JP6353184B2 - Adhesive sheet with protective film, method for producing laminate, and method for producing printed wiring board - Google Patents

Description

  The present invention relates to an adhesive sheet with a protective film, a method for producing a laminate, and a method for producing a printed wiring board.

  As a technique for manufacturing a printed wiring board, a manufacturing method by a build-up method in which insulating layers and conductor layers are alternately stacked is known. In the manufacturing method by the build-up method, the insulating layer is, for example, after laminating the resin composition layer on the circuit board using an adhesive sheet with a protective film having a layer configuration of protective film / resin composition layer / support. It can form by hardening a resin composition layer (patent document 1).

  While further improvement in wiring density is demanded, the number of layers due to build-up of printed wiring boards tends to increase, but as the number of layers increases, cracks due to differences in thermal expansion between insulating layers and conductor layers Generation of circuit distortion becomes a problem. As a technique for suppressing such problems of cracks and circuit distortion, for example, a technique for reducing the thermal expansion coefficient of the formed insulating layer by increasing the content of the inorganic filler in the resin composition layer of the adhesive sheet is proposed. (Patent Document 2).

Japanese Patent Laid-Open No. 11-87927 JP 2010-202865 A

  As a method for efficiently forming an insulating layer of a printed wiring board using an adhesive sheet with a protective film, a method of continuously forming an insulating layer using an auto cutter device and a vacuum laminating device has been proposed. In this method, prior to the laminating process in the vacuum laminating apparatus, first, the adhesive sheet is temporarily attached on the circuit board in the auto cutter apparatus. Specifically, the protective film with the protective film is conveyed from the adhesive sheet with the protective film wound in a roll installed in the auto cutter device to the circuit board, and the protective film is peeled off during the conveyance. The adhesive sheet from which the protective film has been peeled is partially heat-pressed on the circuit board so that the exposed resin composition layer side is bonded to the circuit board. Next, the adhesive sheet is cut according to the size of the circuit board, and the adhesive sheet is temporarily attached to the circuit board.

  The above-mentioned method of forming an insulating layer using an auto cutter device and a vacuum laminating device can form the insulating layer continuously and accurately, and essentially contributes significantly to the production speed of printed wiring boards. is there. However, when the present inventors use an adhesive sheet having a resin composition layer having a high inorganic filler content in such a method, a part of the resin composition layer is peeled off when the protective film is peeled off in an auto cutter device. It was confirmed that a phenomenon (hereinafter also referred to as “resin peeling”) in which the film is peeled off and removed together with the protective film may occur. In particular, it was confirmed that this phenomenon of resin peeling becomes more prominent as the conveyance speed of the adhesive sheet in the auto cutter device increases. Thus, when forming an insulating layer having a low coefficient of thermal expansion using an adhesive sheet having a resin composition layer having a high inorganic filler content, the advantage of using an autocutter device (that is, the production speed of a printed wiring board) Contributed to) was reduced.

  This invention makes it a subject to provide the adhesive sheet with a protective film which has a resin composition layer with high inorganic filler content, and does not produce resin peeling at the time of peeling of the protective film in an autocutter apparatus.

  As a result of intensive studies on the above problems, the present inventors have found that the difference between the peel strength of the protective film for the resin composition layer and the peel strength of the support for the resin composition layer is within a specific range. It was found that even when the content of the inorganic filler in the resin composition is high, the sheet does not peel off when the protective film is peeled off in the auto cutter device.

That is, the present invention includes the following contents.
[1] An adhesive sheet with a protective film, comprising: an adhesive sheet comprising a support and a resin composition layer bonded to the support; and a protective film provided to be bonded to the resin composition layer of the adhesive sheet Because
The resin composition layer includes an inorganic filler and a thermosetting resin,
The content of the inorganic filler in the resin composition layer is 60% by mass or more when the nonvolatile component in the resin composition layer is 100% by mass,
The peel strength (S _A ) of the support with respect to the resin composition layer and the peel strength (S _B ) of the protective film with respect to the resin composition layer satisfy S _A −S _B ≧ 0.0020 [kgf / cm]. Adhesive sheet with protective film.
[2] _{S B} is equal to or less than 0.0080kgf / cm, the protective film with the adhesive sheet according to [1].
[3] [(1] or [2] obtained by providing a protective film so as to be bonded to the resin composition layer under the following temperature conditions: [(minimum melt viscosity temperature of the resin composition layer) −10 ° C.]) The adhesive sheet with a protective film as described in 1.
[4] The adhesive sheet with a protective film according to any one of [1] to [3], wherein each thickness of the support and the protective film is 5 μm to 75 μm, and the protective film is thinner than the support.
[5] The adhesive sheet with a protective film according to any one of [1] to [4], wherein the support is a polyethylene terephthalate film.
[6] The adhesive sheet with a protective film according to any one of [1] to [5], wherein the support has a release layer on the surface bonded to the resin composition layer.
[7] The adhesive sheet with a protective film according to [6], wherein the release layer includes one or more release agents selected from the group consisting of alkyd resins, polyolefin resins, and urethane resins.
[8] The adhesive sheet with a protective film according to any one of [1] to [7], wherein the protective film includes one or more materials selected from the group consisting of polyethylene, polypropylene, and polyethylene terephthalate.
[9] The adhesive sheet with a protective film according to any one of [1] to [8], which is an adhesive sheet with a protective film for a buildup layer of a printed wiring board.
[10] An adhesive sheet with a roll-shaped protective film in which the adhesive sheet with a protective film according to any one of [1] to [9] is wound into a roll.
[11] The adhesive sheet with a roll-shaped protective film according to [10], wherein S _A and S _B are peel strengths in the longitudinal direction.
[12] A method for manufacturing a laminate including a cut adhesive sheet provided on a surface of a circuit board, including the following steps (a-1) to (a-4).
(A-1) The process of peeling a protective film, conveying an adhesive sheet with a protective film from the adhesive sheet with a roll-shaped protective film as described in [10] or [11],
(A-2) a step of arranging the adhesive sheet from which the resin composition layer is exposed so that the resin composition layer is bonded to the circuit board;
(A-3) a step of partially bonding the adhesive sheet to the circuit board by heating and pressing a part of the adhesive sheet from the support side, and (a-4) a cutter according to the size of the circuit board. Step of providing the cut adhesive sheet on the surface of the circuit board by cutting at [13] The method according to [12], wherein the conveyance speed in step (a-1) is 1 m / min to 20 m / min.
[14] A method for producing a printed wiring board, comprising the following steps (b-1) and (b-2).
(B-1) heating and pressurizing the laminate produced by the method of [12] or [13], and laminating an adhesive sheet on the circuit board; and (b-2) thermosetting the resin composition layer. And forming an insulating layer

  ADVANTAGE OF THE INVENTION According to this invention, while having a resin composition layer with high inorganic filler content, the adhesive sheet with a protective film which does not produce resin peeling at the time of peeling of the protective film in an autocutter apparatus can be provided. This makes it possible to manufacture a printed wiring board that does not cause a problem of circuit distortion at a high production rate.

FIG. 1 is a schematic end view of an adhesive sheet with a protective film of the present invention. FIG. 2 is a diagram schematically showing temporary attachment of the adhesive sheet to the circuit board by the auto cutter device.

  Hereinafter, the present invention will be described in detail with reference to preferred embodiments thereof.

[Adhesive sheet with protective film]
The adhesive sheet with a protective film of the present invention includes an adhesive sheet comprising a support and a resin composition layer bonded to the support, and a protective film provided to be bonded to the resin composition layer of the adhesive sheet. When the resin composition layer contains an inorganic filler and a thermosetting resin, and the content of the inorganic filler in the resin composition layer is 100% by mass of the nonvolatile component in the resin composition layer, 60 The peel strength (S _A ) of the support with respect to the resin composition layer and the peel strength (S _B ) of the protective film with respect to the resin composition layer are S _A −S _B ≧ 0.0020 [kgf / Cm].

  In FIG. 1, the schematic end elevation of the adhesive sheet with a protective film of this invention is shown. The adhesive sheet with protective film 1 of the present invention is provided so as to be bonded to a support 2 and an adhesive sheet 4 composed of a resin composition layer 3 bonded to the support, and a resin composition layer of the adhesive sheet. Protective film 5.

<Resin composition layer>
In the adhesive sheet with a protective film of the present invention, the resin composition layer contains an inorganic filler at a high content in order to keep the thermal expansion coefficient of the insulating layer obtained by thermosetting the resin composition layer low. Specifically, the content of the inorganic filler in the resin composition layer is 60% by mass or more when the nonvolatile component in the resin composition layer is 100% by mass. From the viewpoint of sufficiently reducing the coefficient of thermal expansion of the insulating layer, the content of the inorganic filler in the resin composition layer is preferably 65% by mass or more when the nonvolatile component in the resin composition layer is 100% by mass. 70 mass% or more is more preferable.

According to the present invention, the difference (S _A -S _B ) between the peel strength (S _A ) of the support with respect to the resin composition layer and the peel strength (S _B ) of the protective film with respect to the resin composition layer is specified. Even if a resin composition layer having a high inorganic filler content is used, the resin is hardly peeled off when the protective film is peeled off in the auto cutter device. Therefore, in the adhesive sheet with a protective film of the present invention, the content of the inorganic filler in the resin composition layer can be further increased without causing the problem of resin peeling. For example, when the nonvolatile component in the resin composition layer is 100% by mass, the content of the inorganic filler in the resin composition layer is 72% by mass or more, 74% by mass or more, 76% by mass or more, and 78% by mass. As mentioned above, you may raise to 80 mass% or more, 82 mass% or more, or 84 mass% or more.

