JP6852332B2 - Adhesive film - Google Patents

Description

The present invention relates to an adhesive film. Further, the present invention relates to a method for manufacturing a wiring board using an adhesive film, a wiring board, and a semiconductor device.

As a method for manufacturing a wiring board (printed wiring board), a build-up method in which circuit-formed conductor layers and insulating layers are alternately stacked is widely used, and the insulating layer is formed by curing a resin composition. (See, for example, Patent Document 1).

Japanese Unexamined Patent Publication No. 2015-82535

In recent years, electronic devices have been made lighter, thinner, shorter and smaller. Along with this, there is a demand for a flexible wiring board that can be bent and stored in an electronic device. Further, in order to make the wiring board thinner, there is a demand for a wiring board provided with an embedded wiring layer.

As an insulating layer used for a wiring board provided with an embedded wiring layer, the mismatch of the average linear thermal expansion coefficient (CTE, also referred to as the coefficient of thermal expansion) between the wiring layer and parts is reduced. Therefore, a hard material with a high filling of an inorganic filler has been used. However, there is a problem that warpage occurs when manufacturing a wiring board provided with an embedded wiring layer.

Further, as an insulating layer used for a wiring board provided with an embedded wiring layer, the use of a material in which a flexible resin is highly filled with an inorganic filler has been considered in order to reduce the average coefficient of linear thermal expansion. However, there is a problem that cracks occur when manufacturing a wiring board provided with an embedded wiring layer.

An object of the present invention has been made to solve the above problems, and an adhesive film capable of forming an insulating layer that does not warp or crack when manufacturing a wiring board provided with an embedded wiring layer. An object of the present invention is to provide a method for manufacturing a wiring board using the same, a wiring board, and a semiconductor device.

That is, the present invention includes the following contents.
[1] (1) A step of preparing a base material with a wiring layer having a base material and a wiring layer provided on at least one surface of the base material.
(2) An adhesive film containing a thermosetting resin composition layer is laminated on a base material with a wiring layer so that the wiring layer is embedded in the thermosetting resin composition layer, and is thermally cured to form an insulating layer. Process,
(3) Steps of connecting wiring layers between layers, and (4) Steps of removing a base material,
An adhesive film used in the manufacturing method of wiring boards, including
The adhesive film contains a support and a thermosetting resin composition layer.
The average linear thermal expansion coefficient of the cured product obtained by thermally curing the thermosetting resin composition layer at 30 ° C. to 150 ° C. is 16 ppm / ° C. or less.
The elastic modulus of the cured product obtained by thermosetting the thermosetting resin composition layer at 25 ° C. is 12 GPa or less.
An adhesive film having a breaking strength at 25 ° C. of a cured product obtained by thermosetting the thermosetting resin composition layer at 25 MPa or more.
[2] The step (3) is at least one of a step of forming a via hole in the insulating layer to form a conductor layer and a step of polishing or grinding the insulating layer to expose the wiring layer [1]. ] The adhesive film described in.
[3] An adhesive film used for manufacturing a wiring board including an insulating layer and an embedded wiring layer embedded in the insulating layer.
The adhesive film contains a support and a thermosetting resin composition layer.
The insulating layer is a cured product of the thermosetting resin composition layer.
The average linear thermal expansion coefficient of the cured product of the thermosetting resin composition layer at 30 ° C. to 150 ° C. is 16 ppm / ° C. or less.
The elastic modulus of the cured product of the thermosetting resin composition layer at 25 ° C. is 12 GPa or less.
An adhesive film having a breaking strength of a cured product of a thermosetting resin composition layer at 25 ° C. of 45 MPa or more.
[4] The thermosetting resin composition layer is composed of a thermosetting resin composition, and the thermosetting resin composition is (a) an epoxy resin having an aromatic structure, (b) a glass transition temperature of 25 ° C. or less or The adhesive film according to any one of [1] to [3], which comprises a polymer resin that is liquid at 25 ° C., (c) a curing agent, and (d) an inorganic filler.
[5] The component (b) is selected from the group consisting of a polyalkylene structure, a polyalkyleneoxy structure, a polybutadiene structure, a polyisoprene structure, a polyisobutylene structure, a polycarbonate structure, a poly (meth) acrylate structure, and a polysiloxane structure. The adhesive film according to [4], which has one or more structures.
[6] The content of the component (b) is 2% by mass to 13% by mass when the non-volatile component in the thermosetting resin composition is 100% by mass, according to [4] or [5]. Adhesive film.
[7] The adhesive film according to any one of [4] to [6], wherein the component (d) is selected from silica or alumina.
[8] The content of the component (d) is 73% by mass or more when the non-volatile component in the thermosetting resin composition is 100% by mass, according to any one of [4] to [7]. Adhesive film.
[9] Any of [4] to [8], wherein the mixing ratio (mass ratio) of the component (d) and the component (b) is (component (d) / component (b)) 5 to 45. The adhesive film described.
[10] (1) A step of preparing a base material with a wiring layer having a base material and a wiring layer provided on at least one surface of the base material.
(2) The adhesive film according to any one of [1] to [9] is laminated on a base material with a wiring layer and heat-cured so that the wiring layer is embedded in the thermosetting resin composition layer. The process of forming an insulating layer,
(3) The process of connecting the wiring layers between layers and
(4) Step of removing the base material,
A method of manufacturing a wiring board, including.
[11] The step (3) is at least one of a step of forming a via hole in the insulating layer to form a conductor layer and a step of polishing or grinding the insulating layer to expose the wiring layer [10]. ] The method described in.
[12] The method according to [10] or [11], wherein the step (3) is a step of forming a via hole in the insulating layer and forming a conductor layer, which is performed by laser irradiation.
[13] The method according to [12], which comprises a step of performing a roughening treatment before forming a conductor layer.
[14] The method according to any one of [10] to [13], wherein the wiring board is a flexible wiring board.
[15] The method according to any one of [10] to [14], wherein the minimum pitch of the wiring pattern is 40 μm or less.
[16] Wiring including an insulating layer which is a cured product of the thermosetting resin composition layer of the adhesive film according to any one of [1] to [9] and an embedded wiring layer embedded in the insulating layer. Board.
[17] The wiring board according to [16], which is a flexible wiring board.
[18] The wiring board according to [16] or [17], wherein the thickness of the insulating layer is 2 μm or more.
[19] A semiconductor device including the wiring board according to any one of [16] to [18].

According to the present invention, an adhesive film capable of forming an insulating layer that does not warp or crack when manufacturing a wiring board provided with an embedded wiring layer, a method for manufacturing a wiring board using the adhesive film, a wiring board, and the like. And semiconductor devices can be provided.

FIG. 1 is a schematic cross-sectional view for explaining a manufacturing process of a wiring board. FIG. 2 is a schematic cross-sectional view for explaining the manufacturing process of the wiring board. FIG. 3 is a schematic cross-sectional view for explaining the manufacturing process of the wiring board. FIG. 4 is a schematic cross-sectional view for explaining the manufacturing process of the wiring board. FIG. 5 is a schematic cross-sectional view for explaining the manufacturing process of the wiring board. FIG. 6 is a schematic cross-sectional view for explaining the manufacturing process of the wiring board. FIG. 7 is a schematic cross-sectional view for explaining the manufacturing process of the wiring board. FIG. 8 is a schematic cross-sectional view for explaining the manufacturing process of the wiring board. FIG. 9 is a schematic cross-sectional view for explaining the manufacturing process of the wiring board. FIG. 10 is a schematic cross-sectional view for explaining the manufacturing process of the wiring board. FIG. 11 is a schematic cross-sectional view for explaining the manufacturing process of the wiring board. FIG. 12 is a schematic cross-sectional view for explaining the manufacturing process of the wiring board. FIG. 13 is a schematic cross-sectional view for explaining the manufacturing process of the wiring board. FIG. 14 is a schematic cross-sectional view for explaining the manufacturing process of the wiring board. FIG. 15 is a schematic cross-sectional view for explaining the manufacturing process of the wiring board. FIG. 16 is a schematic cross-sectional view for explaining the manufacturing process of the wiring board. FIG. 17 is a schematic cross-sectional view for explaining the manufacturing process of the wiring board. FIG. 18 is a schematic cross-sectional view for explaining the manufacturing process of the wiring board. FIG. 19 is a schematic cross-sectional view for explaining the manufacturing process of the wiring board. FIG. 20 is a schematic cross-sectional view for explaining the manufacturing process of the wiring board. FIG. 21 is a schematic cross-sectional view for explaining the manufacturing process of the wiring board. FIG. 22 is a schematic cross-sectional view for explaining the wiring board. FIG. 23 is a schematic cross-sectional view for explaining the wiring board. FIG. 24 is a cross-sectional photograph of the thermosetting resin composition layer of Comparative Example 2.

Hereinafter, the adhesive film of the present invention, the method for manufacturing a wiring board, the wiring board, and the semiconductor device will be described in detail.

[Adhesive film]
The adhesive film of the present invention comprises (1) a step of preparing a base material with a wiring layer having a base material and a wiring layer provided on at least one surface of the base material, and (2) a thermosetting resin composition. A step of laminating an adhesive film containing a layer on a base material with a wiring layer so that the wiring layer is embedded in a thermosetting resin composition layer and thermosetting to form an insulating layer, (3) An adhesive film used in a method for manufacturing a wiring board, which includes a step of connecting between layers and (4) a step of removing a base material, wherein the adhesive film comprises a support and a thermosetting resin composition layer. The average linear thermal expansion coefficient of the cured product obtained by thermosetting the thermosetting resin composition layer at 30 ° C. to 150 ° C. is 16 ppm / ° C. or less, and the thermosetting resin composition layer is thermosetting. The elastic rate of the cured product obtained in 25 ° C. is 12 GPa or less, and the breaking strength (also referred to as “breaking strength”) of the cured product obtained by thermosetting the thermosetting resin composition layer at 25 ° C. is 45 MPa or more. It is characterized by being.

Further, the adhesive film of the present invention is an adhesive film used for manufacturing a wiring plate including an insulating layer and an embedded wiring layer embedded in the insulating layer, and the adhesive film is a support and thermosetting. The insulating layer includes a thermosetting resin composition layer, and the insulating layer is composed of a cured product of the thermosetting resin composition layer, and the average linear thermal expansion coefficient of the cured product of the thermosetting resin composition layer at 30 ° C. to 150 ° C. is 16 ppm. / ° C., The elasticity of the cured product of the thermosetting resin composition layer at 25 ° C. is 12 GPa or less, and the breaking strength of the cured product of the thermosetting resin composition layer at 25 ° C. is 45 MPa or more. It is characterized by.

