mixture of bisphenol A-type epoxy resin and bisphenol F-type epoxy resin) manufactured by Nippon Steel Chemical & Material Co., Ltd.; "EX-721" (glycidyl ester-type epoxy resin) manufactured by Nagase ChemteX Corporation; "Celloxide 2021P" (alicyclic epoxy resin having an ester skeleton) manufactured by Daicel Corporation; "PB-3600" (epoxy resin having a butadiene structure) manufactured by Daicel Corporation; "ZX1658", "ZX1658GS" (liquid 1,4-glycidylcyclohexane-type epoxy resin) manufactured by Nippon Steel Chemical & Material Co., Ltd. These may be used alone or in combination of two or more.

[0031] As the solid epoxy resin, a solid epoxy resin having three or more epoxy groups in one molecule is preferable, and an aromatic solid epoxy resin having three or more epoxy groups in one molecule is more preferable.

[0032] Examples of the solid epoxy resin include a bicyclol type epoxy resin, a naphthalene type epoxy resin, a naphthalene type tetrafunctional epoxy resin, a cresol novolak type epoxy resin, a dicyclopentadiene type epoxy resin, a trisphenol type epoxy resin, a naphthol type epoxy resin, a biphenyl type epoxy resin, a naphthylene ether type epoxy resin, an anthracene type epoxy resin, a bisphenol A type epoxy resin, a bisphenol AF type epoxy resin, and a tetraphenylethane type epoxy resin. Among them, a naphthalene type tetrafunctional epoxy resin, a bicyclol type epoxy resin, and a biphenyl type epoxy resin are preferred, and a naphthalene type tetrafunctional epoxy resin, a bicyclol type epoxy resin, and a biphenyl type epoxy resin are more preferred.

[0033] Specific examples of the solid epoxy resin include "HP4032H" (naphthalene-type epoxy resin), "HP-4700", "HP-4710" (tetrafunctional naphthalene-type epoxy resin), "N-690" (cresol novolak-type epoxy resin), "N-695" (cresol novolak-type epoxy resin), "HP-7200", "HP-7200HH", "HP-7200H" (dicyclopentadiene-type epoxy resin), "EXA-7311", "EXA-7311-G3", "EXA-7311-G4", "EXA-7311-G4S", "HP6000" (naphthylene ether-type epoxy resin) manufactured by DIC Corporation; "EPPN-502H" (trisphenol-type epoxy resin), "NC7000L" (naphthol novolak-type epoxy resin), "NC3000H", "NC3000", "NC3000L", "NC3100" (biphenyl-type epoxy resin) manufactured by Nippon Kayaku Co., Ltd.; "ESN475V" (naphthalene-type epoxy resin), "ESN485" (naphthol novolak-type epoxy resin) manufactured by Nippon Steel Chemical & Material Co., Ltd.; "YX4000H", "YL6121" (biphenyl-type epoxy resin), "YX4000HK" (bixylenol-type epoxy resin), "YX8800" (anthracene-type epoxy resin) manufactured by Mitsubishi Chemical Corporation; "PG-100", "CG-500" manufactured by Osaka Gas Chemical Co., Ltd., "YL7760" (bisphenol AF-type epoxy resin), "YL7800" (fluorene-type epoxy resin), "jER1010" (solid bisphenol A-type epoxy resin), "jER1031S" (tetraphenylethane-type epoxy resin) manufactured by Mitsubishi Chemical Corporation, etc. These may be used alone or in combination of two or more.

[0034] When a liquid epoxy resin and a solid epoxy resin are used in combination as component (a), their quantitative ratio (liquid epoxy resin: solid epoxy resin) is preferably 1:0.1 to 1:20, more preferably 1:1 to 1:10, and particularly preferably 1:5 to 1:5 in terms of mass ratio. When the quantitative ratio of the liquid epoxy resin and the solid epoxy resin is within such a range, the desired effects of the present invention can be remarkably obtained. Further, usually, when used in the form of an adhesive sheet, appropriate adhesiveness is brought about. Also, usually, when used in the form of an adhesive sheet, sufficient flexibility can be obtained, and the handleability is improved. Further, usually, a cured product having sufficient breaking strength can be obtained.

[0035] The epoxy equivalent of the epoxy resin as component (a) is preferably 50 g / eq. to 5000 g / eq., more preferably 50 g / eq. to 3000 g / eq., still more preferably 80 g / eq. to 2000 g / eq., and even more preferably 110 g / eq. to 1000 g / eq. Being within this range can provide a cured product of the resin composition with a sufficient crosslink density. The epoxy equivalent is the mass of the epoxy resin containing 1 equivalent of epoxy groups. This epoxy equivalent can be measured according to JIS K7236.

[0036] From the viewpoint of remarkably obtaining the desired effects of the present invention, the weight average molecular weight (Mw) of the epoxy resin as component (a) is preferably 100 to 5000, more preferably 250 to 3000, and still more preferably 400 to 1500. The weight average molecular weight of the epoxy resin is the weight average molecular weight in terms of polystyrene measured by the gel permeation chromatography (GPC) method.

[0037] (a) The content of the epoxy resin as a component is preferably 1% by mass or more, more preferably 5% by mass or more, still more preferably 10% by mass or more, when the non-volatile components in the resin composition are 100% by mass, from the viewpoint of obtaining a cured product exhibiting good mechanical strength and insulation reliability. The upper limit of the content of the epoxy resin is preferably 45% by mass or less, more preferably 40% by mass or less, still more preferably 35% by mass or less, from the viewpoint of significantly obtaining the desired effects of the present invention. In the present invention, the content of each component in the resin composition is a value when the non-volatile components in the resin composition are 100% by mass, unless otherwise specified.

[0038] As the active ester resin as component (a), a resin having one or more active ester groups in one molecule can be used. Among them, as the active ester resin, a resin having two or more highly reactive ester groups in one molecule, such as phenolic esters, thiophenolic esters, N-hydroxyamine esters, esters of heterocyclic hydroxy compounds, etc., is preferable. The active ester resin is preferably obtained by a condensation reaction of a carboxylic acid compound and / or a thiocarboxylic acid compound with a hydroxy compound and / or a thiol compound. In particular, from the viewpoint of improving heat resistance, an active ester resin obtained from a carboxylic acid compound and a hydroxy compound is preferable, and an active ester resin obtained from a carboxylic acid compound and a phenol compound and / or a naphthol compound is more preferable.

[0039] Examples of the carboxylic acid compound include benzoic acid, acetic acid, succinic acid, maleic acid, itaconic acid, phthalic acid, isophthalic acid, terephthalic acid, pyromellitic acid, etc.

[0040] Examples of the phenolic compound or naphthol compound include hydroquinone, resorcinol, bisphenol A, bisphenol F, bisphenol S, phenolphthalein, methylated bisphenol A, methylated bisphenol F, methylated bisphenol S, phenol, o-cresol, m-cresol, p-cresol, catechol, α-naphthol, β-naphthol, 1,5-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, dihydroxybenzophenone, trihydroxybenzophenone, tetrahydroxybenzophenone, phloroglucin, benzenetriol, dicyclopentadiene-type diphenol compound, phenol novolak, and the like. Here, the "dicyclopentadiene-type diphenol compound" refers to a diphenol compound obtained by condensing two molecules of phenol with one molecule of dicyclopentadiene.

[0041] Preferable specific examples of the active ester resin include an active ester resin containing a dicyclopentadiene-type diphenol structure, an active ester resin containing a naphthalene structure, an active ester resin containing an acetylated product of phenol novolak, and an active ester resin containing a benzoylated product of phenol novolak. Among them, an active ester resin containing a naphthalene structure and an active ester resin containing a dicyclopentadiene-type diphenol structure are more preferable. The "dicyclopentadiene-type diphenol structure" represents a divalent structural unit composed of phenylene-dicyclopentylene-phenylene.