  The upper limit of the content of the inorganic filler in the resin composition layer is when the nonvolatile component in the resin composition layer is 100% by mass from the viewpoint of the mechanical strength of the insulating layer obtained by thermosetting the resin composition layer. Preferably, it is 95 mass% or less, More preferably, it is 90 mass% or less, More preferably, it is 85 mass% or less.

  Examples of the inorganic filler include silica, alumina, barium sulfate, talc, clay, mica powder, aluminum hydroxide, magnesium hydroxide, calcium carbonate, magnesium carbonate, magnesium oxide, boron nitride, aluminum borate, barium titanate, Examples include strontium titanate, calcium titanate, magnesium titanate, bismuth titanate, titanium oxide, barium zirconate, and calcium zirconate. Among these, silica such as amorphous silica, fused silica, crystalline silica, synthetic silica, and hollow silica is particularly suitable. Moreover, spherical silica is preferable as the silica. An inorganic filler may be used individually by 1 type, or may use 2 or more types together.

  The average particle size of the inorganic filler is preferably in the range of 0.01 μm to 2 μm, more preferably in the range of 0.05 μm to 1.5 μm, in that the viscosity of the resin varnish can be adjusted and the fine wiring can be formed. 0.1 μm to 1 μm is more preferable, and 0.15 μm to 0.7 μm is particularly preferable. The average particle diameter of the inorganic filler can be measured by a laser diffraction / scattering method based on Mie scattering theory. Specifically, the particle size distribution of the inorganic filler can be created on a volume basis by a laser diffraction particle size distribution measuring device, and the median diameter can be measured as the average particle diameter. As the measurement sample, an inorganic filler dispersed in water by ultrasonic waves can be preferably used. As a laser diffraction type particle size distribution measuring apparatus, LA-500 manufactured by Horiba, Ltd. can be used.

  Inorganic filler is one kind of aminosilane coupling agent, epoxysilane coupling agent, mercaptosilane coupling agent, silane coupling agent, organosilazane compound, titanate coupling agent, etc. for improving moisture resistance. Or it is preferable to process with 2 or more types of surface treating agents. Examples of commercially available surface treatment agents include “KBM403” (3-glycidoxypropyltrimethoxysilane) manufactured by Shin-Etsu Chemical Co., Ltd., and “KBM803” (3-mercaptopropyltrimethoxy manufactured by Shin-Etsu Chemical Co., Ltd.). Silane), Shin-Etsu Chemical "KBE903" (3-aminopropyltriethoxysilane), Shin-Etsu Chemical "KBM573" (N-phenyl-3-aminopropyltrimethoxysilane), Shin-Etsu Chemical "SZ-31" (Hexamethyldisilazane) manufactured by Co., Ltd.

  The degree of the surface treatment with the surface treatment agent can be quantified by the amount of carbon per unit surface area of the inorganic filler after washing with a solvent (for example, methyl ethyl ketone (MEK)). Specifically, a sufficient amount of MEK as a solvent is added to the inorganic filler surface-treated with the surface treatment agent and ultrasonically cleaned at 25 ° C. for 5 minutes. After removing the supernatant and drying the solid, the carbon amount 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.

Carbon content per unit surface area of the inorganic filler, from the viewpoint of improving dispersibility of the inorganic filler is preferably 0.02 mg / ^{m 2} or more, 0.1 mg / ^{m 2} or more preferably, 0.2 mg / ^{m 2} The above is more preferable. On the other hand, from the viewpoint of suppressing increase in the melt viscosity of the resin varnish and the melt viscosity of the resin composition layer, 1 mg / m ² or less is preferable, 0.8 mg / m ² or less is more preferable, and 0.5 mg / m ² or less is more preferable. preferable.

In the adhesive sheet with a protective film of the present invention, the resin composition layer contains at least a thermosetting resin in addition to the inorganic filler. As a thermosetting resin, the conventionally well-known thermosetting resin used in the adhesive sheet for insulating layer formation can be used, and an epoxy resin is especially preferable. The resin composition layer may further contain additives such as a thermoplastic resin, a curing accelerator, a flame retardant, and rubber particles as necessary.
Hereinafter, an epoxy resin, a curing agent, and an additive that can be used as a material for the resin composition layer will be described.

(Epoxy resin)
Examples of the epoxy resin include 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 epoxy resin, naphthol novolac epoxy resin, phenol novolac. Type epoxy resin, tert-butyl-catechol type epoxy resin, naphthalene type epoxy resin, glycidylamine type epoxy resin, glycidyl ester type epoxy resin, cresol novolac type epoxy resin, biphenyl type epoxy resin, linear aliphatic epoxy resin, alicyclic Epoxy resin, heterocyclic epoxy resin, spiro ring-containing epoxy resin, cyclohexanedimethanol type epoxy resin, naphthylene ether type epoxy resin and tri Chiroru type epoxy resins. An epoxy resin may be used individually by 1 type, or may use 2 or more types together.

  The epoxy resin preferably contains an epoxy resin having two or more epoxy groups in one molecule. When the nonvolatile component of the epoxy resin is 100% by mass, at least 50% by mass or more is preferably an epoxy resin having two or more epoxy groups in one molecule. Among them, it has two or more epoxy groups in one molecule and has a liquid epoxy resin (hereinafter referred to as “liquid epoxy resin”) at a temperature of 20 ° C. and three or more epoxy groups in one molecule. And a solid epoxy resin at a temperature of 20 ° C. (hereinafter referred to as “solid epoxy resin”). By using a liquid epoxy resin and a solid epoxy resin in combination as the epoxy resin, a resin composition layer having excellent flexibility can be obtained. For this reason, the adhesive sheet with a protective film formed using the resin composition layer is excellent in handleability. Moreover, the breaking strength of the insulating layer formed by curing the resin composition layer is also improved.

  As the liquid epoxy resin, bisphenol A type epoxy resin, bisphenol F type epoxy resin, phenol novolac type epoxy resin, or naphthalene type epoxy resin are preferable, and naphthalene type epoxy resin is more preferable. Specific examples of the liquid epoxy resin include “HP4032” (naphthalene type epoxy resin), “HP4032D” (naphthalene type epoxy resin), “EXA4032SS” (naphthalene type epoxy resin) manufactured by DIC Corporation, Mitsubishi Chemical Corporation. “JER828EL” (bisphenol A type epoxy resin), “jER807” (bisphenol F type epoxy resin), “jER152” (phenol novolak type epoxy resin), “ZX1059” (bisphenol A) manufactured by Nippon Steel Chemical Co., Ltd. Type epoxy resin and bisphenol F type epoxy resin). These may be used individually by 1 type, or may use 2 or more types together.

  Examples of solid epoxy resins include tetrafunctional naphthalene type epoxy resins, cresol novolac type epoxy resins, dicyclopentadiene type epoxy resins, trisphenol epoxy resins, naphthol novolac epoxy resins, biphenyl type epoxy resins, and naphthylene ether type epoxy resins. A tetrafunctional naphthalene type epoxy resin, a biphenyl type epoxy resin, or a naphthylene ether type epoxy resin is more preferable. Specific examples of the solid epoxy resin include “HP-4700” (tetrafunctional naphthalene type epoxy resin), “N-690” (cresol novolac type epoxy resin), “N-695” (cresol) manufactured by DIC Corporation. Novolac type epoxy resin), "HP-7200" (dicyclopentadiene type epoxy resin), "EXA7311" (naphthylene ether type epoxy resin), "EXA7310" (naphthylene ether type epoxy resin), "EXA7311-G3" ( Naphthylene ether type epoxy resin), “EPPN-502H” (trisphenol epoxy resin), “NC7000L” (naphthol novolak epoxy resin), “NC3000H” (biphenyl type epoxy resin), “NC3000” manufactured by Nippon Kayaku Co., Ltd. (Biphenyl type epoxy resin "NC3000L" (biphenyl type epoxy resin), "NC3100" (biphenyl type epoxy resin), "ESN475" (naphthol novolak type epoxy resin) manufactured by Tohto Kasei Co., Ltd., "ESN485" (naphthol novolak type epoxy resin), Examples thereof include “YX4000H” (biphenyl type epoxy resin), “YX4000HK” (bixylenol type epoxy resin), etc., manufactured by Mitsubishi Chemical Corporation.

  When a liquid epoxy resin and a solid epoxy resin are used in combination as the epoxy resin, the quantitative ratio thereof (liquid epoxy resin: solid epoxy resin) is in the range of 1: 0.1 to 1: 5 by mass ratio. preferable. By making the quantity ratio of the liquid epoxy resin and the solid epoxy resin within such a range, i) suitable adhesiveness is obtained when used in the form of an adhesive sheet, ii) when used in the form of an adhesive sheet Sufficient flexibility is obtained, handling properties are improved, and iii) a sufficient breaking strength can be obtained in the cured product of the resin composition. From the viewpoint of the effects i) to iii) above, the quantitative ratio of liquid epoxy resin to solid epoxy resin (liquid epoxy resin: solid epoxy resin) is in the range of 1: 0.5 to 1: 4 by mass ratio. Is more preferable.