The adhesive film of the present invention includes a support and a thermosetting resin composition layer, and in one embodiment, the adhesive film comprises a support and a thermosetting resin composition layer bonded to the support. The thermosetting resin composition layer is composed of the thermosetting resin composition. Hereinafter, each layer constituting the adhesive film will be described in detail.

<Support>
The adhesive film of the present invention includes a support. Examples of the support include a film made of a plastic material, a metal foil, and a paper pattern, and a film made of a plastic material and a metal leaf are preferable.

When a film made of a plastic material is used as the support, the plastic material may be, for example, polyethylene terephthalate (hereinafter, may be abbreviated as "PET") or polyethylene naphthalate (hereinafter, abbreviated as "PEN"). ) Etc., polyester, polycarbonate (hereinafter sometimes abbreviated as "PC"), acrylic such as polymethylmethacrylate (PMMA), cyclic polyolefin, triacetylcellulose (TAC), polyethersulfide (PES), polyether. Examples thereof include ketones and polyimides. Of these, polyethylene terephthalate and polyethylene naphthalate are preferable, and inexpensive polyethylene terephthalate is particularly preferable.

When a metal foil is used as the support, examples of the metal foil include copper foil and aluminum foil, and copper foil is preferable. As the copper foil, a foil made of a single metal of copper may be used, and a foil made of an alloy of copper and another metal (for example, tin, chromium, silver, magnesium, nickel, zirconium, silicon, titanium, etc.) may be used. You may use it. Further, as the metal foil, one in which a plurality of metal foils are laminated may be used.

The support may be matted or corona-treated on the surface to be joined to the thermosetting resin composition layer.

Further, as the support, a support with a release layer having a release layer on the surface to be joined with the thermosetting resin composition layer may be used. Examples of the release agent used for the release layer of the support with the release layer include one or more release agents selected from the group consisting of alkyd resin, polyolefin resin, urethane resin, and silicone resin. .. As the support with a release layer, a commercially available product may be used. For example, "SK-1" manufactured by Lintec Co., Ltd., which is a PET film having a release layer containing an alkyd resin-based release agent as a main component. , "AL-5", "AL-7", "Lumirror T6AM" manufactured by Toray Industries, Inc., and the like.

The thickness of the support is not particularly limited, but is preferably in the range of 5 μm to 75 μm, and more preferably in the range of 10 μm to 60 μm. When a support with a release layer is used, the thickness of the entire support with a release layer is preferably in the above range.

<Thermosetting resin composition layer>
The adhesive film of the present invention contains a thermosetting resin composition layer, and the thermosetting resin composition layer is composed of a thermosetting resin composition. Although the details will be described later, when the wiring board is manufactured, the wiring layer is embedded in the thermosetting resin composition layer, whereby an embedded wiring layer is formed. The thermosetting resin composition (hereinafter, also referred to as “resin composition”) constituting the thermosetting resin composition layer is not particularly limited, and the cured product may have sufficient insulating properties. Examples of such a thermosetting resin composition include a composition containing a thermosetting resin and a curing agent thereof. As the thermosetting resin, a conventionally known thermosetting resin used for forming an insulating layer of a wiring board can be used, and among them, an epoxy resin having an aromatic structure is preferable. Further, from the viewpoint of lowering the elastic coefficient and the average linear thermal expansion coefficient of the cured product of the thermosetting resin composition layer, and in order to suppress the occurrence of warpage of the wiring plate that can be manufactured by using the adhesive film of the present invention. The thermosetting resin composition contains a polymer resin having a glass transition temperature of 25 ° C. or lower or a liquid at 25 ° C., and an inorganic filler. Therefore, in one embodiment, the thermosetting resin composition is (a) an epoxy resin having an aromatic structure, (b) a polymer resin having a glass transition temperature of 25 ° C. or lower or a liquid at 25 ° C., and (c) a curing agent. , And (d) include an inorganic filler. The thermosetting resin composition further contains additives such as (e) a curing accelerator, (f) a thermoplastic resin (excluding those corresponding to the component (b)), and (g) a flame retardant, if necessary. May include.

-(A) Epoxy resin having an aromatic structure-
The epoxy resin having an aromatic structure (hereinafter, also simply referred to as “epoxy resin”) is not particularly limited as long as it has an aromatic structure. The aromatic structure is a chemical structure generally defined as aromatic, and also includes polycyclic aromatics and aromatic heterocycles. 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 type epoxy resin, and naphthol novolac type epoxy resin. Phenol novolac type epoxy resin, tert-butyl-catechol type epoxy resin, naphthalene type epoxy resin, naphthol type epoxy resin, anthracene type epoxy resin, bisilylenol type epoxy resin, glycidylamine type epoxy resin having aromatic structure, aromatic structure Glycidyl ester type epoxy resin, cresol novolac type epoxy resin, biphenyl type epoxy resin, linear aliphatic epoxy resin having aromatic structure, epoxy resin having butadiene structure having aromatic structure, alicyclic type having aromatic structure Epoxy resin, heterocyclic epoxy resin, spiro-ring-containing epoxy resin having an aromatic structure, cyclohexanedimethanol type epoxy resin having an aromatic structure, naphthylene ether type epoxy resin, trimethylol type epoxy resin having an aromatic structure, Examples thereof include a tetraphenylethane type epoxy resin having an aromatic structure. The epoxy resin may be used alone or in combination of two or more. The component (a) is preferably one or more selected from the group consisting of a bisphenol A type epoxy resin, a bisphenol F type epoxy resin, and a biphenyl type epoxy resin.

The epoxy resin preferably contains an epoxy resin having two or more epoxy groups in one molecule. When the non-volatile 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, an epoxy resin having two or more epoxy groups in one molecule and liquid at a temperature of 20 ° C. (hereinafter referred to as "liquid epoxy resin") and three or more epoxy groups in one molecule. It is preferable to contain a solid epoxy resin (hereinafter referred to as "solid epoxy resin") at a temperature of 20 ° C. By using a liquid epoxy resin and a solid epoxy resin in combination as the epoxy resin, a resin composition having excellent flexibility can be obtained. In addition, the breaking strength of the cured product of the resin composition is also improved.

Examples of the liquid epoxy resin include bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol AF type epoxy resin, naphthalene type epoxy resin, glycidyl ester type epoxy resin having an aromatic structure, and glycidylamine type epoxy resin having an aromatic structure. , Phenol novolac type epoxy resin, alicyclic epoxy resin having an ester skeleton having an aromatic structure, cyclohexanedimethanol type epoxy resin having an aromatic structure, and epoxy resin having a butadiene structure having an aromatic structure are preferable, and bisphenol A is preferable. Type epoxy resin, bisphenol F type epoxy resin, bisphenol AF type epoxy resin and naphthalene type epoxy resin are more preferable, and bisphenol A type epoxy resin and bisphenol F type epoxy resin are further preferable. Specific examples of the liquid epoxy resin include "HP4032", "HP4032D", "HP4032SS" (naphthalene type epoxy resin) manufactured by DIC Co., Ltd., "828US", "jER828EL" manufactured by Mitsubishi Chemical Co., Ltd. (bisphenol A). Type epoxy resin), "jER807" (bisphenol F type epoxy resin), "jER152" (phenol novolac type epoxy resin), "630", "630LSD" (glycidylamine type epoxy resin), manufactured by Nippon Steel & Sumitomo Metal Corporation "ZX1059" (mixture of bisphenol A type epoxy resin and bisphenol F type epoxy resin), "EX-721" (glycidyl ester type epoxy resin) manufactured by Nagase ChemteX Corporation, "Selokiside 2021P" manufactured by Daicel Co., Ltd. "(Alicyclic epoxy resin having an ester skeleton)," ZX1658 "," ZX1658GS "(liquid 1,4-glycidylcyclohexane) manufactured by Nippon Steel Chemical Co., Ltd. can be mentioned. These may be used individually by 1 type, and may be used in combination of 2 or more type.

Examples of the solid epoxy resin include naphthalene type tetrafunctional epoxy resin, cresol novolac type epoxy resin, dicyclopentadiene type epoxy resin having an aromatic structure, trisphenol type epoxy resin, naphthol type epoxy resin, biphenyl type epoxy resin, and naphthylene. Ether type epoxy resin, anthracene type epoxy resin, bisphenol A type epoxy resin, and tetraphenylethane type epoxy resin are preferable, and naphthalene type tetrafunctional epoxy resin, naphthol type epoxy resin, biphenyl type epoxy resin, and naphthylene ether type epoxy resin are preferable. More preferably, a naphthalene type tetrafunctional epoxy resin and a naphthylene ether type epoxy resin are further preferable. Specific examples of the solid epoxy resin include "HP4032H" (naphthalene type epoxy resin), "HP-4700", "HP-4710" (naphthalene type tetrafunctional epoxy resin), and "N-690" manufactured by DIC Co., Ltd. (Cresol novolac type epoxy resin), "N-695" (cresol novolac type epoxy resin), "HP-7200" (dicyclopentadiene type epoxy resin), "HP-7200HH", "HP-7200H", "EXA7311" , "EXA7311-G3", "EXA7311-G4", "EXA7311-G4S", "HP6000" (naphthylene ether type epoxy resin), "EPPN-502H" (trisphenol type epoxy) manufactured by Nippon Kayaku Co., Ltd. Resin), "NC7000L" (naphthol novolac type epoxy resin), "NC3000H", "NC3000", "NC3000L", "NC3100" (biphenyl type epoxy resin), "ESN475V" (naphthol type) manufactured by Nippon Steel & Sumitomo Metal Corporation Epoxy resin), "ESN485" (naphthol novolac type epoxy resin), "YX4000H", "YL6121" (biphenyl type epoxy resin), "YX4000HK" (bixilenol type epoxy resin), "YX8800" manufactured by Mitsubishi Chemical Corporation (Anthracen type epoxy resin), "PG-100" and "CG-500" manufactured by Osaka Gas Chemical Co., Ltd., "YL7800" (fluorene type epoxy resin) manufactured by Mitsubishi Chemical Co., Ltd., manufactured by Mitsubishi Chemical Co., Ltd. "JER1010" (solid bisphenol A type epoxy resin), "jER1031S" (tetraphenylethane type epoxy resin), "YL7760" (bisphenol AF type epoxy resin) and the like.

The liquid epoxy resin has two or more epoxy groups in one molecule, and an aromatic epoxy resin that is liquid at a temperature of 20 ° C. is preferable, and the solid epoxy resin has three or more epoxy groups in one molecule. A solid aromatic epoxy resin having a temperature of 20 ° C. is preferable. The aromatic epoxy resin in the present invention means an epoxy resin having an aromatic ring structure in its molecule.