[0042] Examples of commercially available active ester resins include, as active ester resins containing a dicyclopentadiene type diphenol structure, "EXB9451", "EXB9460", "EXB9460S", "EXB9460S-65T", "HPC-8000-65T", "HPC-8000H-65TM", "EXB-8000L-65TM" (manufactured by DIC Corporation); as naphthalene type active ester resins containing a naphthalene structure, "EXB9416-70BK", "EXB-8100L-65T", "EXB-8150L-65T", "EXB-8150-65T", "HPC-8150-60T", "HPC-8150-62T", "HPB-8151-62T" (manufactured by DIC Corporation), "PC1300-02-65T" (manufactured by Air Water, Inc.); as active ester resins containing an acetylated product of phenol novolak, "DC808" (manufactured by Mitsubishi Chemical Corporation); as active ester resins containing a benzoylated product of phenol novolak, "YLH1026" (manufactured by Mitsubishi Chemical Corporation); as active ester resins that are acetylated products of phenol novolak, "DC808" (manufactured by Mitsubishi Chemical Corporation); as active ester resins that are benzoylated products of phenol novolak, "YLH1026" (manufactured by Mitsubishi Chemical Corporation), "YLH1030" (manufactured by Mitsubishi Chemical Corporation), "YLH1048" (manufactured by Mitsubishi Chemical Corporation); "EXB-8500-65T" (manufactured by DIC Corporation); and the like.

[0043] (a) From the viewpoint of significantly obtaining the effects of the present invention, the content of the active ester resin as the component (a) is preferably 1% by mass or more, more preferably 5% by mass or more, still more preferably 10% by mass or more, and preferably 25% by mass or less, more preferably 20% by mass or less, still more preferably 15% by mass or less, based on 100% by mass of the non-volatile components in the resin composition.

[0044] (a) As the phenolic resin and naphthol resin as the component (a), those having a novolak structure are preferable from the viewpoints of heat resistance and water resistance. Further, from the viewpoint of adhesion to the conductor layer, a nitrogen-containing phenolic resin is preferable, and a phenolic resin containing a triazine skeleton is more preferable.

[0045] Specific examples of the phenolic resin and the naphthol resin include, for example, "MEH-7700", "MEH-7810", "MEH-7851" manufactured by Meiwa Kasei Co., Ltd., "NHN", "CBN", "GPH" manufactured by Nippon Kayaku Co., Ltd., "SN170", "SN180", "SN190", "SN475", "SN485", "SN495", "SN-495V", "SN375", "SN395" manufactured by Nippon Steel Chemical & Material Co., Ltd., "TD-2090", "LA-7052", "LA-7054", "LA-1356", "LA-3018-50P", "EXB-9500" manufactured by DIC Corporation, and the like.

[0046] From the viewpoint of significantly obtaining the effects of the present invention, the content of the phenolic resin and the naphthol resin as the component (a) is preferably 1% by mass or more, more preferably 10% by mass or more, still more preferably 20% by mass or more, and preferably 50% by mass or less, more preferably 40% by mass or less, still more preferably 30% by mass or less, based on 100% by mass of the non-volatile components in the resin composition.

[0047] Examples of the cyanate ester resin as component (a) include bifunctional cyanate resins such as bisphenol A dicyanate, polyphenol cyanate, oligo(3-methylene-1,5-phenylene cyanate), 4,4'-methylenebis(2,6-dimethylphenyl cyanate), 4,4'-ethylidenediphenyl dicyanate, hexafluorobisphenol A dicyanate, 2,2-bis(4-cyanate) phenylpropane, 1,1-bis(4-cyanate phenylmethane), bis(4-cyanate-3,5-dimethylphenyl) methane, 1,3-bis(4-cyanate phenyl-1-(methylethylidene)) benzene, bis(4-cyanate phenyl) thioether, and bis(4-cyanate phenyl) ether; polyfunctional cyanate resins derived from phenol novolac and cresol novolac; prepolymers in which part of these cyanate resins is triazine-formed; and the like. Specific examples of the cyanate ester resin include "PT30", "PT30S", and "PT60" (phenol novolac type polyfunctional cyanate ester resin), "ULL-950S" (polyfunctional cyanate ester resin), "BA230", "BA230S75" (prepolymer in which part or all of bisphenol A dicyanate is triazine-formed and becomes a trimer), etc. manufactured by Lonza Japan Co., Ltd. The cyanate ester resin is preferably used as a curing agent when the resin composition does not contain component (b) an inorganic filler.

[0048] Specific examples of the benzoxazine resin as component (a) include "JBZ-OD100" (benzoxazine ring equivalent 218 g / eq.), "JBZ-OP100D" (benzoxazine ring equivalent 218 g / eq.), "ODA-BOZ" (benzoxazine ring equivalent 218 g / eq.) manufactured by JFE Chemical Corporation; "P-d" (benzoxazine ring equivalent 217 g / eq.), "F-a" (benzoxazine ring equivalent 217 g / eq.) manufactured by Shikoku Chemicals Corporation; "HFB2006M" (benzoxazine ring equivalent 432 g / eq.) manufactured by Showa Highpolymer Co., Ltd., and the like.

[0049] Specific examples of the carbodiimide resin as a component include Carbodilite (registered trademark) V-03 (carbodiimide group equivalent: 216 g / eq.), V-05 (carbodiimide group equivalent: 216 g / eq.), V-07 (carbodiimide group equivalent: 200); V-09 (carbodiimide group equivalent: 200 g / eq.) manufactured by Nisshinbo Chemicals, Inc.; and Stabaxol (registered trademark) P (carbodiimide group equivalent: 302 g / eq.) manufactured by Rhein Chemie.

[0050] (a) As the amine resin as a component, resins having one or more amino groups in one molecule can be mentioned. For example, aliphatic amines, polyether amines, alicyclic amines, aromatic amines, etc. can be mentioned. Among them, from the viewpoint of achieving the desired effects of the present invention, aromatic amines are preferred. The amine resin is preferably a primary amine or a secondary amine, and more preferably a primary amine. Specific examples of the amine resin include 4,4'-methylenebis(2,6-dimethylaniline), diphenyldiaminosulfone, 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylsulfone, 3,3'-diaminodiphenylsulfone, m-phenylenediamine, m-xylylenediamine, diethyltoluenediamine, 4,4'-diaminodiphenyl ether, 3,3'-dimethyl-4,4'-diaminobiphenyl, 2,2'-dimethyl-4,4'-diaminobiphenyl, 3,3'-dihydroxybenzidine, 2,2-bis(3-amino-4-hydroxyphenyl)propane, 3,3-dimethyl-5,5-diethyl-4,4-diphenylmethanediamine, 2,2-bis(4-aminophenyl)propane, 2,2-bis(4-(4-aminophenoxy)phenyl)propane, 1,3-bis(3-aminophenoxy)benzene, 1,3-bis(4-aminophenoxy)benzene, 1,4-bis(4-aminophenoxy)benzene, 4,4'-bis(4-aminophenoxy)biphenyl, bis(4-(4-aminophenoxy)phenyl)sulfone, bis(4-(3-aminophenoxy)phenyl)sulfone, etc. The amine resin may be a commercially available product. For example, "KAYABOND C-200S", "KAYABOND C-100", "KAYAHARD A-A", "KAYAHARD A-B", "KAYAHARD A-S" manufactured by Nippon Kayaku Co., Ltd., "EPICURE W" manufactured by Mitsubishi Chemical Corporation, etc. can be mentioned.

[0051] As the acid anhydride resin as component (a), resins having one or more acid anhydride groups in one molecule can be mentioned. Specific examples of the acid anhydride resin include phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methylhexahydrophthalic anhydride, methyl nadic anhydride, hydrogenated methyl nadic anhydride, trialkyltetrahydrophthalic anhydride, dodecenyl succinic anhydride, 5-(2,5-dioxotetrahydro-3-furanyl)-3-methyl-3-cyclohexene-1,2-dicarboxylic anhydride, trimellitic anhydride, pyromellitic anhydride, benzophenone tetracarboxylic dianhydride, biphenyltetracarboxylic dianhydride, naphthalene tetracarboxylic dianhydride, oxydiphthalic dianhydride, 3,3'-4,4'-diphenylsulfone tetracarboxylic dianhydride, 1,3,3a,4,5,9b-hexahydro-5-(tetrahydro-2,5-dioxo-3-furanyl)-naphtho[1,2-c]furan-1,3-dione, ethylene glycol bis(anhydrotrimellitate), and polymer-type acid anhydrides such as a styrene-maleic acid resin obtained by copolymerizing styrene and maleic acid, etc.

[0052] When the epoxy resin and a curing agent are contained as component (a), the quantitative ratio of the epoxy resin and all the curing agents is preferably in the range of [total number of epoxy groups of the epoxy resin]:[total number of reactive groups of the curing agent] at a ratio of 1:0.01 to 1:5, more preferably 1:0.05 to 1:3, and even more preferably 1:0.1 to 1:2. Here, the "number of epoxy groups of the epoxy resin" is the total value obtained by summing up the values obtained by dividing the mass of the non-volatile component of the epoxy resin present in the resin composition by the epoxy equivalent. Also, the "number of active groups of the curing agent" is the total value obtained by summing up the values obtained by dividing the mass of the non-volatile component of the curing agent present in the resin composition by the active group equivalent. By setting the quantitative ratio of the epoxy resin and the curing agent as component (a) within such a range, a cured body excellent in flexibility can be obtained.