  The content of the epoxy resin is preferably 3% by mass to 30% by mass, more preferably 5% by mass to 25% by mass, and more preferably 8% by mass to 20% by mass with respect to 100% by mass of the nonvolatile component in the resin composition layer. Is more preferable, and 10% by mass to 20% by mass is particularly preferable.

(Curing agent)
The curing agent is not particularly limited as long as it has a function of curing the epoxy resin, and examples thereof include phenol-based curing agents, active ester-based curing agents, benzoxazine-based curing agents, and cyanate ester-based curing agents. A hardening | curing agent may be used individually by 1 type, or may use 2 or more types together.

  As a phenol type hardening | curing agent, a biphenyl type hardening | curing agent, a naphthalene type hardening | curing agent, a phenol novolak type hardening | curing agent, a naphthylene ether type hardening | curing agent, and a nitrogen-containing phenol type hardening | curing agent are preferable from a heat resistant and water-resistant viewpoint. Further, from the viewpoint of adhesion (peel strength) to the conductor layer, a nitrogen-containing phenol-based curing agent is preferable, and a triazine skeleton-containing phenol-based curing agent is more preferable. Among these, from the viewpoint of highly satisfying heat resistance, water resistance, and adhesiveness (peel strength) to the conductor layer, it is preferable to use a triazine skeleton-containing phenol novolac resin as a curing agent.

  Specific examples of the phenolic curing agent include, for example, biphenyl type curing agents MEH-7700, MEH-7810, MEH-7851 (manufactured by Meiwa Kasei Co., Ltd.), naphthalene type curing agents NHN, CBN, GPH (Nippon Kasei). (Manufactured by Yakuhin Co., Ltd.), SN170, SN180, SN190, SN475, SN485, SN495, SN375, SN395 (manufactured by Nippon Steel Chemical Co., Ltd.), EXB9500 (manufactured by DIC Corporation), TD2090 (phenol novolak type curing agent) DIC Corporation), naphthylene ether type curing agent EXB-6000 (DIC Corporation), triazine skeleton containing phenolic curing agent LA3018, LA7052, LA7054, LA1356 (DIC Corporation) and the like. It is done.

  From the viewpoint of adhesion (peel strength) to the conductor layer, an active ester curing agent is also preferable. When an active ester type curing agent is used as the curing agent, a conductor layer exhibiting sufficient peel strength can be provided on the surface of the insulating layer. Specific examples of the active ester curing agent include “EXB-9460” and “HPC-8000” manufactured by DIC Corporation, “DC808” and “YLH1030” manufactured by Mitsubishi Chemical Corporation.

  Specific examples of the benzoxazine-based curing agent include “HFB2006M” manufactured by Showa Polymer Co., Ltd., “Pd” and “Fa” manufactured by Shikoku Chemicals Co., Ltd.

  Examples of cyanate ester-based curing agents include bisphenol A dicyanate, polyphenol cyanate (oligo (3-methylene-1,5-phenylene cyanate), 4,4′-methylenebis (2,6-dimethylphenyl cyanate), 4,4. '-Ethylidene diphenyl dicyanate, hexafluorobisphenol A dicyanate, 2,2-bis (4-cyanate) phenylpropane, 1,1-bis (4-cyanatephenylmethane), bis (4-cyanate-3,5-dimethyl) Bifunctional cyanate resins such as phenyl) methane, 1,3-bis (4-cyanatephenyl-1- (methylethylidene)) benzene, bis (4-cyanatephenyl) thioether, and bis (4-cyanatephenyl) ether, phenol Novolac and K Examples include polyfunctional cyanate resins derived from sol novolac, prepolymers in which these cyanate resins are partly triazines, etc. Specific examples of cyanate ester curing agents include “PT30” manufactured by Lonza Japan Co., Ltd. “PT60” (both phenol novolac-type polyfunctional cyanate ester resins), “BA230” (prepolymer in which a part or all of bisphenol A dicyanate is triazine-modified), and the like.

  The amount ratio of the epoxy resin and the curing agent is preferably a ratio of [total number of epoxy groups of the epoxy resin]: [total number of reactive groups of the curing agent] in the range of 1: 0.2 to 1: 2. A range of 1: 0.5 to 1: 1.5 is more preferable. Here, the reactive group of the curing agent is an active hydroxyl group, an active ester group or the like, and varies depending on the type of the curing agent. Moreover, the total number of epoxy groups of the epoxy resin is a value obtained by dividing the value obtained by dividing the solid mass of each epoxy resin by the epoxy equivalent for all epoxy resins, and the total number of reactive groups of the curing agent is: The value obtained by dividing the solid mass of each curing agent by the reactive group equivalent is the total value for all curing agents. By making the quantity ratio of an epoxy resin and a hardening | curing agent into such a range, the heat resistance of the hardened | cured material of a resin composition improves.

In one Embodiment, the resin composition layer contained in the adhesive sheet with a protective film of this invention contains the above-mentioned inorganic filler, an epoxy resin, and a hardening | curing agent. From the viewpoint of producing an adhesive sheet with a protective film in which the peel strength (S _A and S _B ) of the support and the protective film with respect to the resin composition layer is in a desired range, the resin composition layer contains silica as an inorganic filler, Mixture of liquid epoxy resin and solid epoxy resin as epoxy resin (mass ratio of liquid epoxy resin: solid epoxy resin is 1: 0.1 to 1: 5, preferably 1: 0.5 to 1: 4) Preferably, each of the curing agents contains at least one selected from the group consisting of a nitrogen-containing phenol curing agent (preferably a triazine skeleton-containing phenol curing agent) and an active ester curing agent. Regarding the resin composition layer containing a combination of such specific components, the preferred contents of the inorganic filler, the epoxy resin, and the curing agent are as described above. Among these, the nonvolatile component in the resin composition is 100%. When the content is mass%, the content of the inorganic filler is preferably 60% by mass to 95% by mass, the content of the epoxy resin is preferably 3% by mass to 30% by mass, and the content of the inorganic filler is 60% by mass. It is more preferable that it is -90 mass% and content of an epoxy resin is 5 mass%-25 mass%. About content of a hardening | curing agent, it is preferable to make it contain so that ratio of the total number of the epoxy groups of an epoxy resin and the total number of the reactive groups of a hardening | curing agent may be 1: 0.2-1: 2, It is more preferable to make it contain so that it may become 1: 0.5-1: 1.5.

  The resin composition layer may further contain additives such as a thermoplastic resin, a curing accelerator, a flame retardant, and rubber particles as necessary.

  Examples of the thermoplastic resin include phenoxy resin, polyvinyl acetal resin, polyimide resin, polyamideimide resin, polyethersulfone resin, and polysulfone resin. A thermoplastic resin may be used individually by 1 type, or may use 2 or more types together.

  The weight average molecular weight in terms of polystyrene of the thermoplastic resin is preferably in the range of 8,000 to 70,000, more preferably in the range of 10,000 to 60,000, and still more preferably in the range of 20,000 to 60,000. The weight average molecular weight in terms of polystyrene of the thermoplastic resin is measured by a gel permeation chromatography (GPC) method. Specifically, the polystyrene-reduced weight average molecular weight of the thermoplastic resin is LC-9A / RID-6A manufactured by Shimadzu Corporation as a measuring device, and Shodex K-800P / K- manufactured by Showa Denko KK as a column. 804L / K-804L can be measured at a column temperature of 40 ° C. using chloroform or the like as a mobile phase, and can be calculated using a standard polystyrene calibration curve.

  Examples of the phenoxy resin include bisphenol A skeleton, bisphenol F skeleton, bisphenol S skeleton, bisphenolacetophenone skeleton, novolac skeleton, biphenyl skeleton, fluorene skeleton, dicyclopentadiene skeleton, norbornene skeleton, naphthalene skeleton, anthracene skeleton, adamantane skeleton, terpene Examples thereof include phenoxy resins having a skeleton and one or more skeletons selected from the group consisting of a trimethylcyclohexane skeleton. The terminal of the phenoxy resin may be any functional group such as a phenolic hydroxyl group or an epoxy group. A phenoxy resin may be used individually by 1 type, or may use 2 or more types together. Specific examples of the phenoxy resin include “1256” and “4250” (both bisphenol A skeleton-containing phenoxy resin), “YX8100” (bisphenol S skeleton-containing phenoxy resin), and “YX6954” (manufactured by Mitsubishi Chemical Corporation). In addition, “FX280” and “FX293” manufactured by Toto Kasei Co., Ltd., “YL7553”, “YL6794”, “YL7213” manufactured by Mitsubishi Chemical Corporation, YL7290 "," YL7482 ", etc. are mentioned.

  Specific examples of the polyvinyl acetal resin include: Electric Butyral 4000-2, 5000-A, 6000-C, 6000-EP manufactured by Denki Kagaku Kogyo Co., Ltd., S-Lec BH Series, BX Series manufactured by Sekisui Chemical Co., Ltd. KS series, BL series, BM series, etc. are mentioned.

  Specific examples of the polyimide resin include “Rika Coat SN20” and “Rika Coat PN20” manufactured by Shin Nippon Rika Co., Ltd. Specific examples of the polyimide resin include linear polyimide obtained by reacting a bifunctional hydroxyl group-terminated polybutadiene, a diisocyanate compound and a tetrabasic acid anhydride (described in JP-A-2006-37083), a polysiloxane skeleton. Examples thereof include modified polyimides such as containing polyimide (described in JP-A No. 2002-12667 and JP-A No. 2000-319386).