When a liquid epoxy resin and a solid epoxy resin are used in combination as the epoxy resin, their quantity ratio (liquid epoxy resin: solid epoxy resin) is in the range of 1: 0.1 to 1: 20 in terms of mass ratio. preferable. By setting the amount ratio of the liquid epoxy resin to the solid epoxy resin in such a range, i) when used in the form of an adhesive film, appropriate adhesiveness is provided, and ii) when used in the form of an adhesive film. Sufficient flexibility can be obtained, handleability is improved, and iii) a cured product having sufficient breaking strength can be obtained. From the viewpoint of the effects of i) to iii) above, the quantitative ratio of the liquid epoxy resin to the solid epoxy resin (liquid epoxy resin: solid epoxy resin) is in the range of 1: 0.3 to 1:10 in terms of mass ratio. Is more preferable, and the range of 1: 0.6 to 1: 9 is even more preferable.

The content of the epoxy resin in the thermosetting resin composition is preferably 4% by mass or more, more preferably 5% by mass or more, still more preferably 5% by mass or more, from the viewpoint of obtaining an insulating layer exhibiting good mechanical strength and insulation reliability. It is 6% by mass or more. The upper limit of the content of the epoxy resin is not particularly limited as long as the effect of the present invention is exhibited, but is preferably 50% by mass or less, more preferably 40% by mass or less.

In the present invention, the content of each component in the thermosetting resin composition is a value when the non-volatile component in the thermosetting resin composition is 100% by mass, unless otherwise specified.

The epoxy equivalent of the epoxy resin is preferably 50 to 5000, more preferably 50 to 3000, still more preferably 80 to 2000, and even more preferably 110 to 1000. Within this range, the crosslink density of the cured product becomes sufficient, and an insulating layer having a small surface roughness can be provided. The epoxy equivalent can be measured according to JIS K7236, and is the mass of the resin containing 1 equivalent of the epoxy group.

The weight average molecular weight of the epoxy resin is preferably 100 to 5000, more preferably 250 to 3000, and even more preferably 400 to 1500. Here, the weight average molecular weight of the epoxy resin is a polystyrene-equivalent weight average molecular weight measured by a gel permeation chromatography (GPC) method.

-(B) Polymer resin that is liquid when the glass transition temperature is 25 ° C or lower or 25 ° C-
The thermosetting resin composition contains the component (b). As the component (b), only a polymer resin having a glass transition temperature of 25 ° C. or lower may be used, or only a polymer resin liquid at 25 ° C. may be used, and the glass transition temperature is as high as 25 ° C. or less. A molecular resin and a polymer resin that is liquid at 25 ° C. may be used in combination. By containing a flexible polymer resin such as the component (b), the elastic modulus and the coefficient of thermal expansion of the cured product of the thermosetting resin composition layer can be reduced, and the adhesive film of the present invention can be used for production. It is possible to suppress the occurrence of warpage of the wiring plate.

The glass transition temperature (Tg) of the component (b) is 25 ° C. or lower, and the glass transition temperature of the polymer resin is preferably 20 ° C. or lower, more preferably 15 ° C. or lower. The lower limit of the glass transition temperature of the component (b) is not particularly limited, but may be usually −15 ° C. or higher.

The component (b) preferably has a functional group capable of reacting with the component (a). That is, the component (b) is preferably a resin having a functional group having a glass transition temperature of 25 ° C. or lower, and preferably one or more resins selected from resins having a functional group that are liquid at 25 ° C. In one preferred embodiment, the functional group contained in the component (b) is one or more functional groups selected from the group consisting of a hydroxyl group, an acid anhydride group, a phenolic hydroxyl group, an epoxy group, an isocyanate group and a urethane group. Is. Among them, as the functional group, a hydroxyl group, an acid anhydride group, an epoxy group and a phenolic hydroxyl group are preferable, and a hydroxyl group, an acid anhydride group and an epoxy group are more preferable. However, when an epoxy group is contained as a functional group, it is preferable that the component (b) does not have an aromatic structure.

The component (b) contains a polyalkylene structure, a polyalkyleneoxy structure, a polybutadiene structure, a polyisoprene structure, a polyisobutylene structure, a polycarbonate structure, and a poly (meth) acrylate from the viewpoint of obtaining a thermosetting resin composition layer having a low elastic modulus. It is preferable to have one or more structures selected from the group consisting of a structure and a polysiloxane structure, and more preferably to have one or more structures selected from the group consisting of a polybutadiene structure and a poly (meth) acrylate structure. In addition, "(meth) acrylate" refers to methacrylate and acrylate.

The polyalkylene structure is preferably a polyalkylene structure having 2 to 15 carbon atoms, more preferably a polyalkylene structure having 3 to 10 carbon atoms, and more preferably a polyalkylene structure having 5 to 6 carbon atoms.

The polyalkyleneoxy structure is preferably a polyalkyleneoxy structure having 2 to 15 carbon atoms, more preferably a polyalkyleneoxy structure having 3 to 10 carbon atoms, and more preferably a polyalkyleneoxy structure having 5 to 6 carbon atoms. is there.

A preferred embodiment of the component (b) is a butadiene resin. The butadiene resin is preferably a butadiene resin that is liquid at 25 ° C. or has a glass transition temperature of 25 ° C. or lower, and is preferably a hydride polybutadiene skeleton-containing resin (for example, a hydride polybutadiene skeleton-containing epoxy resin), a hydroxy group-containing butadiene resin, or a phenolic hydroxyl group-containing butadiene. Consists of resin (resin having a polybutadiene structure and having a phenolic hydroxyl group), carboxy group-containing butadiene resin, acid anhydride group-containing butadiene resin, epoxy group-containing butadiene resin, isocyanate group-containing butadiene resin, and urethane group-containing butadiene resin. One or more resins selected from the group are more preferred, and phenolic hydroxyl group-containing butadiene resins are even more preferred. Here, the "butadiene resin" refers to a resin containing a polybutadiene structure, and in these resins, the polybutadiene structure may be contained in the main chain or the side chain. The polybutadiene structure may be partially or wholly hydrogenated. Here, the "hydrogenated polybutadiene skeleton-containing resin" means a resin in which at least a part of the polybutadiene skeleton is hydrogenated, and the polybutadiene skeleton does not necessarily have to be a completely hydrogenated resin.

The number average molecular weight (Mn) of the butadiene resin is preferably 1,000 to 100,000, more preferably 5,000 to 50,000, more preferably 7,500 to 30,000, still more preferably 10,000 to 10,000. It is 15,000. Here, the number average molecular weight (Mn) of the resin is a polystyrene-equivalent number average molecular weight measured using GPC (gel permeation chromatography).

When the butadiene resin has a functional group, the functional group equivalent is preferably 100 to 10000, more preferably 200 to 5000. The functional group equivalent is the number of grams of the resin containing 1 gram equivalent of the functional group. For example, the epoxy group equivalent can be measured according to JIS K7236. The hydroxyl group equivalent can be calculated by dividing the molecular weight of KOH by the hydroxyl value measured according to JIS K1557-1.

Specific examples of the butadiene resin include "Ricon 657" (polybutadiene containing an epoxy group), "Ricon 130MA8", "Ricon 130MA13", "Ricon 130MA20", "Ricon 131MA5", "Ricon 131MA10", and "Ricon 131MA10" manufactured by Clay Valley. "Ricon 131MA17", "Ricon 131MA20", "Ricon 184MA6" (polybutadiene containing acid anhydride group), "JP-100", "JP-200" (epoxydated polybutadiene), "GQ-1000" (made by Nippon Soda Co., Ltd.) Polybutadiene with hydroxyl group and carboxyl group introduced), "G-1000", "G-2000", "G-3000" (polybutadiene with double-ended hydroxyl groups), "GI-1000", "GI-2000", "GI-3000" ( Bi-terminal hydroxyl hydrogenated polybutadiene), Daicel's "PB3600", "PB4700" (polybutadiene skeleton epoxy resin), "Epofriend A1005", "Epofriend A1010", "Epofriend A1020" (styrene, butadiene, and styrene block Epoxy products of copolymers), "FCA-061L" (hydropolybutadiene skeleton epoxy resin) manufactured by Nagase ChemteX Corporation, "R-45EPT" (polybutadiene skeleton epoxy resin), and the like.

Further, as another preferable embodiment of the component (b), a resin having an imide structure can also be used. As such a component (b), a linear polyimide using hydroxyl group-terminated polybutadiene, a diisocyanate compound, and a tetrabasic acid anhydride as raw materials (polyimide described in JP-A-2006-37083, International Publication No. 2008/153208). And so on. The content of the butadiene structure of the polyimide resin is preferably 60% by mass to 95% by mass, and more preferably 75% by mass to 85% by mass. For details of the polyimide resin, the description of JP-A-2006-37083 and International Publication No. 2008/153208 can be referred to, and the contents thereof are incorporated in the present specification.

A more preferred embodiment of the component (b) is a polyimide resin having a polybutadiene structure, a urethane structure, and an imide structure in the molecule, and the polyimide resin preferably has a phenol structure at the molecular terminal.

The number average molecular weight (Mn) of the polyimide resin is preferably 1000 to 100,000, more preferably 1000 to 15000. Here, the number average molecular weight (Mn) of the resin is a polystyrene-equivalent number average molecular weight measured using GPC (gel permeation chromatography).

The acid value of the polyimide resin is preferably 1 KOH / g to 30 KOH / g, more preferably 10 KOH / g to 20 KOH / g.

The content of the butadiene structure of the polyimide resin is preferably 60% by mass to 95% by mass, more preferably 75% by mass to 85% by mass.

Another preferred embodiment of the component (b) is an acrylic resin. As the acrylic resin, an acrylic resin having a glass transition temperature (Tg) of 25 ° C. or lower is preferable, and a hydroxy group-containing acrylic resin, a phenolic hydroxyl group-containing acrylic resin, a carboxy group-containing acrylic resin, an acid anhydride group-containing acrylic resin, and an epoxy group One or more resins selected from the group consisting of a containing acrylic resin, an isocyanate group-containing acrylic resin, and a urethane group-containing acrylic resin are more preferable. Here, the "acrylic resin" refers to a resin containing a (meth) acrylate structure, and in these resins, the (meth) acrylate structure may be contained in the main chain or the side chain.

The number average molecular weight (Mn) of the acrylic resin is preferably 10,000 to 1,000,000, more preferably 30,000 to 900,000. Here, the number average molecular weight (Mn) of the resin is a polystyrene-equivalent number average molecular weight measured using GPC (gel permeation chromatography).

When the acrylic resin has a functional group, the functional group equivalent is preferably 1000 to 50,000, more preferably 2500 to 30000.