[0053] (a) The content of the curing agent as a component is preferably 1% by mass or more, more preferably 5% by mass or more, still more preferably 10% by mass or more, and preferably 50% by mass or less, more preferably 40% by mass or less, still more preferably 30% by mass or less, based on 100% by mass of the non-volatile components in the resin composition, from the viewpoint of significantly obtaining the effects of the present invention.

[0054] <(b) Inorganic filler> The resin composition contains (b) an inorganic filler as the (b) component. As the material of the (b) inorganic filler, an inorganic compound is used. Examples of the material of the inorganic filler include silica, alumina, aluminosilicate, glass, cordierite, silicon oxide, barium sulfate, barium carbonate, talc, clay, mica powder, zinc oxide, hydrotalcite, boehmite, aluminum hydroxide, magnesium hydroxide, calcium carbonate, magnesium carbonate, magnesium oxide, boron nitride, aluminum nitride, manganese nitride, aluminum borate, strontium carbonate, strontium titanate, calcium titanate, magnesium titanate, bismuth titanate, titanium oxide, zirconium oxide, barium titanate, barium zirconate titanate, barium zirconate, calcium zirconate, zirconium phosphate, and zirconium tungstate phosphate, etc. Among these, calcium carbonate and silica are preferable, and silica is particularly preferable. Examples of silica include amorphous silica, fused silica, crystalline silica, synthetic silica, hollow silica, etc. Also, spherical silica is preferable as the silica. The (b) inorganic filler may be used alone or in combination of two or more.

[0055] (b) Examples of commercially available products of the component include, for example, "UFP-30" manufactured by Denka Co., Ltd.; "SP60-05" and "SP507-05" manufactured by Nippon Steel & Sumitomo Metal Materials Co., Ltd.; "YC100C", "YA050C", "YA050C-MJE", and "YA010C" manufactured by Admatechs Co., Ltd.; "Silfill NSS-3N", "Silfill NSS-4N", and "Silfill NSS-5N" manufactured by Tokuyama Corporation; "SC2500SQ", "SO-C4", "SO-C2", "SO-C1", and "SC2050-SXF" manufactured by Admatechs Co., Ltd.; and the like.

[0056] (b) The specific surface area of the component is preferably 1 m 2 / g or more, more preferably 2 m 2 / g or more, particularly preferably 3 m 2 / g or more. There is no particular limitation on the upper limit, but it is preferably 60 m 2 / g or less, 50 m 2 / g or less, or 40 m 2 / g or less. The specific surface area is obtained by adsorbing nitrogen gas on the sample surface using a specific surface area measuring device (Macsorb HM-1210 manufactured by Mountech Co., Ltd.) in accordance with the BET method and calculating the specific surface area using the BET multipoint method.

[0057] (b) From the viewpoint of significantly obtaining the desired effects of the present invention, the average particle diameter of the component is preferably 0.01 μm or more, more preferably 0.05 μm or more, particularly preferably 0.1 μm or more, and preferably 5 μm or less, more preferably 2 μm or less, and even more preferably 1 μm or less.

[0058] (b) The average particle size of the component can be measured by a laser diffraction / scattering method based on the Mie scattering theory. Specifically, the particle size distribution of the inorganic filler is created on a volume basis using a laser diffraction / scattering type particle size distribution measuring device, and the median diameter thereof is taken as the average particle size for measurement. As the measurement sample, 100 mg of the inorganic filler and 10 g of methyl ethyl ketone can be weighed into a vial and dispersed by ultrasonic waves for 10 minutes for use. The measurement sample is measured for the volume-based particle size distribution of the (b) component in a flow cell method using a laser diffraction type particle size distribution measuring device with the wavelengths of the light sources used being blue and red, and the average particle size can be calculated as the median diameter from the obtained particle size distribution. Examples of the laser diffraction type particle size distribution measuring device include "LA-960" manufactured by Horiba, Ltd.

[0059] (b) From the viewpoint of enhancing moisture resistance and dispersibility, the component is preferably treated with a surface treatment agent. Examples of the surface treatment agent include vinyl silane-based coupling agents, (meth)acrylic-based coupling agents, fluorine-containing silane coupling agents, aminosilane-based coupling agents, epoxy silane-based coupling agents, mercapto silane-based coupling agents, silane-based coupling agents, alkoxysilanes, organosilazane compounds, titanate-based coupling agents, and the like. Among them, from the viewpoint of significantly obtaining the effects of the present invention, vinyl silane-based coupling agents, (meth)acrylic-based coupling agents, and aminosilane-based coupling agents are preferred. Further, the surface treatment agent may be used alone or in any combination of two or more kinds.

[0060] Examples of commercially available surface treatment agents include "KBM1003" (vinyltriethoxysilane) manufactured by Shin-Etsu Chemical Co., Ltd., "KBM503" (3-methacryloxypropyltriethoxysilane) manufactured by Shin-Etsu Chemical Co., Ltd., "KBM403" (3-glycidoxypropyltrimethoxysilane) manufactured by Shin-Etsu Chemical Co., Ltd., "KBM803" (3-mercaptopropyltrimethoxysilane) manufactured by Shin-Etsu Chemical Co., Ltd., "KBE903" (3-aminopropyltriethoxysilane) manufactured by Shin-Etsu Chemical Co., Ltd., "KBM573" (N-phenyl-3-aminopropyltrimethoxysilane) manufactured by Shin-Etsu Chemical Co., Ltd., "SZ-31" (hexamethyldisilazane) manufactured by Shin-Etsu Chemical Co., Ltd., "KBM103" (phenyltrimethoxysilane) manufactured by Shin-Etsu Chemical Co., Ltd., "KBM-4803" (long-chain epoxy type silane coupling agent) manufactured by Shin-Etsu Chemical Co., Ltd., "KBM-7103" (3,3,3-trifluoropropyltrimethoxysilane) manufactured by Shin-Etsu Chemical Co., Ltd., and the like.

[0061] From the viewpoint of improving the dispersibility of the inorganic filler, the degree of surface treatment with the surface treatment agent preferably falls within a predetermined range. Specifically, 100 parts by mass of the inorganic filler is preferably surface-treated with 0.2 to 5 parts by mass of the surface treatment agent, more preferably surface-treated with 0.2 to 3 parts by mass, and still more preferably surface-treated with 0.3 to 2 parts by mass.

[0062] The degree of surface treatment with the surface treatment agent can be evaluated by the amount of carbon per unit surface area of the inorganic filler. From the viewpoint of improving the dispersibility of the inorganic filler, the amount of carbon per unit surface area of the inorganic filler is preferably 0.02 mg / m 2 or more, more preferably 0.1 mg / m 2 or more, and still more preferably 0.2 mg / m 2 or more. On the other hand, from the viewpoint of suppressing an increase in the melt viscosity of the resin varnish and the melt viscosity in the sheet form, it is preferably 1 mg / m 2 or less, more preferably 0.8 mg / m 2 or less, and still more preferably 0.5 mg / m 2 or less.

[0063] The amount of carbon per unit surface area of the inorganic filler can be measured after washing the surface-treated inorganic filler with a solvent (e.g., methyl ethyl ketone (MEK)). Specifically, a sufficient amount of MEK as a solvent is added to the inorganic filler surface-treated with a surface treatment agent, and ultrasonic cleaning is performed at 25 °C for 5 minutes. After removing the supernatant and drying the solid content, the amount of carbon per unit surface area of the inorganic filler can be measured using a carbon analyzer. As the carbon analyzer, "EMIA-320V" manufactured by Horiba, Ltd. can be used.

[0064] (b) From the viewpoint of improving the mechanical strength of the insulating layer, when the non-volatile components in the resin composition are 100% by mass, the content is preferably 10% by mass or more, more preferably 20% by mass or more, still more preferably 30% by mass or more, preferably 90% by mass or less, more preferably 85% by mass or less, and still more preferably 80% by mass or less.

[0065] <(c) Curing accelerator> The resin composition may contain (c) a curing accelerator. Examples of the curing accelerator include phosphorus-based curing accelerators, amine-based curing accelerators, imidazole-based curing accelerators, guanidine-based curing accelerators, metal-based curing accelerators, etc. Amine-based curing accelerators and imidazole-based curing accelerators are preferred, and amine-based curing accelerators are more preferred. The curing accelerator may be used alone or in combination of two or more.