  Specific examples of the polyamide-imide resin include “Bilomax HR11NN” and “Bilomax HR16NN” manufactured by Toyobo Co., Ltd. Specific examples of the polyamideimide resin also include modified polyamideimides such as polysiloxane skeleton-containing polyamideimides “KS9100” and “KS9300” manufactured by Hitachi Chemical Co., Ltd.

  Specific examples of the polyethersulfone resin include “PES5003P” manufactured by Sumitomo Chemical Co., Ltd.

  Specific examples of the polysulfone resin include polysulfone “P1700” and “P3500” manufactured by Solvay Advanced Polymers Co., Ltd.

  It is preferable that content of a thermoplastic resin is 0.1 mass%-10 mass% with respect to 100 mass% of non-volatile components in a resin composition layer. By setting the content of the thermoplastic resin in such a range, the viscosity of the resin composition becomes appropriate, and a resin composition layer having a uniform thickness and properties can be formed. It is easy to embed a wiring pattern on the substrate. As for content of a thermoplastic resin, it is more preferable that it is 0.5 mass%-5 mass% with respect to 100 mass% of non-volatile components in a resin composition layer.

  Examples of the curing accelerator include organic phosphine compounds, imidazole compounds, amine adduct compounds, and tertiary amine compounds. The content of the curing accelerator is preferably used in the range of 0.05% by mass to 3% by mass when the total amount of nonvolatile components of the epoxy resin and the curing agent is 100% by mass. A hardening accelerator may be used individually by 1 type, or may use 2 or more types together.

  Examples of the flame retardant include an organic phosphorus flame retardant, an organic nitrogen-containing phosphorus compound, a nitrogen compound, a silicone flame retardant, and a metal hydroxide. A flame retardant may be used individually by 1 type, or may use 2 or more types together. The content of the flame retardant in the resin composition layer is not particularly limited, but is preferably 0.5% by mass to 10% by mass with respect to 100% by mass of the non-volatile component in the resin composition layer, and 1% by mass to 9%. % By mass is more preferable, and 1.3% by mass to 8% by mass is even more preferable.

  As the rubber particles, for example, those that do not dissolve in the organic solvent used when forming the resin composition layer and are incompatible with the above-described epoxy resin, curing agent, thermoplastic resin, and the like are used. Such rubber particles are generally prepared by increasing the molecular weight of the rubber component to a level at which it does not dissolve in an organic solvent or resin and making it into particles.

  Examples of the rubber particles include core-shell type rubber particles, cross-linked acrylonitrile butadiene rubber particles, cross-linked 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. For example, a two-layer structure in which an outer shell layer is made of a glassy polymer and an inner core layer is made of a rubbery polymer, or Examples include a three-layer structure in which the outer shell layer is made of a glassy polymer, the intermediate layer is made of a rubbery polymer, and the core layer is made of a glassy polymer. The glassy polymer layer is made of, for example, methyl methacrylate polymer, and the rubbery polymer layer is made of, for example, butyl acrylate polymer (butyl rubber). A rubber particle may be used individually by 1 type, or may use 2 or more types together.

  The average particle size of the rubber particles is preferably in the range of 0.005 μm to 1 μm, more preferably in the range of 0.2 μm to 0.6 μm. The average particle diameter of the rubber particles can be measured using a dynamic light scattering method. For example, rubber particles are uniformly dispersed in an appropriate organic solvent by ultrasonic waves, etc., and a particle size distribution of rubber particles is created on a mass basis using a concentrated particle size analyzer (FPAR-1000; manufactured by Otsuka Electronics Co., Ltd.). And it can measure by making the median diameter into an average particle diameter. The content of the rubber particles is preferably 1% by mass to 10% by mass and more preferably 2% by mass to 5% by mass with respect to 100% by mass of the nonvolatile component in the resin composition layer.

  The resin composition layer contained in the adhesive sheet with a protective film of the present invention may contain other additives as necessary. Examples of such other additives include organic copper compounds and organic zinc. Examples include organic metal compounds such as compounds and organic cobalt compounds, and resin fillers such as organic fillers, thickeners, antifoaming agents, leveling agents, adhesion-imparting agents, colorants, and curable resins.

  The thickness of the resin composition layer is preferably 3 μm to 100 μm, more preferably 5 μm to 80 μm, and still more preferably 20 μm to 60 μm.

<Support>
A film made of a plastic material is preferably used as the support. Examples of the plastic material include polyesters such as polyethylene terephthalate (hereinafter sometimes abbreviated as “PET”) and polyethylene naphthalate (hereinafter sometimes abbreviated as “PEN”), polycarbonate (hereinafter referred to as “PET”). PC ”), acrylic such as polymethyl methacrylate (PMMA), cyclic polyolefin, triacetyl cellulose (TAC), polyether sulfide (PES), polyether ketone, polyimide and the like. Among these, polyethylene terephthalate and polyethylene naphthalate are preferable, and inexpensive polyethylene terephthalate is particularly preferable. In a preferred embodiment, the support is a polyethylene terephthalate film.

  The support may be subjected to a mat treatment or a corona treatment on the surface to be joined to the resin composition layer. Also, in order to make the support peelable after the adhesive sheet is laminated on the circuit board, a support with a release layer having a release layer on the surface to be bonded to the resin composition layer is used as the support. It is preferable to do this.

When using a support body with a release layer, in an autocutter apparatus, in the process of conveying an adhesive sheet with a protective film, peeling (floating) easily occurs between the support body and the resin composition layer. When peeling occurs, there arises a problem such that a problem of resin peeling easily occurs when the protective film is peeled off in the auto cutter device. In order to suppress such peeling between the support and the resin composition layer, the peel strength (S _A ) of the support with respect to the resin composition layer in the adhesive sheet with a protective film is preferably 0.0055 kgf / cm or more, more preferably 0.0060 kgf / cm or more, further preferably 0.0065 kgf / cm or more, particularly preferably 0.0070 kgf / cm or more, 0.0080 kgf / cm or more, 0.0090 kgf / cm or more, 0.0100 kgf. / Cm or more, 0.0110 kgf / cm or more, 0.0120 kgf / cm or more, 0.0130 kgf / cm or more, or 0.0140 kgf / cm or more. The upper limit of the peel strength is not particularly set, and it is sufficient that the support can be peeled after the adhesive sheet is laminated on the circuit board, and generally falls within the range of 0.2 kgf / cm or less. In the present invention, the peel strength (S _A ) of the support with respect to the resin composition layer is the peel strength (90 ° when the support is peeled in the direction perpendicular to the resin composition layer (90 ° direction)). Peel strength). Peel strength of support for the resin composition layer (S _A), by measuring in the tensile tester peel strength when peeled off in the vertical direction (90 ° direction) to support the resin composition layer Can be sought. Examples of the tensile tester include AC-50C-SL manufactured by TSE Corporation. The value of S _A in the present invention is a value measured according to the method described in Examples.

The release agent used for the release layer of the support with a release layer is such that the support can be peeled after the adhesive sheet is laminated on the circuit board, and the support for the resin composition layer in the adhesive sheet with a protective film is provided. There is no particular limitation as long as the peel strength (S _A ) of the body is preferable. Suitable release agents include, for example, one or more release agents selected from the group consisting of alkyd resins, polyolefin resins, and urethane resins. In addition, the silicone-based mold release agent widely used for the mold release layer is generally excellent in mold release properties, and when a mold release layer containing this as a main component is used, the resin composition layer in the adhesive sheet with a protective film is used. It may be difficult to set the peel strength (S _A ) of the support within the preferred range. However, the release property of the silicone release agent can be adjusted by blending cellulose derivatives such as methyl cellulose, ethyl cellulose, and acetyl cellulose, alkyd resins, and the like. peel strength (S _a) may be prepared release layer may be a described preferred ranges.
In addition, the thickness of the release layer in the support with a release layer is usually about 0.01 μm to 1 μm, preferably 0.01 μm to 0.2 μm.

  In the present invention, a commercially available product may be used as the support with a release layer. Commercially available products include, for example, “SK-1”, “AL-5”, and “AL-7” manufactured by Lintec Corporation, which are PET films having a release layer mainly composed of an alkyd resin release agent. Or the like.

The peel strength (S _A ) tends to increase as the thickness of the support increases. However, if the thickness of the support is too large, continuous production tends to be difficult, for example, it becomes difficult to carry by vacuum suction in the auto cutter device. Also, if the thickness of the support is too small, the peel strength tends to be too small, and the adhesive sheet temporarily attached to the surface of the circuit board is rolled up (curled), resulting in continuous production. Tend to be difficult. Therefore, in the present invention, the thickness of the support is preferably in the range of 5 μm to 75 μm, more preferably in the range of 10 μm to 60 μm, further preferably in the range of 20 μm to 50 μm, still more preferably in the range of 20 μm to 45 μm, and even more preferably in the range of 23 μm to A range of 40 μm is particularly preferred. In addition, the thickness of the support body in this invention is the thickness of the whole support body with a release layer, when a support body is a support body with a release layer.