Specific examples of the acrylic resin include Teisan resins "SG-70L", "SG-708-6", "WS-023", "SG-700AS", and "SG-280TEA" (carboxy group) manufactured by Nagase ChemteX Corporation. Containing acrylic acid ester copolymer resin, acid value 5 to 34 mgKOH / g, weight average molecular weight 400,000 to 900,000, Tg-30 to 5 ° C), "SG-80H", "SG-80H-3", "SG" -P3 "(epoxy group-containing acrylic ester copolymer resin, epoxy equivalent 4761 to 14285 g / eq, weight average molecular weight 350,000 to 850,000, Tg 11 to 12 ° C.)," SG-600TEA "," SG-790 "" (Hydroxy group-containing acrylic ester copolymer resin, hydroxyl value 20-40 mgKOH / g, weight average molecular weight 500,000-1.2 million, Tg-37-32 ° C), "ME-2000" manufactured by Negami Kogyo Co., Ltd., " "W-116.3" (carboxy group-containing acrylic acid ester copolymer resin), "W-197C" (hydroxyl group-containing acrylic acid ester copolymer resin), "KG-25", "KG-3000" (epoxy group) (Containing acrylic acid ester copolymer resin) and the like.

Moreover, a preferable embodiment of the component (b) is a carbonate resin. As the carbonate resin, a carbonate resin having a glass transition temperature of 25 ° C. or lower is preferable, and a hydroxy group-containing carbonate resin, a phenolic hydroxyl group-containing carbonate resin, a carboxy group-containing carbonate resin, an acid anhydride group-containing carbonate resin, an epoxy group-containing carbonate resin, One or more resins selected from the group consisting of isocyanate group-containing carbonate resins and urethane group-containing carbonate resins are preferred. Here, the "carbonate resin" refers to a resin containing a carbonate structure, and in these resins, the carbonate structure may be contained in the main chain or the side chain.

The number average molecular weight (Mn) and functional group equivalent of the carbonate resin are the same as those of the butadiene resin, and the preferable ranges are also the same.

Specific examples of the carbonate resin include "T6002" and "T6001" (polycarbonate diol) manufactured by Asahi Kasei Chemicals, and "C-1090", "C-2090" and "C-3090" (polycarbonate diol) manufactured by Kuraray. And so on.

Further, a linear polyimide (PCT / JP2016 / 053609) made from a hydroxyl group-terminated polycarbonate, a diisocyanate compound and a tetrabasic acid anhydride can also be used. The content of the carbonate structure of the polyimide resin is preferably 60% by mass to 95% by mass, and more preferably 75% by mass to 85% by mass. For details of the polyimide resin, the description of PCT / JP2016 / 053609 can be referred to, and this content is incorporated in the present specification.

Further, a preferred embodiment of the component (b) is a polysiloxane resin, an alkylene resin, an alkyleneoxy resin, an isoprene resin, or an isobutylene resin.

Specific examples of the polysiloxane resin include "SMP-2006", "SMP-2003PGMEA", "SMP-5005PGMEA" manufactured by Shinetsu Silicone Co., Ltd., amine group-terminated polysiloxane, and linear polyimides made from tetrabasic acid anhydride. International Publication No. 2010/053185) and the like can be mentioned.
Specific examples of the alkylene resin include "PTXG-1000" and "PTXG-1800" manufactured by Asahi Kasei Fibers Corporation, and "YX-7180" (resin containing an alkylene structure having an ether bond) manufactured by Mitsubishi Chemical Corporation. ..
Specific examples of the alkyleneoxy resin include "EXA-4850-150", "EXA-4816", "EXA-4822" manufactured by DIC Corporation, "EP-4000", "EP-4003", and "EP-4010" manufactured by ADEKA. , "EP-4011", "BEO-60E" and "BPO-20E" manufactured by New Japan Chemical Co., Ltd., "YL7175" manufactured by Mitsubishi Chemical Corporation, and "YL7410".
Specific examples of the isoprene resin include "KL-610" and "KL613" manufactured by Kuraray.
Specific examples of the isobutylene resin include "SIBSTAR-073T" (styrene-isobutylene-styrene triblock copolymer) and "SIBSTAR-042D" (styrene-isobutyrene block copolymer) manufactured by Kaneka.

Further, as a preferable embodiment of the component (b), acrylic rubber particles, polyamide fine particles, silicone particles and the like can be mentioned. Specific examples of the acrylic rubber particles include fine particles of a resin that is insoluble and insoluble in an organic solvent by chemically cross-linking a resin exhibiting rubber elasticity such as acrylonitrile butadiene rubber, butadiene rubber, and acrylic rubber. Specifically, XER-91 (manufactured by Nippon Synthetic Rubber Co., Ltd.), Staphyroid AC3355, AC3816, AC3832, AC4030, AC3364, IM101 (manufactured by Ganz Kasei Co., Ltd.), Pararoid EXL2655, EXL2602 (manufactured by Kureha Chemical Industry Co., Ltd.) ) Etc. can be mentioned. Specific examples of the polyamide fine particles may be any aliphatic polyamide such as nylon, and any flexible skeleton such as polyamide-imide. Specifically, VESTOSINT 2070 (manufactured by Daiselhurus) or , SP500 (manufactured by Toray Industries, Inc.) and the like.

From the viewpoint of improving the breaking strength, the component (b) preferably has high compatibility with components other than the component (b). That is, it is preferable that the component (b) is dispersed in the thermosetting resin composition layer. Further, the component (b) may be dispersed by forming a domain in the thermosetting resin composition layer. The average maximum diameter of the domain is preferably 15 μm or less, more preferably 10 μm or less, further preferably 5 μm or less, or not dispersed (the average maximum diameter of the domain is 0 μm).

The average maximum diameter of the domain can be measured as follows. The FIB-SEM composite device (“SMI3050SE” manufactured by SII Nanotechnology Co., Ltd.) was applied to the thermosetting resin composition layer of the adhesive film that was thermally cured at 100 ° C. for 30 minutes and then at 170 ° C. for 30 minutes. Was used to observe the cross section. Specifically, the cross section in the direction perpendicular to the surface of the adhesive film was carved out by FIB (focused ion beam), and a cross section SEM image (observation width 60 μm, observation magnification 2,000 times) was obtained. The cross-sectional SEM images of 5 randomly selected points were observed, and the maximum diameters of 20 arbitrarily selected domains (4 points / each cut surface) were measured, and the average value was taken as the average maximum diameter. The maximum diameter is the maximum diameter of the domain.

The content of the component (b) in the thermosetting resin composition is not particularly limited, but is preferably 13% by mass or less, more preferably 12% by mass or less, and further preferably 11% by mass or less. The lower limit is preferably 2% by mass or more, more preferably 3% by mass or more, and further preferably 4% by mass or more.

-(C) Hardener-
The curing agent is not particularly limited as long as it has a function of curing the epoxy resin, and for example, a phenol-based curing agent, a naphthol-based curing agent, an active ester-based curing agent, a benzoxazine-based curing agent, a cyanate ester-based curing agent, and a curing agent. Examples include carbodiimide-based curing agents. The curing agent may be used alone or in combination of two or more. The component (c) is preferably one or more selected from a phenol-based curing agent, a naphthol-based curing agent, an active ester-based curing agent, and a cyanate ester-based curing agent.

As the phenol-based curing agent and the naphthol-based curing agent, a phenol-based curing agent having a novolak structure or a naphthol-based curing agent having a novolak structure is preferable from the viewpoint of heat resistance and water resistance. Further, from the viewpoint of adhesion to the wiring layer, a nitrogen-containing phenol-based curing agent is preferable, and a triazine skeleton-containing phenol-based curing agent is more preferable. Of these, a triazine skeleton-containing phenol novolac curing agent is preferable from the viewpoint of highly satisfying heat resistance, water resistance, and adhesion to the wiring layer.

Specific examples of the phenol-based curing agent and the naphthol-based curing agent include "MEH-7700", "MEH-7810", "MEH-7851" manufactured by Meiwa Kasei Co., Ltd., and Nippon Kayaku Co., Ltd. "NHN", "CBN", "GPH", "SN170", "SN180", "SN190", "SN475", "SN485", "SN495V", "SN375", "SN395" manufactured by Nippon Steel & Sumitomo Metal Corporation , DIC Corporation "TD-2090", "LA-7052", "LA-7054", "LA-1356", "LA-3018-50P", "EXB-9500", "HPC-9500" And so on.

An active ester-based curing agent is also preferable from the viewpoint of obtaining an insulating layer having excellent adhesion to the wiring layer. The active ester-based curing agent is not particularly limited, but generally contains an ester group having high reactive activity such as phenol esters, thiophenol esters, N-hydroxyamine esters, and esters of heterocyclic hydroxy compounds in one molecule. A compound having two or more esters is preferably used. The active ester-based curing agent is preferably obtained by a condensation reaction between a carboxylic acid compound and / or a thiocarboxylic acid compound and a hydroxy compound and / or a thiol compound. In particular, from the viewpoint of improving heat resistance, an active ester-based curing agent obtained from a carboxylic acid compound and a hydroxy compound is preferable, and an active ester-based curing agent obtained from a carboxylic acid compound and a phenol compound and / or a naphthol compound is more preferable. 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 and the like. Examples of the phenol compound or naphthol compound include hydroquinone, resorcin, bisphenol A, bisphenol F, bisphenol S, phenolphthaline, 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, dihydroxybenzophenol, trihydroxybenzophenol, tetrahydroxybenzophenone, fluoroglusin, Examples thereof include benzenetriol, dicyclopentadiene-type diphenol compounds, and phenol novolac. Here, the "dicyclopentadiene-type diphenol compound" refers to a diphenol compound obtained by condensing two phenol molecules with one dicyclopentadiene molecule.

Specifically, an active ester compound containing a dicyclopentadiene-type diphenol structure, an active ester compound containing a naphthalene structure, an active ester compound containing an acetylated product of phenol novolac, and an active ester compound containing a benzoylated product of phenol novolac are preferable. Of these, an active ester compound containing a naphthalene structure and an active ester compound containing a dicyclopentadiene-type diphenol structure are more preferable. The "dicyclopentadiene-type diphenol structure" represents a divalent structure composed of phenylene-dicyclopentylene-phenylene.