[0066] Examples of the phosphorus-based curing accelerator include triphenylphosphine, phosphonium borate compounds, tetraphenylphosphonium tetraphenylborate, n-butylphosphonium tetraphenylborate, tetrabutylphosphonium decanoate, (4-methylphenyl)triphenylphosphonium thiocyanate, tetraphenylphosphonium thiocyanate, butyltriphenylphosphonium thiocyanate, etc. Triphenylphosphine and tetrabutylphosphonium decanoate are preferred.

[0067] Examples of the amine-based curing accelerator include trialkylamines such as triethylamine and tributylamine, 4-dimethylaminopyridine, benzyldimethylamine, 2,4,6-tris(dimethylaminomethyl)phenol, 1,8-diazabicyclo(5,4,0)undecene, etc., and 4-dimethylaminopyridine and 1,8-diazabicyclo(5,4,0)undecene are preferred.

[0068] Examples of imidazole-based curing accelerators include 2-methylimidazole, 2-undecylimidazole, 2-heptadecylimidazole, 1,2-dimethylimidazole, 2-ethyl-4-methylimidazole, 1,2-dimethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 1-benzyl-2-methylimidazole, 1-benzyl-2-phenylimidazole, 1-cyanoethyl-2-methylimidazole, 1-cyanoethyl-2-undecylimidazole, 1-cyanoethyl-2-ethyl-4-methylimidazole, 1-cyanoethyl-2-phenylimidazole, 1-cyanoethyl-2-undecylimidazolium trimellitate, 1-cyanoethyl-2-phenylimidazolium trimellitate, 2,4-diamino-6-[2'-methylimidazolyl-(1')]-ethyl-s-triazine, 2,4-diamino-6-[2'-undecylimidazolyl-(1')]-ethyl-s-triazine, 2,4-diamino-6-[2'-ethyl-4'-methylimidazolyl-(1')]-ethyl-s-triazine, 2,4-diamino-6-[2'-methylimidazolyl-(1')]-ethyl-s-triazine isocyanuric acid adduct, 2-phenylimidazole isocyanuric acid adduct, 2-phenyl-4,5-dihydroxymethylimidazole, 2-phenyl-4-methyl-5-hydroxymethylimidazole, 2,3-dihydro-1H-pyrrolo[1,2-a]benzimidazole, 1-dodecyl-2-methyl-3-benzylimidazolium chloride, 2-methylimidazoline, 2-phenylimidazoline and adducts of imidazole compounds and epoxy resins. 2-Ethyl-4-methylimidazole and 1-benzyl-2-phenylimidazole are preferred.

[0069] As the imidazole-based curing accelerator, commercially available products may be used. For example, "P200-H50" manufactured by Mitsubishi Chemical Corporation may be mentioned.

[0070] Examples of guanidine-based curing accelerators include dicyandiamide, 1-methylguanidine, 1-ethylguanidine, 1-cyclohexylguanidine, 1-phenylguanidine, 1-(o-tolyl)guanidine, dimethylguanidine, diphenylguanidine, trimethylguanidine, tetramethylguanidine, pentamethylguanidine, 1,5,7-triazabicyclo[4.4.0]dec-5-ene, 7-methyl-1,5,7-triazabicyclo[4.4.0]dec-5-ene, 1-methylbiguanide, 1-ethylbiguanide, 1-n-butylbiguanide, 1-n-octadecylbiguanide, 1,1-dimethylbiguanide, 1,1-diethylbiguanide, 1-cyclohexylbiguanide, 1-allylbiguanide, 1-phenylbiguanide, 1-(o-tolyl)biguanide, etc. Among them, dicyandiamide and 1,5,7-triazabicyclo[4.4.0]dec-5-ene are preferred.

[0071] Examples of metal-based curing accelerators include organometallic complexes or organometallic salts of metals such as cobalt, copper, zinc, iron, nickel, manganese, and tin. Specific examples of organometallic complexes include organocobalt complexes such as cobalt(II) acetylacetonate and cobalt(III) acetylacetonate, organocopper complexes such as copper(II) acetylacetonate, organozinc complexes such as zinc(II) acetylacetonate, organoiron complexes such as iron(III) acetylacetonate, organonickel complexes such as nickel(II) acetylacetonate, and organomanganese complexes such as manganese(II) acetylacetonate. Examples of organometallic salts include zinc octylate, tin octylate, zinc naphthenate, cobalt naphthenate, tin stearate, zinc stearate, etc.

[0072] (c) From the viewpoint of significantly obtaining the effects of the present invention, when the non-volatile components in the resin composition are 100% by mass, the content of the curing accelerator is preferably 0.01% by mass or more, more preferably 0.02% by mass or more, particularly preferably 0.03% by mass or more, and preferably 3% by mass or less, more preferably 1% by mass or less, particularly preferably 0.5% by mass or less.

[0073] <(d) Thermoplastic resin> The resin composition may contain a (d) thermoplastic resin. Examples of the (d) thermoplastic resin include, for example, phenoxy resin, polyvinyl acetal resin, polyolefin resin, polyimide resin, polyamideimide resin, polyetherimide resin, polysulfone resin, polyethersulfone resin, polyphenylene ether resin, polyetheretherketone resin, polyester resin, etc., and phenoxy resin is preferred. The thermoplastic resin may be used alone or in combination of two or more.

[0074] The weight average molecular weight of the (d) thermoplastic resin in terms of polystyrene is preferably 38,000 or more, more preferably 40,000 or more, and still more preferably 42,000 or more. The upper limit is preferably 100,000 or less, more preferably 70,000 or less, and still more preferably 60,000 or less. The weight average molecular weight of the (d) thermoplastic resin in terms of polystyrene is measured by gel permeation chromatography (GPC) method. Specifically, the weight average molecular weight of the (d) thermoplastic resin in terms of polystyrene is measured using LC-9A / RID-6A manufactured by Shimadzu Corporation as the measuring device, Shodex K-800P / K-804L / K-804L manufactured by Showa Denko KK as the column, chloroform or the like as the mobile phase, at a column temperature of 40 ° C, and can be calculated using the calibration curve of standard polystyrene.

[0075] Examples of the phenoxy resin include a phenoxy resin having one or more skeletons selected from the group consisting of a bisphenol A skeleton, a bisphenol F skeleton, a bisphenol S skeleton, a bisphenol acetophenone skeleton, a novolac skeleton, a biphenyl skeleton, a fluorene skeleton, a dicyclopentadiene skeleton, a norbornene skeleton, a naphthalene skeleton, an anthracene skeleton, an adamantane skeleton, a terpene skeleton, and a trimethylcyclohexane skeleton. The terminal of the phenoxy resin may be any functional group such as a phenolic hydroxyl group or an epoxy group. The phenoxy resin may be used alone or in combination of two or more. Specific examples of the phenoxy resin include "1256" and "4250" (both are bisphenol A skeleton-containing phenoxy resins), "YX8100" (bisphenol S skeleton-containing phenoxy resin), and "YX6954" (bisphenol acetophenone skeleton-containing phenoxy resin) manufactured by Mitsubishi Chemical Corporation. In addition, "FX280" and "FX293" manufactured by Nippon Steel Chemical & Material Co., Ltd., "YX7800BH30", "YX8000BH30", "YL7500BH30", "YX6954BH30", "YX7553", "YX7553BH30", "YL7769BH30", "YL6794", "YL7213", "YL7290", and "YL7482" manufactured by Mitsubishi Chemical Corporation, etc. are also included.

[0076] Examples of the polyvinyl acetal resin include a polyvinyl formal resin and a polyvinyl butyral resin, and the polyvinyl butyral resin is preferred. Specific examples of the polyvinyl acetal resin include, for example, "Denka Butyral 4000-2", "Denka Butyral 5000-A", "Denka Butyral 6000-C", "Denka Butyral 6000-EP" manufactured by Denka Co., Ltd., Esrec BH series, BX series (e.g., BX-5Z), KS series (e.g., KS-1), BL series, BM series, etc. manufactured by Sekisui Chemical Co., Ltd.

[0077] Specific examples of the polyimide resin include "Lica Coat SN20" and "Lica Coat PN20" manufactured by Shin Nippon Rika Co., Ltd. Specific examples of the polyimide resin also include linear polyimide obtained by reacting a bifunctional hydroxyl group-terminated polybutadiene, a diisocyanate compound, and a tetracarboxylic dianhydride (the polyimide described in JP-A-2006-37083), and modified polyimides such as polyimide containing a polysiloxane skeleton (the polyimide described in JP-A-2002-12667 and JP-A-2000-319386).