<Protective film>
The protective film has advantages such as protecting the surface of the resin composition layer from physical damage when the adhesive sheet is set in the auto cutter device, and preventing foreign matter such as dust from adhering. Examples of the material for the protective film include polyolefins such as polyethylene, polypropylene, and polyvinyl chloride, polyesters such as PET and PEN, polycarbonate (PC), and polyimide. In a preferred embodiment, the protective film includes one or more materials selected from the group consisting of polyethylene, polypropylene, and polyethylene terephthalate.

Similarly to the support, the protective film may be subjected to mat treatment or corona treatment on the surface to be bonded to the resin composition layer. Moreover, the protective film may have a release layer on the surface on the side to be bonded to the resin composition layer. Peel strength of the protective film to the resin composition layer _{(S B)} is not particularly limited as long as it satisfies the _{S A -S B ≧ 0.0020 [kgf} / cm] in relation to the peel strength _{S A,} practical point of view Therefore, 0.0080 kgf / cm or less is preferable, 0.0070 kgf / cm or less is more preferable, 0.0060 kgf / cm or less is more preferable, 0.0050 kgf / cm or less is more preferable, and 0.0040 kgf / cm or less is particularly preferable. preferable. The lower limit of the peel strength is not particularly set, and it is sufficient that the adhesive sheet is in close contact to protect the adhesive sheet, and generally falls within the range of 0.0010 kgf / cm or more. In the present invention, the peel strength (S _B ) of the protective film with respect to the resin composition layer is the peel strength (90 ° when the protective film is peeled in the direction perpendicular to the resin composition layer (90 ° direction)). Peel strength). Peel strength of the protective film to the resin composition layer (S _B) by measuring in the tensile tester peel strength when peeled off in the vertical direction (90 ° direction) a protective film on the resin composition layer Can be sought. The tensile tester, similarly to the measurement of _{S A,} for example, (Corporation) AC-50C-SL, etc. manufactured by TSE and the like. The value of S _B in the present invention is a value measured according to the method described in Examples.

  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.

In the adhesive sheet with a protective film of the present invention, from the viewpoint of preventing resin peeling at the time of peeling of the protective film in the auto cutter device, the peeling strength (S _A ) of the support with respect to the resin composition and the protective film against the resin composition layer It is important that the peel strength (S _B ) satisfies S _A −S _B ≧ 0.0020 [kgf / cm]. From the viewpoint of preventing the problem of resin peeling even under conditions where the conveying speed of the adhesive sheet with a protective film in the auto cutter device is high, the peel strength (S _A ) of the support with respect to the resin composition layer and the protection against the resin composition layer The peel strength (S _B ) of the film more preferably satisfies S _A −S _B ≧ 0.0022 [kgf / cm], and S _A −S _B ≧ 0.0025 [kgf / cm], S _A − S _B ≧ 0.0030 [kgf / cm], S _A −S _B ≧ 0.0035 [kgf / cm], S _A −S _B ≧ 0.0040 [kgf / cm], S _A −S _B ≧ 0. 0045 [kgf / cm], S _A -S _B ≧ 0.0050 [kgf / cm], S _A -S _B ≧ 0.0055 [kgf / cm], or S _A -S _B ≧ 0.0060 [kgf / cm] cm] Are more preferable. The upper limit of S _A -S _B is not particularly set, but generally ranges such as S _A -S _B ≦ 0.20 [kgf / cm], S _A -S _B ≦ 0.020 [kgf / cm], etc. Will fit in.

In the adhesive sheet with a protective film of the present invention, the thickness of each of the support and the protective film is preferably in the range of 5 μm to 75 μm as described above. From the viewpoint of setting the difference (S _A -S _B ) between the peel strength (S _A ) of the support with respect to the resin composition layer and the peel strength (S _B ) of the protective film with respect to the resin composition layer, the protective film is It is preferably thinner than the support. The thickness of the support and _{D A,} when the thickness of the protective film and _{D B,} the ratio of D B / _{D A} is preferably less than 1, more preferably 0.9 or less, more preferably 0.8 or less, 0.7 or less is particularly preferable.

The adhesive sheet with a protective film of the present invention can be produced, for example, by a production method including the following steps (1) and (2).
(1) A step of forming an adhesive sheet by providing a resin composition layer so as to be bonded to a support,
(2) The process of providing a protective film so that it may join with the resin composition layer of the adhesive sheet obtained by said (1).

  In the step (1), the resin composition layer can be provided by a known method so as to be bonded to the support. For example, preparing a resin varnish in which a resin composition is dissolved in a solvent, applying the resin varnish to a support surface using a coating device such as a die coater, and drying the resin varnish to provide a resin composition layer Can do.

  Solvents used for preparing the resin varnish include, for example, ketones such as acetone, methyl ethyl ketone and cyclohexanone, acetates such as ethyl acetate, butyl acetate, cellosolve acetate, propylene glycol monomethyl ether acetate and carbitol acetate, cellosolve and butylcarbi Examples thereof include carbitols such as Tol, aromatic hydrocarbons such as toluene and xylene, amide solvents such as dimethylformamide, dimethylacetamide and N-methylpyrrolidone. A solvent may be used individually by 1 type or may use 2 or more types together.

The resin varnish may be dried by a known drying method such as heating or hot air blowing. If a large amount of solvent remains in the resin composition layer, it may cause swelling after curing. Therefore, the resin composition layer is dried so that the amount of residual solvent in the resin composition is usually 10% by mass or less, preferably 5% by mass or less. .
From the viewpoint of setting the difference (S _A -S _B ) between the peel strength (S _A ) of the support with respect to the resin composition layer and the peel strength (S _B ) of the protective film with respect to the resin composition layer to a specific range, the resin composition The amount of residual solvent is more preferably in the range of 0.2% by mass to 5% by mass, further preferably in the range of 0.5% by mass to 4.5% by mass, particularly preferably 1.6% by mass to 4.% by mass. Dry to a range of 0% by mass.

  The drying conditions of the resin varnish affect the minimum melt viscosity temperature of the formed resin composition layer. Depending on the composition of the resin composition, in one embodiment, the minimum melt viscosity temperature of the resin composition layer is preferably in the range of 60 ° C to 170 ° C, more preferably in the range of 70 ° C to 160 ° C, and still more preferably. Is dried so as to be in the range of 80 ° C to 150 ° C. Here, the “minimum melt viscosity temperature” of the resin composition layer refers to a temperature at which the resin composition layer exhibits the minimum melt viscosity. The “minimum melt viscosity” of the resin composition layer refers to the lowest viscosity exhibited by the resin composition layer when the resin of the resin composition layer is melted. Specifically, when the resin composition layer is heated at a constant temperature increase rate to melt the resin, the initial stage of the melt viscosity decreases with increasing temperature, and then, when the temperature exceeds a certain temperature, the melt viscosity decreases with increasing temperature. The “minimum melt viscosity” refers to the melt viscosity at such a minimum point. The minimum melt viscosity temperature of the resin composition layer can be measured by a dynamic viscoelastic method. Specifically, the minimum melt viscosity temperature of the resin composition layer is obtained by performing dynamic viscoelasticity measurement under the conditions of a measurement start temperature of 60 ° C., a heating rate of 5 ° C./min, a frequency of 1 Hz, and a strain of 1 deg. Can do. Examples of the dynamic viscoelasticity measuring apparatus include “Rheosol-G3000” manufactured by UBM Co., Ltd.

  Depending on the type of solvent and the composition of the resin composition, the temperature is preferably 50 ° C. to 150 ° C. for 3 minutes to 10 minutes, more preferably 65 ° C. to 140 ° C. for 3 minutes to 10 minutes. The resin composition layer can be formed by drying the resin varnish for 3 minutes to 8 minutes at a temperature of 70 ° C. to 120 ° C. for 3 minutes to 8 minutes. In addition, as long as said residual solvent amount and / or minimum melt viscosity temperature can be achieved, you may employ | adopt drying temperature and drying time different from the said range.

  In the step (2), a protective film is provided so as to be bonded to the resin composition layer of the adhesive sheet obtained in the step (1).

Peel strength of the support and the protective film (S _A and S _B) from easily viewpoint protective film with adhesive sheet was obtained in the desired range for the resin composition layer, in the step (2), roll or press bonding, etc. It is preferable to laminate the protective film on the resin composition layer of the adhesive sheet.

In the laminating process in the step (2), the pressure is usually in the range of 0.02 kgf / cm ^{2 to} 11 kgf / cm ² (0.196 × 10 ⁴ N / m ^{2 to} 107.9 × 10 ⁴ N / m ² ). Preferably in the range of 0.03 kgf / cm ^{2 to 5} kgf / cm ² (0.294 × 10 ⁴ N / m ^{2 to} 78.4 × 10 ⁴ N / m ² ), more preferably 0.04 kgf / cm in the range of ^{2 ~2kgf / cm 2 (0.392 ×} 10 4 N / m 2 ~49 × 10 4 N / m 2).