Commercially available products of active ester-based curing agents include "EXB9451", "EXB9460", "EXB9460S", "HPC-8000-65T", and "HPC-8000H-" as active ester compounds containing a dicyclopentadiene type diphenol structure. "65TM", "EXB-8000L-65TM" (manufactured by DIC Co., Ltd.), "EXB9416-70BK" (manufactured by DIC Co., Ltd.) as an active ester compound containing a naphthalene structure, as an active ester compound containing an acetylated product of phenol novolac. "DC808" (manufactured by Mitsubishi Chemical Corporation), "YLH1026" (manufactured by Mitsubishi Chemical Corporation) as an active ester compound containing a benzoylated product of phenol novolac, and "DC808" as an active ester-based curing agent which is an acetylated product of phenol novolac. (Made by Mitsubishi Chemical Co., Ltd.), "YLH1026" (manufactured by Mitsubishi Chemical Co., Ltd.), "YLH1030" (manufactured by Mitsubishi Chemical Co., Ltd.), "YLH1048" as an active ester-based curing agent which is a benzoylated product of phenol novolac. (Manufactured by Mitsubishi Chemical Co., Ltd.) and the like.

Specific examples of the benzoxazine-based curing agent include "HFB2006M" manufactured by Showa Polymer Co., Ltd., "Pd" and "FA" manufactured by Shikoku Chemicals Corporation.

Examples of the cyanate ester-based curing agent include bisphenol A disicianate, polyphenol cyanate, oligo (3-methylene-1,5-phenylene cyanate), 4,4'-methylenebis (2,6-dimethylphenylcyanate), and 4,4. '-Etilidene diphenyl disianate, hexafluorobisphenol A disyanate, 2,2-bis (4-cyanate) phenylpropane, 1,1-bis (4-cyanate phenylmethane), 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 Examples thereof include polyfunctional cyanate resins derived from novolak and cresol novolak, and prepolymers in which these cyanate resins are partially triazined. Specific examples of the cyanate ester-based curing agent include "PT30" and "PT60" (both phenol novolac type polyfunctional cyanate ester resins), "BA230", and "BA230S75" (bisphenol A disicanate) manufactured by Lonza Japan Co., Ltd. Prepolymers in which some or all of them are triazined to form a trimer) and the like.

Specific examples of the carbodiimide-based curing agent include "V-03" and "V-07" manufactured by Nisshinbo Chemical Co., Ltd.

The amount ratio of the epoxy resin to the curing agent is a ratio of [total number of epoxy groups in the epoxy resin]: [total number of reactive groups in the curing agent], preferably in the range of 1: 0.01 to 1: 2. 1: 0.015 to 1: 1.5 is more preferable, and 1: 0.02 to 1: 1 is even more preferable. Here, the reactive group of the curing agent is an active hydroxyl group, an active ester group, or the like, and differs depending on the type of the curing agent. The total number of epoxy groups in the epoxy resin is the total number of all epoxy resins obtained by dividing the solid content mass of each epoxy resin by the epoxy equivalent, and the total number of reactive groups in the curing agent is The value obtained by dividing the solid content mass of each curing agent by the reaction group equivalent is the total value for all the curing agents. By setting the amount ratio of the epoxy resin and the curing agent within such a range, the heat resistance of the cured product of the thermosetting resin composition is further improved.

In one embodiment, the thermosetting resin composition comprises (a) an epoxy resin and (c) a curing agent described above. The thermosetting resin composition is (a) a mixture of a liquid epoxy resin and a solid epoxy resin as an epoxy resin (the mass ratio of the liquid epoxy resin: the solid epoxy resin is preferably 1: 0.1 to 1:20. More preferably 1: 0.3 to 1:10, still more preferably 1: 0.6 to 1: 9) as the (c) curing agent, a phenol-based curing agent, a naphthol-based curing agent, an active ester-based curing agent, and the like. It is preferable to contain at least one selected from the group consisting of cyanate ester-based curing agents.

The content of the curing agent in the thermosetting resin composition is not particularly limited, but is preferably 30% by mass or less, more preferably 25% by mass or less, and further preferably 20% by mass or less. The lower limit is not particularly limited, but is preferably 2% by mass or more.

-(D) Inorganic filler-
The material of the inorganic filler is not particularly limited, but for example, silica, alumina, glass, cordierite, silicon oxide, barium sulfate, barium carbonate, talc, clay, mica powder, zinc oxide, hydrotalcite, boehmite, water. Aluminum oxide, 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 titanate, barium zirconate, calcium zirconate, zirconium phosphate, zirconium tungstate phosphate and the like. Among these, silica or alumina is preferable, and silica is particularly preferable. Further, as silica, spherical silica is preferable. The inorganic filler may be used alone or in combination of two or more.

From the viewpoint of good embedding property, the average particle size of the inorganic filler is preferably 2 μm or less, more preferably 1 μm or less, still more preferably 0.8 μm or less, and more preferably 0.6 μm or less. The lower limit of the average particle size is not particularly limited, but is preferably 0.01 μm or more, more preferably 0.05 μm or more, and further preferably 0.1 μm or more. Examples of commercially available inorganic fillers having such an average particle size include "YC100C", "YA050C", "YA050C-MJE", "YA010C" manufactured by Admatex Co., Ltd., and Denki Kagaku Kogyo Co., Ltd. "UFP-30", Tokuyama Co., Ltd. "Silfil NSS-3N", "Silfil NSS-4N", "Silfil NSS-5N", Admatex Co., Ltd. "SOC4", "SOC2", "SOC1", "AHP300" manufactured by Nippon Light Metal Co., Ltd., "Arnabeads (registered trademark) CB" manufactured by Showa Denko Co., Ltd. (for example, "CB-P05", "CB-A30S") "DAW-03" "DAW-" manufactured by Denka Co., Ltd. 45 ”,“ DAW-05 ”,“ ASFP-20 ”and the like.

The average particle size of the inorganic filler can be measured by a laser diffraction / scattering method based on the Mie scattering theory. Specifically, it can be measured by creating a particle size distribution of the inorganic filler on a volume basis with a laser diffraction / scattering type particle size distribution measuring device and using the median diameter as the average particle size. As the measurement sample, an inorganic filler dispersed in water by ultrasonic waves can be preferably used. As the laser diffraction / scattering type particle size distribution measuring device, "LA-500" manufactured by HORIBA, Ltd. or the like can be used.

From the viewpoint of enhancing moisture resistance and dispersibility, the inorganic filler is an aminosilane-based coupling agent, an epoxysilane-based coupling agent, a mercaptosilane-based coupling agent, a silane-based coupling agent, an alkoxysilane compound, an organosilazane compound, and titanate. It is preferable that the treatment is performed with one or more surface treatment agents such as a system coupling agent. Commercially available surface treatment agents include, for example, "KBM403" (3-glycidoxypropyltrimethoxysilane) manufactured by Shin-Etsu Chemical Co., Ltd. and "KBM803" (3-mercaptopropyltrimethoxy) manufactured by Shin-Etsu Chemical Co., Ltd. Silane), "KBE903" (3-aminopropyltriethoxysilane) manufactured by Shin-Etsu Chemical Co., Ltd., "KBM573" (N-phenyl-3-aminopropyltrimethoxysilane) manufactured by Shin-Etsu Chemical Co., Ltd., 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) manufactured by Shin-Etsu Chemical Co., Ltd. Silane coupling agent) and the like.

The content of the inorganic filler in the thermosetting resin composition is preferably 60% by mass or more, more preferably 70% by mass or more, still more preferably 73% by mass or more, from the viewpoint of obtaining an insulating layer having a low coefficient of thermal expansion. Is. The upper limit of the content of the inorganic filler in the thermosetting resin composition is preferably 90% by mass or less, more preferably 85% by mass or less, from the viewpoint of the mechanical strength of the insulating layer, particularly the elongation.

The mixing ratio (mass ratio) of the component (d) and the component (b) is (component (d) / component (b)), preferably 5 to 45 from the viewpoint of lowering the coefficient of linear thermal expansion and the elastic modulus. It is more preferably 6 to 35, still more preferably 7 to 25.

-(E) 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, and the like, and phosphorus-based curing accelerators and amine-based curing accelerators. Curing accelerators, imidazole-based curing accelerators, and metal-based curing accelerators are preferable, and amine-based curing accelerators, imidazole-based curing accelerators, and metal-based curing accelerators are more preferable. The curing accelerator may be used alone or in combination of two or more.

Examples of phosphorus-based curing accelerators include triphenylphosphine, phosphonium borate compounds, tetraphenylphosphonium tetraphenylborate, n-butylphosphonium tetraphenylborate, tetrabutylphosphonium decanoate, and (4-methylphenyl) triphenylphosphonium thiosianate. , Tetraphenylphosphonium thiosianate, butyltriphenylphosphonium thiosianate and the like, and triphenylphosphine and tetrabutylphosphonium decanoate are preferable.

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

Examples of the imidazole-based curing accelerator include 2-methylimidazole, 2-undecylimidazole, 2-heptadecylimidazole, 1,2-dimethylimidazole, 2-ethyl-4-methylimidazole, 1,2-dimethylimidazole, and the like. 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'-undecyl Imidazolyl- (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 other imidazole compounds and adducts of the imidazole compound and an epoxy resin are mentioned, with 2-ethyl-4-methylimidazole and 1-benzyl-2-phenylimidazole being preferred.

As the imidazole-based curing accelerator, a commercially available product may be used, and examples thereof include "P200-H50" manufactured by Mitsubishi Chemical Holdings, Inc.

Examples of the guanidine-based curing accelerator include dicyandiamide, 1-methylguanidine, 1-ethylguanidine, 1-cyclohexylguanidine, 1-phenylguanidine, 1- (o-tolyl) guanidine, dimethylguanidine, diphenylguanidine, trimethylguanidine, and the like. Tetramethylguanidine, pentamethylguanidine, 1,5,7-triazabicyclo [4.4.0] deca-5-ene, 7-methyl-1,5,7-triazabicyclo [4.4.0] Deca-5-ene, 1-methylbiguanide, 1-ethylbiguanide, 1-n-butylbiguanide, 1-n-octadecylbiguanide, 1,1-dimethylbiguanide, 1,1-diethylbiguanide, 1-cyclohexylbiguanide, 1 Examples thereof include −allyl biguanide, 1-phenylbiguanide, 1- (o-tolyl) biguanide, and dicyandiamide, 1,5,7-triazabicyclo [4.4.0] deca-5-ene is preferable.

Examples of the metal-based curing accelerator include organometallic complexes or organometallic salts of metals such as cobalt, copper, zinc, iron, nickel, manganese, and tin. Specific examples of the organometallic complex include organic cobalt complexes such as cobalt (II) acetylacetonate and cobalt (III) acetylacetonate, organic copper complexes such as copper (II) acetylacetonate, and zinc (II) acetylacetonate. Examples thereof include organic zinc complexes such as iron (III) acetylacetonate, organic nickel complexes such as nickel (II) acetylacetonate, and organic manganese complexes such as manganese (II) acetylacetonate. Examples of the organic metal salt include zinc octylate, tin octylate, zinc naphthenate, cobalt naphthenate, tin stearate, zinc stearate and the like.