[0078] Specific examples of the polyamideimide resin include "Vironmax HR11NN" and "Vironmax HR16NN" manufactured by Toyobo Co., Ltd. Specific examples of the polyamideimide resin also include modified polyamideimides such as "KS9100" and "KS9300" (polyamideimide containing a polysiloxane skeleton) manufactured by Hitachi Chemical Co., Ltd.

[0079] Specific examples of the polyethersulfone resin include "PES5003P" manufactured by Sumitomo Chemical Co., Ltd. Specific examples of the polyphenylene ether resin include oligophenylene ether-styrene resin "OPE-2St 1200" manufactured by Mitsubishi Gas Chemical Company, Inc. Specific examples of the polyetheretherketone resin include "Sumipro EK" manufactured by Sumitomo Chemical Co., Ltd. Specific examples of the polyetherimide resin include "Ultem" manufactured by GE.

[0080] Specific examples of the polysulfone resin include polysulfones "P1700", "P3500", etc. manufactured by Solvay Advanced Polymers, LLC.

[0081] Examples of the polyolefin resin include ethylene-based copolymer resins such as low-density polyethylene, ultra-low density polyethylene, high-density polyethylene, ethylene-vinyl acetate copolymer, ethylene-ethyl acrylate copolymer, and ethylene-methyl acrylate copolymer; and polyolefin elastomers such as polypropylene and ethylene-propylene block copolymer.

[0082] Examples of the polyester resin include polyethylene terephthalate resin, polyethylene naphthalate resin, polybutylene terephthalate resin, polybutylene naphthalate resin, polytrimethylene terephthalate resin, polytrimethylene naphthalate resin, polycyclohexane dimethyl terephthalate resin, and the like.

[0083] Among them, as the (d) thermoplastic resin, a phenoxy resin and a polyvinyl acetal resin are preferable. Therefore, in a preferred embodiment, the thermoplastic resin contains at least one selected from the group consisting of a phenoxy resin and a polyvinyl acetal resin. Among them, as the thermoplastic resin, a phenoxy resin is preferable, and a phenoxy resin having a weight average molecular weight of 40,000 or more is particularly preferable.

[0084] From the viewpoint of significantly obtaining the effects of the present invention, when the non-volatile components in the resin composition are 100% by mass, the content of the (d) thermoplastic resin is preferably 0.1% by mass or more, more preferably 0.3% by mass or more, and still more preferably 0.5% by mass or more. The upper limit is preferably 20% by mass or less, more preferably 10% by mass or less, and still more preferably 5% by mass or less.

[0085] <(e) Other Additives> In addition to the above-described components, the resin composition may further contain other additives as optional components. Examples of such additives include elastomers; flame retardants; organic fillers; organic metal compounds such as organic copper compounds, organic zinc compounds, and organic cobalt compounds; thickeners; defoamers; leveling agents; adhesion-imparting agents; and resin additives such as colorants. These additives may be used alone or in combination of two or more in any ratio. The content of each can be appropriately set by those skilled in the art.

[0086] The method for preparing the resin composition is not particularly limited, and examples thereof include a method of mixing and dispersing the compounding components using a rotary mixer or the like together with a solvent or the like as necessary.

[0087] The thickness of the resin composition layer is preferably from 3 μm to 200 μm, more preferably from 5 μm to 150 μm, and still more preferably from 20 μm to 100 μm.

[0088] <Protective film> The adhesive sheet with a protective film includes a protective film. The protective film has advantages such as protecting the surface of the resin composition layer from physical damage when setting the adhesive sheet on the temporary fixing device and preventing adhesion of foreign substances such as dust.

[0089] Examples of the material of the protective film include polyolefins such as polyethylene, polypropylene, and polyvinyl chloride, polyesters such as PET and PEN, polycarbonate (PC), polyimide, and the like. In a preferred embodiment, the protective film preferably includes one or more materials selected from the group consisting of polyethylene, polypropylene, and polyethylene terephthalate, and polypropylene is more preferred.

[0090] The thickness of the protective film is preferably in the range of 5 μm to 75 μm, and more preferably in the range of 5 μm to 30 μm.

[0091] <Manufacturing method of the adhesive sheet with a protective film> The adhesive sheet with a protective film can be manufactured, for example, by a manufacturing method including the following steps (1) and (2). Hereinafter, each step of the manufacturing method of the adhesive sheet with a protective film will be described. (1) A step of forming an adhesive sheet by providing a resin composition layer so as to be joined to a support. (2) A step of providing a protective film so as to be joined to the resin composition layer of the adhesive sheet obtained in the above (1).

[0092] In step (1), a resin composition layer is provided so as to be joined to a support to form an adhesive sheet. The resin composition layer can be provided so as to be joined to the support by a known method. For example, a resin varnish obtained by dissolving a resin composition in a solvent is prepared, and this resin varnish is applied to the surface of the support using a coating device such as a die coater, and the resin varnish is dried to provide a resin composition layer.

[0093] Examples of the solvent used for preparing the resin varnish include ketones such as acetone, methyl ethyl ketone, and cyclohexanone; acetate esters such as ethyl acetate, butyl acetate, cellosolve acetate, propylene glycol monomethyl ether acetate, and carbitol acetate; carbitols such as cellosolve and butyl carbitol; aromatic hydrocarbons such as toluene and xylene; amide solvents such as dimethylformamide, dimethylacetamide, and N-methylpyrrolidone. The solvent may be used alone or in combination of two or more.

[0094] The drying of the resin varnish may be carried out by a known drying method such as heating or hot air blowing. The drying conditions are not particularly limited, but the drying is carried out so that the content of the organic solvent in the resin composition layer is 10% by mass or less, preferably 5% by mass or less. Although it also varies depending on the boiling point of the organic solvent in the resin varnish, for example, when using a resin varnish containing 30% by mass to 60% by mass of the organic solvent, the resin composition layer can be formed by drying at 50°C to 150°C for 3 minutes to 10 minutes.

[0095] In step (2), a protective film is provided so as to be joined to the resin composition layer of the adhesive sheet obtained in step (1). In step (2), it is preferable to laminate the protective film on the resin composition layer of the adhesive sheet by roll or press bonding.

[0096] In the laminating process in step (2), the crimping pressure is usually 0.02 kgf / cm 2 ~11 kgf / cm 2 (0.196×10 4 N / m 2~107.9×10 4 N / m 2 ) and preferably in the range of 0.03 kgf / cm 2 ~5 kgf / cm 2 (0.294×10 4 N / m 2 ~78.4×10 4 N / m 2 ), more preferably in the range of 0.04 kgf / cm 2 ~2 kgf / cm 2 (0.392×10 4 N / m 2 ~49×10 4 N / m 2 ).

[0097] After step (2), the obtained adhesive sheet with a protective film can be wound into a roll to produce an adhesive sheet with a roll-shaped protective film. The adhesive sheet with a roll-shaped protective film can be used in the method for manufacturing a printed wiring board described below.

[0098] The method for manufacturing the above adhesive sheet with a protective film can be continuously carried out by continuously conveying the support from the support wound into a roll, forming a resin composition layer on the support by applying and drying a resin varnish, and then providing a protective film (which can utilize the protective film wound into a roll) so as to be joined to the resin composition layer.

[0099] [Method for manufacturing a printed wiring board, temporary fixing device] The method for manufacturing a printed wiring board of the present invention comprises (A) a step of preparing an adhesive sheet with a protective film including a support and an adhesive sheet composed of a resin composition layer joined to the support, and a protective film provided so as to be joined to the resin composition layer of the adhesive sheet, (B) a step of peeling the protective film, (C) a step of arranging the adhesive sheet with the resin composition layer exposed so that the resin composition layer is joined to a circuit board, and heating the adhesive sheet with a protective film before peeling the protective film in step (B).

[0100] Further, the method for manufacturing a printed wiring board of the present invention may include the following steps (D) and (E) as necessary. (D) A step of heating and pressing a laminate in which an adhesive sheet is temporarily attached on a circuit board, and laminating the adhesive sheet on the circuit board (E) A step of thermosetting the resin composition layer to form an insulating layer Hereinafter, each step of the method for manufacturing a printed wiring board will be described.

[0101] In step (A), an adhesive sheet with a protective film is prepared. The adhesive sheet with a protective film is as described above.