In producing an adhesive sheet with a protective film in which the peel strength (S _A and S _B ) of the support and the protective film with respect to the resin composition layer is in a desired range, [minimum melt viscosity temperature of the resin composition layer −10 ° C.] It is preferable to implement a process (2) on the following temperature conditions. From the viewpoint of obtaining sufficient adhesion between the support or the protective film and the resin composition layer, and preventing the resin from peeling when the protective film is peeled off in the auto cutter device, the step (2) is [minimum of the resin composition layer]. More preferably, it is carried out under the following temperature conditions: [Minimum Melt Viscosity Temperature of Resin Composition Layer—80 ° C.] to [Minimum Melt Viscosity Temperature of Resin Composition Layer—30 ° C.] More preferably, it is carried out under a temperature condition within the range, and is carried out under a temperature condition ranging from [minimum melt viscosity temperature of the resin composition layer−55 ° C.] to [minimum melt viscosity temperature of the resin composition layer−30 ° C.]. It is particularly preferable to do this.

Depending on the composition of the resin composition layer, from the viewpoint of peel strength of the support and the protective film to the resin composition layer (S _A and S _B) to produce a adhesive sheet with protective films in the desired range,
In step (1), the resin varnish is adjusted so that the amount of residual solvent in the resin composition is in the range of 0.2% by mass to 5% by mass and the minimum melt viscosity temperature of the resin composition layer is in the range of 60 ° C to 170 ° C. Is dried to form a resin composition layer, and in the step (2), the [minimum melt viscosity temperature of the resin composition layer −80 ° C.] to the [minimum melt viscosity temperature of the resin composition layer −10 ° C.]. Resin composition under conditions of pressure bonding pressure of 0.02 kgf / cm ^{2 to} 11 kgf / cm ² (0.196 × 10 ⁴ N / m ^{2 to} 107.9 × 10 ⁴ N / m ² ) at a temperature in the range. It is preferable to provide a protective film so as to join the physical layer,
In step (1), the amount of residual solvent in the resin composition is in the range of 0.5 mass% to 4.5 mass%, and the minimum melt viscosity temperature of the resin composition layer is in the range of 70 ° C. to 160 ° C. The resin varnish is dried to form a resin composition layer, and in the step (2), [minimum melt viscosity temperature of the resin composition layer −55 ° C.] to [minimum melt viscosity temperature of the resin composition layer −20 ° C. ] At a temperature in the range of 0.04 kgf / cm ^{2 to 2} kgf / cm ² (0.392 × 10 ⁴ N / m ² to 49 × 10 ⁴ N / m ² ), and the resin composition. It is more preferable to provide a protective film so as to be bonded to the physical layer.

A roll-shaped adhesive sheet with a protective film can be manufactured by winding the obtained adhesive sheet with a protective film into a roll after the step (2). A roll-shaped adhesive sheet with a protective film can be used for the manufacturing method of the laminated body and printed wiring board which are mentioned later. In addition, in a roll-shaped adhesive sheet with a protective film, the longitudinal direction corresponds to the MD direction in the manufacturing method of the laminated body and printed wiring board mentioned later. Therefore, in the roll-shaped adhesive sheet with a protective film, it is preferable that at least the peel strength in the longitudinal direction satisfies the relationship of the above S _A and S _B.

  The manufacturing method of said adhesive film with a protective film is after conveying a support body from the support body wound up by roll shape, and forming a resin composition layer on a support body by application | coating and drying of a resin varnish. By providing a protective film (a protective film wound in a roll shape can be used) so as to be joined to the resin composition layer, it can be carried out continuously.

  Since the adhesive sheet with a protective film of the present invention does not cause the resin peeling at the time of peeling the protective film in the auto cutter device, it becomes possible to produce a printed wiring board that does not cause a problem of circuit distortion at a high production rate. It is suitable as an adhesive sheet with a protective film for a buildup layer of a printed wiring board.

[Manufacturing Method of Laminate with Cut Adhesive Sheet on Surface of Circuit Board]
Using the adhesive sheet with a roll-shaped protective film of the present invention, a laminate in which the cut adhesive sheet is provided on the surface of the circuit board (hereinafter also simply referred to as “laminate”) can be continuously produced. it can.

That is, the manufacturing method of the laminated body of this invention includes the following process (a-1) thru | or (a-4).
(A-1) The process of peeling a protective film, conveying an adhesive sheet with a protective film from the adhesive sheet with a roll-shaped protective film of this invention,
(A-2) a step of arranging the adhesive sheet from which the resin composition layer is exposed so that the resin composition layer is bonded to the circuit board;
(A-3) a step of partially bonding the adhesive sheet to the circuit board by heating and pressing a part of the adhesive sheet from the support side, and (a-4) a cutter according to the size of the circuit board. The process of providing the cut adhesive sheet on the surface of the circuit board by cutting with

  The manufacturing method of the laminated body of this invention can be implemented using an auto cutter apparatus. Hereinafter, an embodiment of the method for producing a laminate of the present invention will be described with reference to FIG.

  First, the adhesive sheet 11 with a roll-shaped protective film slit in advance in the width of the circuit board 6 is set in the auto cutter device 10. FIG. 2 shows an embodiment in which the adhesive sheet 4 is provided on one side (the upper surface in FIG. 2) of the circuit board 6, and one adhesive sheet 11 with a roll-shaped protective film is set above the circuit board 6. In the following, an embodiment in which the adhesive sheet 4 is provided on one side of the circuit board 6 will be described based on the description of FIG. 2, but one adhesive sheet 11 with a roll-shaped protective film is also provided below the circuit board 6. Further, the adhesive sheet 4 may be provided on both sides of the circuit board 6 by setting.

  In the step (a-1), the protective film 5 is peeled while the adhesive sheet 1 with a protective film is conveyed from the adhesive sheet 11 with a roll-shaped protective film of the present invention.

  For example, the protective film 5 can be peeled from the adhesive sheet 4 when the adhesive sheet with protective film 1 passes through the protective film take-out tool 13. The peeled protective film 5 can be collected by the protective film take-up roll 12. The shape and mechanism of the protective film take-out tool 13 are not particularly limited as long as the adhesive sheet with a protective film of the present invention is used, but are generally cylindrical or prismatic. In addition, as shown in FIG. 2, a shape and mechanism that allows the protective film 5 to be taken out in a direction substantially perpendicular to the conveying direction of the adhesive sheet 1 with the protective film (that is, 90 ± 45 degrees direction with respect to the conveying direction). When it is, it can peel more easily. In a preferred embodiment, the protective film removal tool 13 has a prismatic shape with a protective film removal angle of 90 ± 45 degrees.

  The adhesive sheet 4 from which the protective film 5 is peeled and the resin composition layer is exposed is conveyed to the circuit board 6.

  The conveyance speed of the adhesive sheet with a protective film 11 (or adhesive sheet 4) in the step (a-1) is not particularly limited as long as the adhesive sheet with a protective film of the present invention is used. From the viewpoint of contributing to an improvement in the production speed of the printed wiring board, the transport speed is preferably 1 m / min or more.

  The adhesive sheet with a protective film of the present invention does not cause the resin to peel off when the protective film is peeled off even under a high conveying speed. Therefore, the conveyance speed may be 2 m / min or more, 3 m / min or more, 4 m / min or more, or 5 m / min or more.

  In the present invention, the transport speed of the protective film-attached adhesive sheet 11 (or adhesive sheet 4) in the step (a-1) is selected in the range of 1 m / min to 20 m / min according to the subsequent process speed. can do. Thus, the present invention significantly contributes to the production speed of the printed wiring board.

  In addition, the conveyance means of the adhesive sheet 11 with a protective film (or adhesive sheet 4) in the step (a-1) is not particularly limited. For example, after fixing the adhesive sheet by suction from the support side by vacuum suction, Can be done automatically.

  In the step (a-2), the adhesive sheet 4 from which the resin composition layer is exposed is disposed so that the resin composition layer is bonded to the circuit board 6. For example, the adhesive sheet 4 can be aligned by the guide rolls 16 and 17 with respect to the circuit board 6 conveyed by the conveyor device 15.

  In the present invention, the “circuit board” is mainly patterned on one or both sides of a substrate such as a glass epoxy substrate, a metal substrate, a polyester substrate, a polyimide substrate, a BT resin substrate, and a thermosetting polyphenylene ether substrate. This means that a conductor layer (circuit) is formed. Further, when the printed wiring board is manufactured, an inner layer circuit board of an intermediate product on which an insulating layer and / or a conductor layer is to be formed is also included in the “circuit board” in the present invention.

  In the step (a-3), the adhesive sheet 4 is partially bonded to the circuit board 6 by partially heating and pressing a part of the adhesive sheet 4 from the support side.

  For example, a part of the adhesive sheet 4 in an unnecessary part that does not overlap with a circuit that requires a lamination process among a part in the front in the feeding direction of the circuit board 6 (a part on the right side of the circuit board 6 in FIG. 2). The adhesive sheet 4 can be partially bonded to the circuit board 6 by heating and pressurizing from the support side by the contact heater device 18 or the like.

Although depending on the resin composition used for the resin composition layer and its melt viscosity characteristics, the temperature is usually 60 ° C. to 130 ° C. (preferably 60 ° C. to 120 ° C.) for 1 second to 20 seconds (preferably 5 seconds). The adhesive sheet 4 is partially bonded to the circuit board 6 for about 15 seconds). The pressure during pressure bonding is preferably in the range of 0.02 kgf / cm ^{2 to} 0.25 kgf / cm ² (0.196 N / m ^{2 to} 2.45 N / m ² ), more preferably 0.05 kgf / cm ^{2 to} 0. .20 kgf / cm ² (0.49 N / m ^{2 to} 1.96 N / m ² ).