The content of the curing accelerator in the thermosetting resin composition is not particularly limited, but is preferably 0.01% by mass to 3% by mass when the total amount of the non-volatile components of the epoxy resin and the curing agent is 100% by mass.

-(F) Thermoplastic resin (excluding those corresponding to component (b))-
As the thermoplastic resin, for example, a phenoxy resin, a polyvinyl acetal resin, a polyimide resin, a polyamideimide resin, a polysulfone resin, a polyethersulfone resin, a polyphenylene ether resin is preferable, and a phenoxy resin is more preferable. The thermoplastic resin may be used alone or in combination of two or more.

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

Examples of the phenoxy resin include bisphenol A skeleton, bisphenol F skeleton, bisphenol S skeleton, bisphenol acetphenone skeleton, novolak skeleton, biphenyl skeleton, fluorene skeleton, dicyclopentadiene skeleton, norbornene skeleton, naphthalene skeleton, anthracene skeleton, adamantan skeleton, and terpen. Examples thereof include a phenoxy resin having one or more skeletons selected from the group consisting of a 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 bisphenol A skeleton-containing phenoxy resin), "YX8100" (bisphenol S skeleton-containing phenoxy resin), and "YX6954" (both manufactured by Mitsubishi Chemical Corporation). Bisphenol acetophenone skeleton-containing phenoxy resin), and in addition, "FX280" and "FX293" manufactured by Nippon Steel & Sumitomo Metal Corporation, "YX6954BH30", "YX7553", "YX7553BH30" manufactured by Mitsubishi Chemical Corporation, Examples thereof include "YL7769BH30", "YL6794", "YL7213", "YL7290" and "YL7482".

Examples of the polyvinyl acetal resin include polyvinyl formal resin and polyvinyl butyral resin, and polyvinyl butyral resin is preferable. Specific examples of the polyvinyl acetal resin include "Electrified Butyral 4000-2", "Electrified Butyral 5000-A", "Electrified Butyral 6000-C", and "Electrified Butyral 6000-EP" manufactured by Denki Kagaku Kogyo Co., Ltd. , Sekisui Chemical Co., Ltd. Eslek BH series, BX series (for example, BX-5Z), KS series (for example, KS-1), BL series, BM series and the like.

Specific examples of the polyimide resin include "Ricacoat SN20" and "Ricacoat PN20" manufactured by New Japan Chemical Co., Ltd.

Specific examples of the polyamide-imide resin include "Vilomax HR11NN" and "Vilomax HR16NN" manufactured by Toyobo Co., Ltd.

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

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

Specific examples of the polyphenylene ether resin include oligophenylene ether styrene resin "OPE-2St 1200" manufactured by Mitsubishi Gas Chemical Company, Inc.

Among them, as the thermoplastic resin, a phenoxy resin and a polyvinyl acetal resin are preferable. Therefore, in one preferred embodiment, the thermoplastic resin comprises one or more selected from the group consisting of phenoxy resins and polyvinyl acetal resins.

When the thermosetting resin composition contains a thermoplastic resin, the content of the thermoplastic resin is preferably 0.5% by mass to 60% by mass, more preferably 3% by mass to 50% by mass, still more preferably 5. It is from mass% to 40% by mass.

-(G) Flame retardant-
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. The flame retardant may be used alone or in combination of two or more.

As the flame retardant, a commercially available product may be used, and examples thereof include "HCA-HQ" manufactured by Sanko Co., Ltd. and "PX-200" manufactured by Daihachi Chemical Industry Co., Ltd.

When the thermosetting resin composition contains a flame retardant, the content of the flame retardant is not particularly limited, but is preferably 0.5% by mass to 20% by mass, more preferably 0.5% by mass to 15% by mass. More preferably, 0.5% by mass to 10% by mass is further preferable.

-Other ingredients-
The thermosetting resin composition may further contain other additives, if necessary, and such other additives include, for example, organic copper compounds, organozinc compounds, organocobalt compounds, and the like. Examples thereof include metal compounds, thickeners, defoaming agents, leveling agents, adhesion imparting agents, resin additives such as colorants, and the like.

The thickness of the thermosetting resin composition layer is preferably 100 μm or less, more preferably 80 μm or less, still more preferably 60 μm or less, still more preferably 40 μm or less or 20 μm or less from the viewpoint of thinning the wiring board. The lower limit of the thickness of the thermosetting resin composition layer is not particularly limited, but is preferably 2 μm or more, more preferably 5 μm or more.

The adhesive film may include other layers in addition to the support and the thermosetting resin composition layer. For example, the adhesive film may have a protective film layer described later on the outermost surface.

<Manufacturing method of adhesive film>
The method for producing the adhesive film is not particularly limited as long as it includes the support and the thermosetting resin composition layer bonded to the support. For the adhesive film, for example, a resin varnish in which a resin composition is dissolved in an organic solvent is prepared, the resin varnish is applied onto a support using a die coater or the like, and further dried to form a resin composition layer. It can be manufactured by.

Examples of the organic solvent include ketones such as acetone, methyl ethyl ketone (MEK) and cyclohexanone, acetic acid esters such as ethyl acetate, butyl acetate, cellosolve acetate, propylene glycol monomethyl ether acetate and carbitol acetate, cellosolve and butyl carbitol and the like. Carbitols, aromatic hydrocarbons such as toluene and xylene, and amide solvents such as dimethylformamide, dimethylacetamide (DMAc) and N-methylpyrrolidone can be mentioned. The organic solvent may be used alone or in combination of two or more.

Drying may be carried out by a known method such as heating or blowing hot air. The drying conditions are not particularly limited, but the thermosetting resin composition layer is dried so that the content of the organic solvent is 10% by mass or less, preferably 5% by mass or less. Although it depends on the boiling point of the organic solvent in the resin varnish, for example, when a resin varnish containing 30% by mass to 60% by mass of an organic solvent is used, it is thermoset by drying at 50 ° C. to 150 ° C. for 3 to 15 minutes. The sex resin composition layer can be formed.

In the adhesive film, a protective film similar to the support can be further laminated on the surface of the thermosetting resin composition layer that is not bonded to the support (that is, the surface opposite to the support). The thickness of the protective film is not particularly limited, but is, for example, 1 μm to 40 μm. By laminating the protective film, it is possible to prevent dust and the like from adhering to the surface of the thermosetting resin composition layer and scratches. The adhesive film can be rolled up and stored. If the adhesive film has a protective film, it can be used by peeling off the protective film.

As the protective film, a film made of a plastic material is preferable.

Examples of the plastic material include polyesters such as polyethylene terephthalate (hereinafter sometimes abbreviated as "PET") and polyethylene naphthalate (hereinafter sometimes abbreviated as "PEN"), and polyolefins such as polyethylene and polypropylene. Examples thereof include polycarbonate (hereinafter sometimes abbreviated as "PC"), acrylics such as polymethylmethacrylate (PMMA), cyclic polyolefins, triacetylcellulose (TAC), polyethersulfide (PES), polyetherketones, polyimides and the like. Be done. Of these, polyethylene terephthalate, polyethylene naphthalate, and polypropylene are preferable, and inexpensive polyethylene terephthalate is particularly preferable.

Further, as the protective film, a support with a release layer having a release layer on the surface to be joined with the thermosetting resin composition layer may be used. Examples of the release agent used for the release layer of the support with the release layer include one or more release agents selected from the group consisting of alkyd resin, polyolefin resin, urethane resin, and silicone resin. .. As the support with a release layer, a commercially available product may be used. For example, "SK-1" manufactured by Lintec Co., Ltd., which is a PET film having a release layer containing an alkyd resin-based release agent as a main component. , "AL-5", "AL-7", "Lumirror T6AM" manufactured by Toray Industries, Inc., and the like.

The thickness of the protective film is not particularly limited, but is preferably in the range of 5 μm to 75 μm, and more preferably in the range of 10 μm to 60 μm. When a support with a release layer is used, the thickness of the entire support with a release layer is preferably in the above range.

The thermosetting resin composition layer in the present invention exhibits good embedding property. When laminating on a base material with a wiring layer, the thermosetting resin composition layer can be laminated on the wiring layer without voids.

In the adhesive film of the present invention, a cured product obtained by thermally curing a thermosetting resin composition layer (for example, a cured product obtained by curing at 190 ° C. for 90 minutes (thermosetting resin composition layer after thermosetting)). ) Shows a good average linear thermal expansion coefficient at 30 to 150 ° C. That is, it provides an insulating layer showing a good average coefficient of linear thermal expansion. The average linear thermal expansion coefficient of the cured product obtained by curing the thermosetting resin composition layer at 30 ° C. to 150 ° C. is 16 ppm / ° C. or lower, preferably 15 ppm / ° C. or lower, and more preferably 14 ppm / ° C. or lower. , 13 ppm / ° C. or less. The lower limit is not particularly limited, but is 0.1 ppm / ° C. or higher. The method for measuring the average linear thermal expansion coefficient can be measured according to the method described in <Measurement of average linear thermal expansion coefficient (thermal expansion coefficient)> described later.

In the adhesive film of the present invention, a cured product obtained by thermally curing a thermosetting resin composition layer (for example, a cured product obtained by curing at 190 ° C. for 90 minutes (thermosetting resin composition layer after thermosetting)). ) Indicates a good elastic modulus (25 ° C.). That is, it provides an insulating layer showing a good elastic modulus. The elastic modulus of the thermosetting resin composition layer after curing at 25 ° C. is 12 GPa or less, preferably 11 GPa or less, and more preferably 10 GPa or less. The lower limit is not particularly limited, but is 0.1 GPa or more. The elastic modulus can be measured according to the method described in <Measurement of elastic modulus and breaking strength> described later.

In the adhesive film of the present invention, a cured product obtained by thermally curing a thermosetting resin composition layer (for example, a cured product obtained by curing at 190 ° C. for 90 minutes (thermosetting resin composition layer after thermosetting)). ) Indicates a good breaking strength (25 ° C.). That is, it provides an insulating layer showing good breaking strength. The breaking strength of the thermosetting resin composition layer after curing at 25 ° C. is 45 MPa or more, preferably 50 MPa or more, and more preferably 60 MPa or more. The upper limit is not particularly limited, but is 500 MPa or less. The breaking strength can be measured according to the method described in <Measurement of elastic modulus and breaking strength> described later.