[0102] In step (B), the adhesive sheet with a protective film is heated before peeling the protective film, and then the protective film is peeled off. In step (C), the adhesive sheet with the resin composition layer exposed is arranged so that the resin composition layer is joined to the circuit board.

[0103] FIG. 2 is a schematic diagram showing an example of the temporary fixing device of the present invention. The temporary fixing device 10 is a device for peeling the protective film 5 of the adhesive sheet 1 with a protective film including an adhesive sheet 4 composed of a support and a resin composition layer joined to the support, and temporarily fixing the adhesive sheet 4 with the resin composition layer exposed on the circuit board 6 so that the resin composition layer is joined to the circuit board 6. The temporary fixing device 10 of the present invention includes a heating means for heating the adhesive sheet 1 with a protective film. As shown in an example in FIG. 2, in step (B), a roll-shaped adhesive sheet 11 with a protective film pre-slit to an appropriate width is set in the temporary fixing device (auto-cutter device) 10. In FIG. 2, an embodiment is shown in which the adhesive sheet 4 is provided on one side (the upper surface in FIG. 2) of the circuit board 6, and one roll-shaped adhesive sheet 11 with a protective film is set above the circuit board 6. In the following, based on the description of FIG. 2, the embodiment of providing the adhesive sheet 4 on one side of the circuit board 6 will be described. However, one more roll-shaped adhesive sheet 11 with a protective film may be further set below the circuit board 6, and the adhesive sheet 4 may be provided on both sides of the circuit board 6.

[0104] In step (B), the adhesive sheet 1 with a protective film is conveyed from the roll-shaped adhesive sheet 11 with a protective film, heated by the heating means, and then the protective film 5 is peeled off. The details of step (B) are that the protective film 5 is peeled off from the adhesive sheet 1 with a protective film when the adhesive sheet 1 with a protective film passes through the protective film extractor 13. The peeled protective film 5 can be collected by the protective film winding roll 12. Note that the shape and mechanism of the protective film extractor (tool) 13 are not particularly limited, and for example, it may be columnar (such as a roll) or prismatic (such as a blade). Also, the extraction angle of the protective film with respect to the conveyance direction of the adhesive sheet 1 with a protective film is not particularly limited and may be set arbitrarily.

[0105] The temporary attachment device 10 includes a heating means for heating the adhesive sheet with a protective film. As the heating means, any known heating means can be used as long as it can heat the adhesive sheet with a protective film. The heating of the adhesive sheet with a protective film may be performed on the entire adhesive sheet with a protective film, from the protective film side, or from the support side. Within the range of the thickness of the adhesive sheet with a protective film that is usually used, the entire adhesive sheet with a protective film tends to be easily heated regardless of whether it is heated from the entire adhesive sheet with a protective film, from the protective film side, or from the support side. Examples of the heating method of the adhesive sheet with a protective film 1 by the heating means include a method of providing a heating means such as a hot plate on the protective film extractor 13 to heat the adhesive sheet with a protective film 1, a method of heating the entire inside of the temporary attachment device 10 to heat the adhesive sheet with a protective film 1, and a method of heating the adhesive sheet with a protective film 1 with a heating means (not shown) such as a hot plate before passing the adhesive sheet with a protective film 1 through the protective film extractor 13. Among these, from the viewpoint of significantly obtaining the effects of the present invention, the method of providing a heating means on the protective film extractor 13 is preferable.

[0106] By heating the adhesive sheet with a protective film, the occurrence of resin peeling when peeling the protective film can be suppressed. In the present invention, regarding the reason why the resin peeling when peeling the protective film can be suppressed by heating the adhesive sheet with a protective film, it is presumed that components such as the curable resin contained in the resin composition layer of the adhesive sheet become moderately soft, and as a result, cracks in the resin composition layer that cause resin peeling are less likely to occur when peeling the protective film, thereby suppressing resin peeling.

[0107] As the heating temperature, it is preferable to heat at a temperature higher than the temperature (20 to 25°C) in the constant-temperature clean room when laminating the resin composition layer and the circuit board at the surface temperature of the protective film. Specifically, the surface temperature of the protective film is preferably 1°C or more, more preferably 2°C or more, still more preferably 3°C or more, still more preferably 5°C or more higher than the temperature in the constant-temperature clean room. Or depending on the season, it can also be heated so that it is 10°C or more, preferably 15°C or more higher. Specifically, the surface temperature of the protective film is preferably 26°C or more, more preferably 27°C or more, still more preferably 28°C or more, still more preferably 29°C or more. Or it can be preferably 30°C or more, preferably 35°C or more, preferably 40°C or more. On the other hand, when the temperature is too high, the resin composition layer becomes overly softened, and when peeling the protective film, a phenomenon may occur where a part of the resin composition layer adheres to the surface of the protective film (hereinafter sometimes referred to as "resin adhesion"). Therefore, as the upper limit of the heating temperature, it is preferably below the temperature at which no resin adhesion is observed (no resin adhesion occurs) on the protective film after peeling. Although it varies depending on the resin composition, for example, the surface temperature of the protective film is preferably 110°C or less, more preferably 80°C or less, still more preferably 70°C or less, still more preferably 65°C or less, still more preferably 60°C or less, still more preferably 55°C or less.

[0108] The conveyance speed of the adhesive sheet 1 with a protective film (or the adhesive sheet 4) in step (B) is not particularly limited. However, from the viewpoint of contributing to the improvement of the production speed of the printed wiring board, the conveyance speed is preferably 1 m / min or more, more preferably 2 m / min or more, still more preferably 3 m / min or more. The upper limit is not particularly limited, and it can be 10 m / min or more, etc. According to the present invention in which the adhesive sheet with a protective film is heated, even when the conveyance speed is high, it is advantageous because resin peeling during peeling of the protective film can be suppressed.

[0109] The conveying means of the adhesive sheet 1 (or the adhesive sheet 4) with the protective film in the step (B) is not particularly limited. For example, after fixing the adhesive sheet by sucking it from the support side by vacuum adsorption, it can be mechanically performed.

[0110] In the step (C), the adhesive sheet 4 with the resin composition layer exposed is arranged so that the resin composition layer is joined to the circuit board 6. For example, the adhesive sheet 4 can be aligned with respect to the circuit board 6 conveyed by the conveyor device 15 by the guide rolls 16 and 17.

[0111] The circuit board mainly refers to a substrate such as a glass epoxy substrate, a metal substrate, a polyester substrate, a polyimide substrate, a BT resin substrate, or a thermosetting polyphenylene ether substrate, on one or both sides of which a conductor layer (circuit) formed by pattern processing is formed. Also, in the production of a printed wiring board, an inner layer circuit board of an intermediate product on which an insulating layer and / or a conductor layer is to be further formed is also included in the "circuit board" referred to in the present invention.

[0112] In the step (C), a part of the adhesive sheet 4 may be partially adhered to the circuit board 6 by heating and pressing from the support side. For example, in a part of the front part in the feeding direction of the circuit board 6 (a part on the right side of the circuit board 6 in FIG. 2), in an unnecessary part that does not overlap the circuit that requires lamination processing, a part of the adhesive sheet 4 is heated and pressed from the support side by a contact heater device 18 or the like, so that the adhesive sheet 4 can be partially adhered to the circuit board 6. The heating temperature when partially crimping the adhesive sheet 4 to the circuit board 6 depends on the resin composition used for the resin composition layer and its melt viscosity characteristics, but is preferably 60°C to 130°C, more preferably 60°C to 120°C. The heating time is preferably 1 second to 20 seconds, more preferably 5 seconds to 15 seconds. The pressure during crimping is preferably 0.02 kgf / cm 2 ~0.25 kgf / cm 2 (0.196 N / m 2 ~2.45 N / m 2 )、more preferably 0.05 kgf / cm2 ~0.20 kgf / cm 2 (0.49 N / m 2 ~1.96 N / m 2 ) is.

[0113] After the completion of step (C), the cut adhesive sheet may be provided on the surface of the circuit board by cutting the adhesive sheet 4 with a cutter 14 according to the size of the circuit board 6. When cutting, it is preferable that a cutter backup heater heated in the range of 40°C to 80°C is installed for the purpose of reducing the generation of resin chips (resin chips) of the resin composition.