  In the step (a-4), the adhesive sheet 4 is cut with a cutter 14 in accordance with the size of the circuit board 6 to provide the cut adhesive sheet on the surface of the circuit board.

  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 occurrence of cutting residue (resin chips) of the resin composition.

  All the above steps (a-1) to (a-4) can be carried out continuously in the auto cutter device. Examples of commercially available autocutter devices include dry film laminator Mach series manufactured by Hakuto Co., Ltd., Shinei Kiko Co., Ltd. autocutter FAC500, SAC-500 / 600, and the like.

  The laminate manufactured by the method of the present invention is a laminate in which the cut adhesive sheet is provided on the surface of the circuit board, and this is a laminate in which the cut adhesive sheet is temporarily attached to the surface of the circuit board. Is the body.

[Method of manufacturing printed wiring board]
A printed wiring board can be manufactured using the laminate obtained by the above and having the cut adhesive sheet provided on the surface of the circuit board.

The method for producing a printed wiring board of the present invention includes the following steps (b-1) and (b-2).
(B-1) heating and pressurizing the laminate produced by the method of the present invention, and laminating an adhesive sheet on the circuit board; and (b-2) thermosetting the resin composition layer to form an insulating layer. Forming process

  Step (b-1) is a step of heating and pressing the laminate produced by the method of the present invention and laminating an adhesive sheet on the circuit board. In this step (b-1), the entire adhesive sheet is laminated on the surface of the circuit board.

  The laminated body can be heated and pressurized by, for example, pressing a heated metal plate such as a SUS mirror plate from the support side. In this case, it is preferable not to press the metal plate directly, but to press through an elastic material such as heat-resistant rubber so that the adhesive sheet sufficiently follows the circuit irregularities of the circuit board.

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

  In the step (b-1), the laminate is preferably heated and pressurized under a reduced pressure of 20 mmHg (26.7 hPa) or less.

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

  The laminating process (and the smoothing process) can be continuously performed using a commercially available vacuum laminator. Examples of the commercially available vacuum laminator include a vacuum pressure laminator manufactured by Meiki Seisakusho, a vacuum applicator manufactured by Nichigo Morton, and the like.

  After the laminating process (and smoothing process), the support is peeled off to expose the resin composition layer. Or you may implement peeling of a support body after a process (b-2). The support may be peeled off manually or mechanically by an automatic peeling device.

  In the step (b-2), the resin composition layer is thermoset to form an insulating layer.

  The thermosetting conditions of the resin composition layer in the step (b-2) vary depending on the type of the resin composition, but generally the curing temperature is in the range of 170 ° C. to 190 ° C., and the curing time is in the range of 15 minutes to 60 minutes. It can be.

  The method for producing a printed wiring board of the present invention includes a drilling step for drilling an insulating layer, a roughening step for roughening the insulating layer, a plating step for forming a conductor layer by plating on the surface of the roughened insulating layer, and A circuit forming step of forming a circuit on the conductor layer may be further included. These steps can be performed according to various methods used for manufacturing a printed wiring board, which are known to those skilled in the art.

  EXAMPLES The present invention will be specifically described below with reference to examples, but the present invention is not limited to these examples.

First, various measurement methods and evaluation methods will be described.

<Measurement of peel strength>
(1) Measurement of peel strength (S _A ) of support for resin composition layer 30 mm wide and 100 mm long adhesive sheet with roll-shaped protective film produced in Examples and Comparative Examples is vertically long in the longitudinal direction. Then, the protective film was peeled off to obtain a measurement sample. A high-end thick paper (stock) with a 25 mm wide and 95 mm long double-sided tape (“Nystack” manufactured by Nichiban Co., Ltd.) attached to the surface of the obtained resin composition layer side and cut to a width of 27 mm and a length of 100 mm It was adhered to “Kona Snow 210 (super-thick)” manufactured by JITTA. Gripping in the jaws peel off the end of the support was measured a load at the time of peeling off the 30mm support vertically at room temperature (23 ° C.) under, 50 mm / min to determine the peel strength S _A . For the measurement, a tensile testing machine (“AC-50C-SL” manufactured by TSE Co., Ltd.) was used.

(2) Measurement of peel strength (S _B ) of protective film for resin composition layer 30 mm width and length of adhesive sheet with roll-shaped protective film produced in Examples and Comparative Examples so as to be vertically long in the longitudinal direction Cut to 100 mm to obtain a measurement sample. A high-end cardboard paper (manufactured by JITTA CORPORATION) with a double-sided tape having a width of 25 mm and a length of 95 mm (“Nystack” manufactured by Nichiban Co., Ltd.) attached to the surface of the support of the obtained sample and cut to a width of 27 mm and a length of 100 mm "Kona snow 210 (super-thick)"). Grasp one end of the peeled jaws of the protective film to measure the load when peeling off 30mm pull the protective film in the vertical direction at room temperature (23 ° C.) under, 50 mm / min to determine the peel strength S _B. For the measurement, a tensile tester (“AC-50C-SL” manufactured by TSE Co., Ltd.) was used.

<Evaluation of resin peeling at the time of protective film peeling in an auto cutter device>
The adhesive sheet with a roll-shaped protective film produced in Examples and Comparative Examples was set in an auto cutter device (manufactured by Shinei Kiko Co., Ltd., “SAC-500”). In this evaluation, the adhesive sheet with a roll-shaped protective film was set one by one on the upper and lower sides of the circuit board.
The protective film was peeled off from the adhesive sheet with a roll-shaped protective film while conveying the adhesive sheet with a protective film at a conveyance speed of 5 m / min. 30 sheets of the adhesive sheet with the resin composition layer exposed are continuously provided on both surfaces of the inner circuit board so that the resin composition layer is bonded to the inner circuit board (510 × 340 mm size, 0.6 mm thickness) ( Temporary attachment was performed (per one side) (conveying speed of the inner layer circuit board at the time of temporary attachment 2 m / min, temporary attachment temperature 100 ° C., temporary attachment time 10 seconds, temporary attachment pressure 0.15 kgf / cm ² ).
The state at the time of temporary attachment was observed, and according to the following evaluation criteria, evaluation of resin peeling at the time of peeling the protective film was performed.
Evaluation criteria:
○: No abnormality (no resin peeling)
×: Resin peeling

<Measurement of minimum melt viscosity temperature of resin composition layer>
The minimum melt viscosity temperature of the resin composition layer in the adhesive sheet with a roll-shaped protective film manufactured in Examples and Comparative Examples is a dynamic viscoelasticity measuring device ("Reosol-G3000" manufactured by UBM Co., Ltd.). ). About 1 g of the sample resin composition, using a parallel plate with a diameter of 18 mm, the temperature was raised from a starting temperature of 60 ° C. to 200 ° C. at a heating rate of 5 ° C./minute, a measurement temperature interval of 2.5 ° C., a frequency of 1 Hz, The temperature at the lowest melt viscosity was measured under the condition of strain of 1 deg.

<Example 1>
An adhesive sheet with a roll-shaped protective film was produced according to the following method.

(Preparation of resin varnish)
6 parts by mass of naphthalene type epoxy resin (epoxy equivalent 144, “EXA4032SS” manufactured by DIC Corporation), 12 parts by mass of bixylenol type epoxy resin (epoxy equivalent 190, “YX4000HK” manufactured by Mitsubishi Chemical Corporation), and biphenyl type epoxy 9 parts by mass of a resin (epoxy equivalent of about 290, “NC3000H” manufactured by Nippon Kayaku Co., Ltd.) was dissolved in a mixed solvent of 4 parts by mass of methyl ethyl ketone (MEK) and 25 parts by mass of solvent naphtha with stirring. 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, 65% by mass of a non-volatile component in toluene), phenoxy resin ( Weight average molecular weight 35000, Mitsubishi Chemical Corporation “YL7553BH30”, 5 parts by mass of MEK solution having a solid content of 30% by mass, 5 parts by mass of 5% by mass of 4-dimethylaminopyridine as a curing accelerator, and phenyl Spherical silica surface-treated with aminosilane (manufactured by Shin-Etsu Chemical Co., Ltd., “KBM573”) (“SC2500SQ” manufactured by Admatechs Co., Ltd.), average particle size 0.5 μm, carbon amount per unit area 0.39 mg / m ² ) 160 parts by mass was mixed and uniformly dispersed with a high-speed rotary mixer to prepare a resin varnish.

(Preparation of adhesive sheet)
A polyethylene terephthalate film (thickness: 38 μm, manufactured by Lintec Corporation, “AL5”) with an alkyd resin release layer was prepared as a support. The resin varnish obtained above is uniformly applied to the release layer side surface of the support with a die coater and dried at 80 ° C. to 105 ° C. (average 90 ° C.) for 4.5 minutes to obtain a resin composition layer Formed. The resin composition layer had a thickness of 30 μm, a residual solvent amount of 2.5 mass%, and a minimum melt viscosity temperature of 115 ° C.

(Manufacture of adhesive sheet with roll-shaped protective film)
A polypropylene film (manufactured by Oji Specialty Paper Co., Ltd., “Alphan MA-411”, smooth surface side, thickness 15 μm) as a protective film on the resin composition layer side surface of the adhesive sheet obtained above, under normal pressure, 60 Lamination was performed at 0 ° C. and 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 two adhesive sheets with a roll-shaped protective film.