The adhesive film of the present invention provides a thermosetting resin composition layer that imparts a cured product showing good results in average linear thermal expansion coefficient at 30 ° C. to 150 ° C., elastic modulus at 25 ° C., and breaking strength at 25 ° C. Since it is contained, the occurrence of warpage and cracks is suppressed in the wiring board manufactured by using the adhesive film of the present invention. Therefore, the adhesive film of the present invention can be suitably used for forming an insulating layer of a printed wiring board provided with an embedded wiring layer, and more preferably used for forming an interlayer insulating layer of the printed wiring board. can do.

[Manufacturing method of wiring board]
The method for manufacturing a wiring board of the present invention
(1) A step of preparing a base material with a wiring layer having a base material and a wiring layer provided on at least one surface of the base material.
(2) A step of laminating the adhesive film of the present invention on a base material with a wiring layer so that the wiring layer is embedded in a thermosetting resin composition layer, and heat-curing to form an insulating layer.
It is characterized by including (3) a step of connecting wiring layers between layers and (4) a step of removing a base material.

The step (3) is not particularly limited as long as the wiring layers can be interconnected, but is a step of forming a via hole in the insulating layer to form a conductor layer and a step of polishing or grinding the insulating layer to expose the wiring layer. It is preferable that the step is at least one of the above steps.

Hereinafter, the case where the step (3) is a step of forming a via hole in the insulating layer and forming a conductor layer is the first embodiment, and the step (3) is a step of polishing or grinding the insulating layer to expose the wiring layer. A certain case will be described as a second embodiment.

1. 1. 1st Embodiment <Step (1)>
The step (1) is a step of preparing a base material with a wiring layer having a base material and a wiring layer provided on at least one surface of the base material. As an example shown in FIG. 1, the base material 10 with a wiring layer has a first metal layer 12 and a second metal layer 13 which are a part of the base material 11 on both sides of the base material 11, respectively, and one of the first metal layers 13 is provided. The wiring layer 14 is provided on the surface of the metal layer 13 opposite to the surface of the metal layer 13 on the base material 11 side.

The details of the step (1) are as follows: a dry film (photosensitive resist film) is laminated on a base material, and exposed and developed under predetermined conditions using a photomask to form a pattern dry film. The developed pattern dry film is used as a plating mask to form a wiring layer by an electric field plating method, and then the pattern dry film is peeled off.

The material used for the first and second metal layers is not particularly limited. In a preferred embodiment, the first and second metal layers are preferably chromium, nickel, titanium, aluminum, zinc, gold, palladium, silver or copper from the viewpoint of cost, ease of etching, peeling and the like, and copper is preferable. More preferred.

The base material is not particularly limited as long as steps (1) to (4) can be carried out. Examples of the substrate include a glass epoxy substrate, a metal substrate, a polyester substrate, a polyimide substrate, a BT resin substrate, a thermosetting polyphenylene ether substrate, and the like, and a metal layer such as a copper foil is formed on the substrate surface. You may.

The dry film is not particularly limited as long as it is a photosensitive dry film made of a photoresist composition, and for example, a dry film such as a novolak resin or an acrylic resin can be used. As the dry film, a commercially available product may be used. For example, "ALPHO 20A263" manufactured by Nikko Materials Co., Ltd., which is a dry film with a PET film, can be used. The dry film may be laminated on one surface of the base material, or may be laminated on both sides of the base material as in the second embodiment described later.

The laminating conditions of the base material and the dry film are the same as the conditions for laminating the adhesive film in the step (2) described later so as to be embedded in the wiring layer, and the preferable range is also the same.

After laminating the dry film on the substrate, exposure and development are performed under predetermined conditions using a photomask to form a desired pattern on the dry film.

The line (circuit width) / space (width between circuits) ratio of the wiring layer is not particularly limited, but is preferably 20/20 μm or less (that is, the pitch is 40 μm or less), and more preferably 18/18 μm or less (pitch 36 μm or less). More preferably, it is 15/15 μm or less (pitch 30 μm or less). The lower limit of the line / space ratio of the wiring layer is not particularly limited, but is preferably 0.5 / 0.5 μm or more, and more preferably 1/1 μm or more. The pitch does not have to be the same throughout the wiring layer.

The minimum pitch of the wiring layer may be 40 μm or less, 36 μm or less, or 30 μm or less.

After forming the pattern of the dry film, a wiring layer is formed and the dry film is peeled off. Here, the formation of the wiring layer can be carried out by a plating method using a dry film having a desired pattern formed as a plating mask.

The conductor material used for the wiring layer is not particularly limited. In a preferred embodiment, the wiring layer is one or more selected from the group consisting of gold, platinum, palladium, silver, copper, aluminum, cobalt, chromium, zinc, nickel, titanium, tungsten, iron, tin and indium. Contains metal. The wiring layer may be a single metal layer or an alloy layer, and the alloy layer may be, for example, an alloy of two or more metals selected from the above group (for example, nickel-chromium alloy, copper, etc.). Nickel alloys and copper-titanium alloys). Among them, from the viewpoint of versatility of wiring layer formation, cost, ease of patterning, etc., a single metal layer of chromium, nickel, titanium, aluminum, zinc, gold, palladium, silver or copper, or a nickel-chromium alloy, copper, etc. An alloy layer of a nickel alloy or a copper-titanium alloy is preferable, and a single metal layer of chromium, nickel, titanium, aluminum, zinc, gold, palladium, silver or copper, or an alloy layer of a nickel-chromium alloy is more preferable. A metal layer is more preferred.

The thickness of the wiring layer depends on the desired wiring board design, but is preferably 3 μm to 35 μm, more preferably 5 μm to 30 μm, still more preferably 10 to 20 μm, or 15 μm.

After forming the wiring layer, the dry film is peeled off. The peeling of the dry film can be carried out using, for example, an alkaline stripping solution such as a sodium hydroxide solution. If necessary, an unnecessary wiring pattern can be removed by etching or the like to form a desired wiring pattern. The pitch of the wiring layer to be formed is as described above.

<Process (2)>
Step (2) is a step of laminating the adhesive film of the present invention on a base material with a wiring layer so that the wiring layer is embedded in the thermosetting resin composition layer, and heat-curing to form an insulating layer. is there. Since the thermosetting resin composition layer in the present invention exhibits good embedding property, it can be laminated without voids when laminated on a base material with a wiring layer. As an example shown in FIG. 2, the wiring layer 14 of the base material with the wiring layer obtained in the above step (1) is laminated so as to be embedded in the thermosetting resin composition layer 21 of the adhesive film 20. The thermosetting resin composition layer 21 of the adhesive film 20 is thermoset. The adhesive film 20 is formed by laminating the thermosetting resin composition layer 21 and the support 22 in this order.

First, as shown in FIG. 2, the thermosetting resin composition layer 21 of the adhesive film 20 is laminated on the base material with a wiring layer so that the wiring layer 14 is embedded.

The wiring layer and the adhesive film can be laminated by, for example, heat-pressing the adhesive film to the wiring layer from the support side after removing the protective film of the adhesive film. Examples of the member for heat-pressing the adhesive film to the wiring layer (hereinafter, also referred to as “heat-bonding member”) include a heated metal plate (SUS end plate or the like) or a metal roll (SUS roll). It is preferable not to press the heat-bonded member directly onto the adhesive film, but to press it through an elastic material such as heat-resistant rubber so that the adhesive film sufficiently follows the surface irregularities of the wiring layer.

The wiring layer and the adhesive film may be laminated by a vacuum laminating method after removing the protective film of the adhesive film. In the vacuum laminating method, the heat crimping temperature is preferably in the range of 60 ° C. to 160 ° C., more preferably 80 ° C. to 140 ° C., and the heat crimping pressure is preferably 0.098 MPa to 1.77 MPa, more preferably 0. It is in the range of .29 MPa to 1.47 MPa, and the heat crimping time is preferably in the range of 20 seconds to 400 seconds, more preferably 30 seconds to 300 seconds. Lamination is preferably carried out under reduced pressure conditions at a pressure of 13 hPa or less.

Lamination can be performed by a commercially available vacuum laminator. Examples of commercially available vacuum laminators include vacuum pressurized laminators manufactured by Nikko Materials Co., Ltd., vacuum pressurized laminators manufactured by Meiki Seisakusho Co., Ltd., and vacuum applicators manufactured by Nikko Materials Co., Ltd. Can be mentioned.

After the lamination, the laminated adhesive film may be smoothed by pressing the heat-bonded member from the support side under normal pressure (under atmospheric pressure), for example. The press conditions for the smoothing treatment can be the same as the heat-bonding conditions for the above-mentioned lamination. The smoothing process can be performed by a commercially available laminator. The lamination and smoothing treatment may be continuously performed using the above-mentioned commercially available vacuum laminator.

The thermosetting resin composition layer is laminated on the base material with the wiring layer so that the wiring layer is embedded, and then the thermosetting resin composition layer is thermally cured to form an insulating layer. The thermosetting conditions of the thermosetting resin composition layer are not particularly limited, and the conditions usually adopted when forming the insulating layer of the wiring board may be used.

For example, the thermosetting conditions of the thermosetting resin composition layer differ depending on the type of the thermosetting resin composition and the like, but the curing temperature is in the range of 120 ° C. to 240 ° C. (preferably in the range of 150 ° C. to 220 ° C.). It can be more preferably in the range of 170 ° C. to 200 ° C., and the curing time can be in the range of 5 minutes to 120 minutes (preferably 10 minutes to 100 minutes, more preferably 15 minutes to 90 minutes).

The thermosetting resin composition layer may be preheated at a temperature lower than the curing temperature before the thermosetting resin composition layer is thermally cured. For example, prior to thermosetting the thermosetting resin composition layer, the thermosetting is performed at a temperature of 50 ° C. or higher and lower than 120 ° C. (preferably 60 ° C. or higher and 110 ° C. or lower, more preferably 70 ° C. or higher and 100 ° C. or lower). The sex resin composition layer may be preheated for 5 minutes or longer (preferably 5 minutes to 150 minutes, more preferably 15 minutes to 120 minutes).

The support of the adhesive film may be peeled off after the adhesive film is laminated on the base material with a wiring layer and heat-cured, or the support may be peeled off before the adhesive film is laminated on the base material with a wiring layer. Good. Further, the support may be peeled off before the roughening treatment step described later.

The thickness of the insulating layer is the same as the thickness of the thermosetting resin composition layer, and the preferable range is also the same.

<Process (3)>
The step (3) in the first embodiment is a step of forming a via hole in the insulating layer and forming a conductor layer. Hereinafter, the description will be divided into a step of forming a via hole in the insulating layer (hereinafter, also referred to as “step (3-1)”) and a step of forming a conductor layer (hereinafter, also referred to as “step (3-2)”). To do.