[0114] All of the above steps (A) to (C) can be continuously performed in a temporary fixing device. Examples of commercially available temporary fixing devices include the Dry Film Laminator Mach series manufactured by Hakuto Co., Ltd.; the Auto Cutter FAC500, SAC-500, SAC-500 / 600 manufactured by Shin Ei Kiko Co., Ltd.; the NT-100, NT-300 manufactured by Nichco Materials Co., Ltd., and the like.

[0115] In step (D), the laminate with the adhesive sheet temporarily fixed on the circuit board is heated and pressurized to laminate the adhesive sheet on the circuit board. In such step (D), the entire adhesive sheet is laminated on the surface of the circuit board.

[0116] The heating and pressurization of the laminate can be performed, for example, by pressing a heated metal plate such as a SUS mirror plate from the support side. In this case, it is preferable to perform the pressing through an elastic material such as heat-resistant rubber so that the adhesive sheet sufficiently follows the circuit unevenness of the circuit board instead of directly pressing the metal plate.

[0117] The pressing temperature is preferably in the range of 70°C to 140°C, and the pressing pressure is preferably 1 kgf / cm 2 ~11 kgf / cm 2 (9.8×10 4 N / m 2 ~107.9×10 4 N / m 2 ) is performed in the range.

[0118] In step (D), the laminate is preferably heated and pressed under a reduced pressure of 20 mmHg (26.7 hPa) or less.

[0119] After the laminating process, preferably, the smoothed process of the laminated adhesive sheet is performed by hot pressing with a metal plate. The smoothing process is performed by heating and pressing the adhesive sheet with a metal plate such as a heated SUS mirror plate under normal pressure (atmospheric pressure). The heating and pressing conditions can be the same as those of the above laminating process.

[0120] The laminating process (and the smoothing process) can be continuously performed by a commercially available vacuum laminator. Examples of commercially available vacuum laminators include a vacuum pressure type laminator manufactured by Meiki Seisakusho Co., Ltd., a Vacuum Applicator manufactured by Nichigo-Morton Co., Ltd., and the like.

[0121] After the laminating process (and the smoothing process), the support is peeled off to expose the resin composition layer. Alternatively, the peeling of the support may be performed after step (E). The peeling of the support may be performed manually or mechanically by an automatic peeling device.

[0122] In step (E), the resin composition layer is thermoset to form an insulating layer.

[0123] The thermosetting conditions of the resin composition layer in step (E) vary depending on the type of the resin composition and the like, but generally, the curing temperature can be in the range of 170°C to 190°C, and the curing time can be in the range of 15 minutes to 60 minutes.

[0124] The method for manufacturing a printed wiring board of the present invention may further include a drilling step of drilling holes in the insulating layer, a roughening step of roughening the insulating layer, a plating step of forming a conductor layer by plating on the roughened surface of the insulating layer, and a circuit forming step of forming a circuit on the conductor layer. These steps can be performed according to various methods known to those skilled in the art and used in the manufacture of printed wiring boards.

Example

[0125] Hereinafter, the present invention will be specifically described by way of examples, but the present invention is not limited to these examples.

[0126] <Measurement of the surface temperature of the adhesive sheet> The temperature of the adhesive sheet with the protective film before peeling the protective film was measured from the protective film side using a non-contact thermometer (OPTEX, THERMO-HUNTER PT-2LD).

[0127] <Method for determining resin peeling> When the protective film was peeled off from the adhesive sheet with the protective film, if a part of the resin composition layer was peeled off together with the protective film and the support was exposed, it was determined that there was resin peeling. The presence or absence of resin peeling was visually determined and evaluated according to the following criteria. 〇: There is no resin peeling. ×: There is resin peeling.

[0128] <Method for determining resin adhesion> When the protective film was peeled off from the adhesive sheet with the protective film, although the resin composition layer was not peeled off together with the protective film until the support was exposed, if a part of the resin composition layer adhered to the surface of the protective film, it was determined that there was resin adhesion. The presence or absence of resin adhesion was visually determined and evaluated according to the following criteria. 〇: There is no resin adhesion. △: There is resin adhesion on the protective film. ×: There is resin adhesion on more than half of the area of the protective film.

[0129] <Example 1> 1. Preparation of resin varnish 28 parts by mass of liquid bisphenol A type epoxy resin (epoxy equivalent: 180 g / eq., "jER828EL" manufactured by Mitsubishi Chemical Corporation), and 28 parts by mass of naphthalene type tetrafunctional epoxy resin (epoxy equivalent: 163 g / eq., "HP-4700" manufactured by DIC Corporation) were dissolved by heating with stirring in a mixed solvent of 15 parts by mass of methyl ethyl ketone (hereinafter abbreviated as "MEK") and 15 parts by mass of cyclohexanone. Then, 110 parts of a novolak-structured naphthol-based curing agent (phenolic hydroxyl group equivalent: 215, "SN-485" manufactured by Nippon Steel & Sumikin Chemical Co., Ltd., MEK solution with a solid content of 50%), 0.1 part by mass of a curing accelerator ("2E4MZ" manufactured by Shikoku Chemicals Corporation), 70 parts by mass of spherical silica ("SO-C2" manufactured by Admatechs Co., Ltd., average particle diameter: 0.5 μm), and 35 parts by mass of a polyvinyl butyral resin solution ("KS-1" manufactured by Sekisui Chemical Co., Ltd., glass transition temperature: 105°C, mixed solution of ethanol and toluene at a ratio of 1:1 with a solid content of 15%) were mixed and uniformly dispersed with a high-speed rotary mixer to prepare a resin varnish. The content of the inorganic filler in the resin varnish was 38% by mass when the non-volatile components in the resin varnish were assumed to be 100% by mass.

[0130] 2. Preparation of Adhesive Sheet A polyethylene terephthalate film with an alkyd resin-based release layer ("AL5" manufactured by Lintec Corporation, thickness: 38 μm) was prepared as a support. The roll-shaped support was sent out, and the resin varnish obtained above was uniformly applied to the surface of the support on the release layer side with a die coater and dried at 80°C to 105°C (average: 90°C) for 4.5 minutes to form a resin composition layer. In the obtained adhesive sheet, the thickness of the resin composition layer was 30 μm and the residual solvent amount was 2.9% by mass.

[0131] 3. Preparation of Adhesive Sheet with Protective Film Subsequently, a polypropylene film (Alphan MA-411, thickness 15 μm, manufactured by Oji Special Paper Co., Ltd.) was continuously laminated as a protective film on the surface of the resin composition layer of the adhesive sheet obtained above at 60°C and a line pressure of 6 kgf / cm under normal pressure to produce an adhesive sheet 1 with a protective film. The obtained adhesive sheet with a protective film was wound into a roll (winding length 60 m). The obtained roll-shaped body was slit to a width of 340 mm to obtain an adhesive sheet with a roll-shaped protective film (width 340 mm, length 60 m).

[0132] 4. Peeling of the protective film An adhesive sheet a with a protective film of 290 mm × 210 mm was cut out from the adhesive sheet with a roll-shaped protective film, placed on a hot plate heated to 30°C from the support body side, and after confirming that the surface temperature on the protective film side of the adhesive sheet a with a protective film reached the same temperature as the hot plate setting temperature, the protective film was peeled off by hand. Resin peeling after the protective film was peeled off and resin adhesion to the protective film were evaluated by the above method. The peeling of the protective film was carried out in a constant temperature clean room environment at 22°C.

[0133] <Example 2> In Example 1, the temperature of the hot plate was changed from 30°C to 40°C. Except for the above matters, the protective film of the adhesive sheet a with a protective film was peeled off in the same manner as in Example 1, and resin peeling and resin adhesion were evaluated.

[0134] <Example 3> In Example 1, the temperature of the hot plate was changed from 30°C to 50°C. Except for the above matters, the protective film of the adhesive sheet a with a protective film was peeled off in the same manner as in Example 1, and resin peeling and resin adhesion were evaluated.

[0135] <Example 4> In Example 1, the temperature of the hot plate was changed from 30°C to 60°C. Except for the above matters, the protective film of the adhesive sheet a with a protective film was peeled off in the same manner as in Example 1, and resin peeling and resin adhesion were evaluated.

[0136] <Example 5> In Example 1, the temperature of the hot plate was changed from 30°C to 80°C. Except for the above matters, the protective film of the adhesive sheet a with a protective film was peeled off in the same manner as in Example 1, and the evaluation of resin peeling and resin adhesion was performed.

[0137] <Example 6> In Example 1, the temperature of the hot plate was changed from 30°C to 100°C. Except for the above matters, the protective film of the adhesive sheet a with a protective film was peeled off in the same manner as in Example 1, and the evaluation of resin peeling and resin adhesion was performed.