The obtained adhesive sheet with a roll protective film, as well as measuring the peel strength of the support and the protective film to the resin composition layer (S _A and S _B), the peeling resin during protective film peeling in the automatic cutting device evaluation did. The results are shown in Table 1.

<Example 2>
In the same manner as in Example 1, except that a polyethylene terephthalate film with a alkyd resin release layer (thickness 25 μm, manufactured by Lintec Corporation, “AL5”) was used as the protective film instead of the polypropylene film, roll-shaped protection Two adhesive sheets with a film were obtained.
The obtained adhesive sheet with a roll protective film, as well as measuring the peel strength of the support and the protective film to the resin composition layer (S _A and S _B), the peeling resin during protective film peeling in the automatic cutting device evaluation did. The results are shown in Table 1.

<Example 3>
An adhesive sheet with a roll-shaped protective film was produced according to the following method.

(Preparation of resin varnish)
5 parts of bisphenol type epoxy resin (epoxy equivalent of about 165, “ZX1059” manufactured by Nippon Steel Chemical Co., Ltd., 1: 1 mixture of bisphenol A type and bisphenol F type), bixylenol type epoxy resin (epoxy equivalent of about 190, 10 parts "YX4000HK" manufactured by Mitsubishi Chemical Corporation, 10 parts biphenyl type epoxy resin (epoxy equivalent of about 290, "NC3000H" manufactured by Nippon Kayaku Co., Ltd.), and phenoxy resin (weight average molecular weight 35000, Mitsubishi Chemical Corporation) ) 10 parts of “YL7553BH30” manufactured by MEK solution having a solid content of 30% by mass was dissolved in 30 parts of solvent naphtha with stirring. After cooling to room temperature, 10 parts of an active ester compound (active group equivalent: about 223, “HPC-8000-65T” manufactured by DIC Corporation, toluene solution with a nonvolatile content of 65% by mass), triazine-containing cresol-based curing 10 parts of an agent (hydroxyl equivalent 151, “LA-3018-50P” manufactured by DIC Corporation, methoxypropanol solution having a solid content of 50% by mass), curing accelerator (4-dimethylaminopyridine, MEK solution having a solid content of 2% by mass) ) 3.5 parts, flame retardant (“HCA-HQ” manufactured by Sanko Co., Ltd., 10- (2,5-dihydroxyphenyl) -10-hydro-9-oxa-10-phosphaphenanthrene-10-oxide , 2 parts of average particle size), spherical silica (ADMATEX Co., Ltd.) surface-treated with phenylaminosilane (“KBM573” manufactured by Shin-Etsu Chemical Co., Ltd.) "SOC1", average particle size 0.24 .mu.m, carbon amount per unit area 0.36mg ^/ m 2) 110 parts, were mixed and uniformly dispersed in a high-speed rotary mixer to prepare a resin varnish.

(Preparation of adhesive sheet)
A polyethylene terephthalate film (thickness: 38 μm, manufactured by Lintec Corporation, “AL5”) with an alkyd resin release layer was prepared as a support. The resin varnish obtained above is uniformly applied to the release layer side surface of the support with a die coater and dried at 80 ° C. to 110 ° C. (average 95 ° C.) for 4 minutes to form a resin composition layer. did. The resin composition layer had a thickness of 30 μm, a residual solvent amount of 2.9% by mass, and a minimum melt viscosity temperature of 119 ° C.

(Manufacture of adhesive sheet with roll-shaped protective film)
Using the adhesive sheet obtained above, two adhesive sheets with a roll-shaped protective film were obtained in the same manner as in Example 1.

The obtained adhesive sheet with a roll protective film, as well as measuring the peel strength of the support and the protective film to the resin composition layer (S _A and S _B), the peeling resin during protective film peeling in the automatic cutting device evaluation did. The results are shown in Table 1.

<Comparative Example 1>
The resin varnish was dried at 80 ° C. to 110 ° C. (average 95 ° C.) for 5.5 minutes to obtain a resin composition layer having a thickness of 30 μm, a residual solvent amount of 1.5% by mass, and a minimum melt viscosity temperature of 130 ° C. In addition, two adhesive sheets with a roll-shaped protective film were obtained in the same manner as in Example 1 except that the protective film was laminated at a temperature of 70 ° C.
The obtained adhesive sheet with a roll protective film, as well as measuring the peel strength of the support and the protective film to the resin composition layer (S _A and S _B), the peeling resin during protective film peeling in the automatic cutting device evaluation did. The results are shown in Table 1.

<Comparative example 2>
In the same manner as in Example 1, except that a polyethylene terephthalate film with a alkyd resin release layer (thickness 38 μm, manufactured by Lintec Corporation, “AL5”) was used as the protective film instead of the polypropylene film, roll-shaped protection Two adhesive sheets with a film were obtained.
The obtained adhesive sheet with a roll protective film, as well as measuring the peel strength of the support and the protective film to the resin composition layer (S _A and S _B), the peeling resin during protective film peeling in the automatic cutting device evaluation did. The results are shown in Table 1.

The peel strength (S _A ) of the support with respect to the resin composition layer and the peel strength (S _B ) of the protective film with respect to the resin composition layer do not satisfy S _A −S _B ≧ 0.0020 [kgf / cm]. As for the adhesive sheet with a protective film of Comparative Examples 1 and 2, resin peeling occurred when the protective film was peeled off in the auto cutter device. On the other hand, the adhesive sheet with a protective film of Examples 1, 2, and 3 satisfying S _A -S _B ≧ 0.0020 [kgf / cm] is a protective film even under conditions where the conveyance speed of the adhesive sheet is as high as 5 m / min. No resin peeling occurred during peeling.

DESCRIPTION OF SYMBOLS 1 Adhesive sheet with protective film 2 Support body 3 Resin composition layer 4 Adhesive sheet 5 Protective film 6 Circuit board 10 Auto cutter device 11 Adhesive sheet with roll-shaped protective film 12 Protective film take-up roll 13 Protective film take-out tool 14 Cutter 15 Conveyor Device 16, 17 Induction roll 18 Contact heater

Claims (12)

An adhesive sheet comprising a support and a resin composition layer bonded to the support, and a protective film provided so as to be bonded to the resin composition layer of the adhesive sheet . It is an adhesive sheet with a protective film for a build-up layer of a printed wiring board for peeling ,
The resin composition layer includes an inorganic filler and a thermosetting resin,
The content of the inorganic filler in the resin composition layer is 60% by mass or more when the nonvolatile component in the resin composition layer is 100% by mass,
The peel strength (S _A ) of the support with respect to the resin composition layer and the peel strength (S _B ) of the protective film with respect to the resin composition layer satisfy S _A −S _B ≧ 0.0020 [kgf / cm] , S _B is equal to or less than 0.0010kgf / cm or more 0.0080kgf / cm,
The support has a release layer on the surface on the side bonded to the resin composition layer,
An adhesive sheet with a protective film in which the protective film is thinner than the support. The adhesive sheet with a protective film according to claim 1, wherein S _A −S _B ≧ 0.0022 [kgf / cm] .   The adhesive sheet with a protective film according to claim 1 or 2, wherein each thickness of the support and the protective film is 5 µm to 75 µm.   The adhesive sheet with a protective film according to any one of claims 1 to 3, wherein the support is a polyethylene terephthalate film.   The adhesive sheet with a protective film according to any one of claims 1 to 4, wherein the release layer contains one or more release agents selected from the group consisting of alkyd resins, polyolefin resins, and urethane resins.   The adhesive sheet with a protective film according to any one of claims 1 to 5, wherein the protective film contains one or more materials selected from the group consisting of polyethylene, polypropylene, and polyethylene terephthalate. The adhesive sheet with a roll-shaped protective film by which the adhesive sheet with a protective film of any one of Claims 1-6 was wound up in roll shape. S _A and S _B are the peel strength in the longitudinal direction, the rolled protective film with adhesive sheet according to claim 7. The manufacturing method of the adhesive sheet with a protective film of any one of Claims 1-6 including following process (1) and (2).
(1) a step of forming an adhesive sheet by providing a resin composition layer so as to be bonded to a support;
(2) A step of providing a protective film under the temperature condition of [(minimum melt viscosity temperature of the resin composition layer) −10 ° C.] so as to be bonded to the resin composition layer of the adhesive sheet obtained in (1) above. The manufacturing method of the laminated body in which the cut adhesive sheet was provided in the surface of the circuit board including the following process (a-1) thru | or (a-4).
(A-1) The process of peeling a protective film, conveying an adhesive sheet with a protective film from the adhesive sheet with a roll-shaped protective film of Claim 7 or 8 ,
(A-2) a step of arranging the adhesive sheet from which the resin composition layer is exposed so that the resin composition layer is bonded to the circuit board;
(A-3) a step of partially bonding the adhesive sheet to the circuit board by heating and pressing a part of the adhesive sheet from the support side, and (a-4) a cutter according to the size of the circuit board. The process of providing the cut adhesive sheet on the surface of the circuit board by cutting with The method of Claim 10 that the conveyance speed in a process (a-1) is 1 m / min-20 m / min. The manufacturing method of a printed wiring board including the following process (b-1) and (b-2).
(B-1) heating and pressing the laminate produced by the method of claim 10 or 11 , laminating an adhesive sheet on the circuit board, and (b-2) thermosetting the resin composition layer, Step of forming an insulating layer

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