[0138] <Example 7> 1. Preparation of Resin Varnish 6 parts by mass of a naphthalene-type epoxy resin (epoxy equivalent 144 g / eq., "EXA4032SS" manufactured by DIC Corporation), 12 parts by mass of a bixylenol-type epoxy resin (epoxy equivalent 190 g / eq., "YX4000HK" manufactured by Mitsubishi Chemical Corporation), and 9 parts by mass of a biphenyl-type epoxy resin (epoxy equivalent of about 290 g / eq., "NC3000H" manufactured by Nippon Kayaku Co., Ltd.) were heated and dissolved with stirring in a mixed solvent of 4 parts by mass of methyl ethyl ketone (MEK) and 25 parts by mass of solvent naphtha. After cooling to room temperature, 45 parts by mass of an active ester curing agent (active group equivalent of about 223, "EXB-9460S-65T" manufactured by DIC Corporation, toluene solution with a non-volatile component of 65% by mass), 5 parts by mass of a phenoxy resin (weight average molecular weight 35000, "YL7553BH30" manufactured by Mitsubishi Chemical Corporation, MEK solution with a solid content of 30% by mass), 5 parts by mass of a 5% by mass MEK solution of 4-dimethylaminopyridine as a curing accelerator, and 160 parts by mass of spherical silica (surface-treated with phenylaminosilane (manufactured by Shin-Etsu Chemical Co., Ltd., "KBM573"), "SC2500SQ" manufactured by Admatechs Co., Ltd., average particle diameter 0.5 μm) were mixed and uniformly dispersed with a high-speed rotary mixer to prepare a resin varnish. The content of the inorganic filler in the resin varnish was 73% by mass when the non-volatile component in the resin varnish was 100% by mass.

[0139] 2. Preparation of Adhesive Sheet A polyethylene terephthalate film with an alkyd resin-based release layer (manufactured by Lintec Corporation, "AL5", thickness 38 μm) was prepared as a support. The roll-shaped support was sent out, and the resin varnish obtained above was uniformly applied to the surface of the support on the release layer side with a die coater, and dried at 80°C to 105°C (average 90°C) for 4.5 minutes to form a resin composition layer. In the obtained adhesive sheet, the thickness of the resin composition layer was 30 μm and the residual solvent amount was 2.5% by mass.

[0140] 3. Preparation of an Adhesive Sheet with a Protective Film Subsequently, a polypropylene film (smooth surface side of "Alpha MA-411" manufactured by Oji Special Paper Co., Ltd., thickness 15 μm) was used as a protective film on the surface of the resin composition layer side of the adhesive sheet obtained above, and laminated at normal pressure, 60°C, and a pressure bonding pressure of 0.06 kgf / cm 2 to produce an adhesive sheet with a protective film. The obtained adhesive sheet with a protective film was wound into a roll (winding length 50 m). The obtained roll-shaped body was slit to a width of 507 mm to obtain a roll-shaped adhesive sheet with a protective film.

[0141] 4. Peeling of the Protective Film An adhesive sheet b with a protective film of 290 mm × 210 mm was cut out from the roll-shaped adhesive sheet with a protective film, placed on a hot plate heated to 30°C from the support side, and after confirming that the surface temperature on the protective film side of the adhesive sheet b with a protective film reached the same temperature as the hot plate setting temperature, the protective film was peeled off by hand. The resin peeling after the protective film peeling and the resin adhesion to the protective film were evaluated by the above method. The peeling of the protective film was carried out in a constant temperature clean room environment at 22°C.

[0142] <Example 8> In Example 7, the temperature of the hot plate was changed from 30°C to 40°C. Except for the above matters, the protective film of the adhesive sheet b with a protective film was peeled off in the same manner as in Example 7, and the resin peeling and resin adhesion were evaluated.

[0143] <Example 9> In Example 7, the temperature of the hot plate was changed from 30°C to 50°C. Except for the above matters, the protective film of the adhesive sheet b with a protective film was peeled off in the same manner as in Example 7, and the evaluation of resin peeling and resin adhesion was performed.

[0144] <Example 10> In Example 7, the temperature of the hot plate was changed from 30°C to 60°C. Except for the above matters, the protective film of the adhesive sheet b with a protective film was peeled off in the same manner as in Example 7, and the evaluation of resin peeling and resin adhesion was performed.

[0145] <Example 11> In Example 7, the temperature of the hot plate was changed from 30°C to 80°C. Except for the above matters, the protective film of the adhesive sheet b with a protective film was peeled off in the same manner as in Example 7, and the evaluation of resin peeling and resin adhesion was performed.

[0146] <Example 12> In Example 7, the temperature of the hot plate was changed from 30°C to 100°C. Except for the above matters, the protective film of the adhesive sheet b with a protective film was peeled off in the same manner as in Example 7, and the evaluation of resin peeling and resin adhesion was performed.

[0147] <Comparative Example 1> In Example 1, the hot plate was not heated. The surface temperature on the protective film side was 22°C. Except for the above matters, the protective film of the adhesive sheet a with a protective film was peeled off in the same manner as in Example 1, and the evaluation of resin peeling and resin adhesion was performed.

[0148] <Comparative Example 2> In Example 7, the hot plate was not heated. The surface temperature on the protective film side was 22°C. Except for the above matters, the protective film of the adhesive sheet b with a protective film was peeled off in the same manner as in Example 7, and the evaluation of resin peeling and resin adhesion was performed.

[0149]

Table 1

[0150]

Table 2

[0151]

Table 3

[0152] In Examples 1 to 12 where the adhesive sheet with a protective film was heated before peeling the protective film, it can be seen that resin peeling was suppressed. In Comparative Examples 1 and 2 where the adhesive sheet with a protective film was not heated before peeling the protective film, resin peeling occurred.

Explanation of Reference Signs

[0153] 1 Adhesive sheet with a protective film 2 Support 3 Resin composition layer 4 Adhesive sheet 5 Protective film 6 Circuit board 10 Temporary fixing device (auto cutter device) 11 Adhesive sheet with a roll-shaped protective film 12 Protective film winding roll 13 Protective film extractor 14 Cutter 15 Conveyor device 16, 17 Guide roll 18 Contact heater

Claims

1. (A) A step of preparing an adhesive sheet with a protective film, which includes a support and a resin composition layer joined to the support, and a protective film provided so as to be joined to the resin composition layer of the adhesive sheet; (B) A step of peeling off the protective film; and (C) A step of arranging the adhesive sheet with the resin composition layer exposed so that the resin composition layer is joined to a circuit board, including: The resin composition layer is made of a resin composition, and the resin composition includes (a) a curable resin and (b) an inorganic filler. A method for manufacturing a printed wiring board, wherein before peeling off the protective film in step (B), the surface temperature of the protective film of the adhesive sheet with the protective film is heated to be 26°C or higher and 110°C or lower.

2. The method for manufacturing a printed wiring board according to claim 1, wherein in step (B), the surface temperature of the protective film of the adhesive sheet with the protective film when peeling off the protective film is 80°C or lower.

3. (D) A step of heating and pressing a laminate with the adhesive sheet temporarily attached on a circuit board to laminate the adhesive sheet on the circuit board; and (E) A step of thermally curing the resin composition layer to form an insulating layer, including the method for manufacturing a printed wiring board according to claim 1 or 2.

4. The method for manufacturing a printed wiring board according to any one of claims 1 to 3, wherein (a) the curable resin includes an epoxy resin and a curing agent.

5. A temporary attachment device that peels off the protective film of an adhesive sheet with a protective film, which includes a support and a resin composition layer joined to the support, and a protective film provided so as to be joined to the resin composition layer of the adhesive sheet, and temporarily attaches the adhesive sheet with the resin composition layer exposed on a circuit board so that the resin composition layer is joined to the circuit board. The resin composition layer is made of a resin composition, and the resin composition includes (a) a curable resin and (b) an inorganic filler. The temporary attachment device is provided with a heating means for heating the surface temperature of the protective film of the adhesive sheet with the protective film to be 26°C or higher and 110°C or lower before peeling off the protective film. The resin composition layer is made of a resin composition, and the resin composition includes (a) a curable resin and (b) an inorganic filler. The temporary attachment device is provided with a heating means for heating the surface temperature of the protective film of the adhesive sheet with the protective film to be 26°C or higher and 110°C or lower before peeling off the protective film.

6. The temporary attachment device according to claim 5, wherein (a) the curable resin includes an epoxy resin and a curing agent.

Images