-Step (3-1)-
The formation of the via hole is not particularly limited, and examples thereof include laser irradiation, etching, and mechanical drilling, but it is preferable that the via hole is formed by laser irradiation. For details, as shown in FIG. 3, in the step (3), after the support 22 is peeled off, laser irradiation is performed from the surface side of the adhesive film 20 to penetrate the support 22 and the insulating layer 21'. To form a via hole 31 that exposes the wiring layer 14.

This laser irradiation can be performed by using an arbitrary suitable laser processing machine that uses a carbon dioxide gas laser, a YAG laser, an excimer laser, or the like as a light source. Examples of the laser processing machine that can be used include a CO ₂ laser processing machine "LC-2k212 / 2C" manufactured by Via Mechanics Co., Ltd., 605GTWIII (-P) manufactured by Mitsubishi Electric Corporation, and Matsushita Welding System Co., Ltd. Laser processing machine can be mentioned.

The conditions of laser irradiation are not particularly limited, and laser irradiation can be carried out by any suitable step according to a conventional method according to the selected means.

The shape of the via hole, that is, the shape of the contour of the opening when viewed in the extending direction is not particularly limited, but is generally circular (substantially circular). Hereinafter, the term "diameter" of the via hole means the diameter (diameter) of the contour of the opening when viewed in the extending direction. In the present specification, the top diameter r1 means the diameter of the contour on the insulating layer 21'side of the via hole, and the bottom diameter r2 means the diameter of the contour on the wiring layer 14 side of the via hole (see FIGS. 3 and 4). ..

It is preferable to form the via hole so that the top diameter r1 of the via hole is 120 μm or less, preferably 90 μm or less.

As shown in FIG. 3, the via hole 31 may be formed so that r1 is larger than r2, and as shown in FIG. 4, the top diameter r1 of the via hole is the same as the bottom diameter r2 of the via hole 31. The via hole 31 may be formed so as to be.

By doing so, the embedding property of the via hole is improved, the generation of voids can be suppressed, and as a result, the reliability of the electrical connection by the filled via, which will be described later, can be improved.

After forming the via hole, a so-called desmear step, which is a smear removing step in the via hole, may be performed. When the step (3-2) described later is performed by the plating step, the via hole may be subjected to, for example, a wet desmear treatment, and when the step (3-2) is performed by the sputtering step, the via hole may be subjected to, for example, a wet desmear treatment. For example, a dry desmear step such as a plasma treatment step may be performed. Further, the desmear step may also serve as a roughening treatment step.

The step of performing the roughening treatment may be included before the step (3-2). The roughening treatment is performed on the via hole and the insulating layer, and the procedure and conditions of the roughening treatment are not particularly limited. For example, known procedures and conditions usually used for forming the insulating layer of the multilayer printed wiring board are used. Can be adopted. Examples of the dry roughening treatment include plasma treatment, and examples of the wet roughening treatment include a swelling treatment with a swelling liquid, a roughening treatment with an oxidizing agent, and a neutralization treatment with a neutralizing liquid in this order. Can be mentioned.

In the wet roughening treatment, for example, the swelling treatment with a swelling liquid, the roughening treatment with an oxidizing agent, and the neutralization treatment with a neutralizing liquid can be carried out in this order to roughen the insulating layer 21'. The swelling solution is not particularly limited, and examples thereof include an alkaline solution and a surfactant solution, and an alkaline solution is preferable, and the alkaline solution is more preferably a sodium hydroxide solution and a potassium hydroxide solution. Examples of commercially available swelling liquids include Swelling Dip Security SBU and Swelling Dip Security SBU manufactured by Atotech Japan Co., Ltd.

The swelling treatment with the swelling liquid is not particularly limited, but can be performed, for example, by immersing the insulating layer 21'in the swelling liquid at 30 ° C. to 90 ° C. for 1 minute to 20 minutes. From the viewpoint of suppressing the swelling of the resin of the insulating layer 21'to an appropriate level, it is preferable to immerse the insulating layer 21'in a swelling liquid at 40 ° C. to 80 ° C. for 5 seconds to 15 minutes. The oxidizing agent is not particularly limited, and examples thereof include an alkaline permanganate solution in which potassium permanganate or sodium permanganate is dissolved in an aqueous solution of sodium hydroxide. The roughening treatment with an oxidizing agent such as an alkaline permanganate solution is preferably carried out by immersing the insulating layer 21'in an oxidizing agent solution heated to 60 ° C. to 80 ° C. for 10 minutes to 30 minutes. The concentration of permanganate in the alkaline permanganate solution is preferably 5% by mass to 10% by mass. Examples of commercially available oxidizing agents include alkaline permanganate solutions such as Concentrate Compact P and Dozing Solution Security P manufactured by Atotech Japan Co., Ltd. The neutralizing solution is preferably an acidic aqueous solution, and examples of commercially available products include Reduction Solution Security P manufactured by Atotech Japan Co., Ltd.

The treatment with the neutralizing solution can be carried out by immersing the treated surface that has been roughened with the oxidizing agent solution in the neutralizing solution at 30 ° C. to 80 ° C. for 5 to 30 minutes. From the viewpoint of workability and the like, a method of immersing the object roughened with the oxidizing agent solution in a neutralizing solution at 40 ° C. to 70 ° C. for 5 to 20 minutes is preferable.

-Step (3-2)-
The conductor material constituting the conductor layer is not particularly limited. In a preferred embodiment, it can be formed of the same material as the conductor material used for the wiring pattern, and copper is preferably used as the material.

The conductor layer may have a single-layer structure, a single metal layer made of different types of metals or alloys, or a multi-layer structure in which two or more alloy layers are laminated. When the conductor layer has a multi-layer structure, the layer in contact with the insulating layer is preferably a single metal layer of chromium, zinc or titanium, or an alloy layer of nickel-chromium alloy.

The thickness of the conductor layer is generally 3 μm to 35 μm, preferably 5 μm to 30 μm, depending on the desired wiring board design.

The conductor layer can be formed by any conventionally known suitable method such as plating, sputtering, and thin film deposition, and is preferably formed by plating. In one preferred embodiment, the surface of the insulating layer can be plated by, for example, a conventionally known technique such as a semi-additive method or a full-additive method to form a conductor layer having a desired wiring pattern. Further, when the support in the adhesive film is a metal foil, a conductor layer having a desired wiring pattern can be formed by a conventionally known technique such as a subtractive method.

Specifically, a plating seed layer is formed on the surface of the insulating layer 21'by electroless plating. Next, a mask pattern that exposes a part of the plating seed layer corresponding to a desired wiring pattern is formed on the formed plating seed layer. An electric field plating layer is formed on the exposed plating seed layer by electrolytic plating, and then the mask pattern is removed. After that, the unnecessary plating seed layer can be removed by etching or the like to form a conductor layer having a desired wiring pattern.

As an example shown in FIG. 5, a plating seed layer 41 to be bonded to the surface of the exposed insulating layer 21'is formed. First, the surface of the insulating layer 21'is cleaned and alkaline cleaning is performed for charge adjustment. Next, a soft etching step is performed for cleaning the inside of the via hole 31. Specifically, the treatment may be carried out under arbitrary suitable conditions using an etchant such as an aqueous solution of sodium sulfate acidic peroxodisulfate. Next, a predip step of adjusting the charge on the surface of the insulating layer 21'is performed in order to apply Pd (palladium) to the surface of the insulating layer 21'. Next, Pd, which is an activator, is applied to the surface, and Pd applied to the insulating layer 21'is reduced. Next, copper (Cu) is deposited on the surface of the insulating layer 21'to form the plating seed layer 41. At this time, the plating seed layer 41 is formed so as to cover the inside of the via hole 31, that is, the side wall and the wiring layer 14 exposed from the via hole 31.

As shown in FIG. 6, after forming the plating seed layer 41, a mask pattern 50 that exposes a part of the plating seed layer 41 is formed. The mask pattern 50 can be formed, for example, by joining a dry film to the plating seed layer 41 and performing exposure, development, and washing under predetermined conditions.

The dry film that can be used in the step (3-2) is the same as the above-mentioned dry film, and the preferable range is also the same.

As an example shown in FIG. 7, an electric field plating layer 42 is formed on the exposed plating seed layer 41 by an electroplating treatment under the condition that the via holes 31 are filled, and the via holes are also embedded by the electric field plating treatment to fill the filled via 61. To form.

As an example shown in FIG. 8, the mask pattern is then peeled off and removed, and flash etching is performed under arbitrary suitable conditions to remove only the exposed plating seed layer 41 to form the pattern conductor layer 40.

The conductor layer may include not only linear wiring but also, for example, an electrode pad (land) on which an external terminal can be mounted. Further, the conductor layer may be composed of only the electrode pads.

Further, the conductor layer may be formed by forming an electric field plating layer and a filled via without using a mask pattern after forming the plating seed layer, and then performing patterning by etching.

<Process (4)>
The step (4) is a step of removing the base material and forming the wiring board of the present invention as shown in FIG. 9 as an example. The method for removing the base material is not particularly limited. In one preferred embodiment, the base material is peeled off from the wiring board at the interface between the first and second metal layers, and the second metal layer is removed by etching with, for example, an aqueous solution of copper chloride.

If necessary, the base material may be peeled off while the conductor layer 40 is protected by a protective film. The protective film is the same as the protective film used for the adhesive film, and the preferable range is also the same.

By such a manufacturing method of the present invention, it is possible to manufacture a wiring board in which the wiring layer 14 is embedded in the insulating layer 21'. Further, by including at least one insulating layer 21', a flexible wiring board can be obtained. Further, if necessary, the formation of the insulating layer and the conductor layer in the steps (2) to (3) may be repeated to form the multilayer wiring board. When manufacturing the multilayer wiring board, at least one adhesive film of the present invention may be used. Further, when a plurality of steps (3) are performed, in addition to the step of forming a via hole in the insulating layer and forming the conductor layer, a step of polishing or grinding the insulating layer to expose the wiring layer may be performed. Flexible means that the wiring board can be bent at least once without causing cracks or changes in resistance value.

2. Second Embodiment The first embodiment is a case where the step (3) is a step of forming a via hole in the insulating layer and forming a conductor layer, but in the second embodiment, the step (3) is a step of forming an insulating layer. It is the same as that of the first embodiment except that it is a step of polishing or grinding to expose the wiring layer. In each of the figures used in the following description, similar components may be indicated by the same reference numerals, and duplicate description may be omitted.

The step (1) is a step of preparing a base material with a wiring layer having a base material and wiring layers provided on both sides of the base material. The method of forming the wiring layer 14 is the same as that of the first embodiment. In the step (1) in the second embodiment, as shown by an example in FIG. 10, it is preferable that the thickness of each wiring layer 14 in the second embodiment is different.

The thickness of the thickest wiring layer (conductive pillar) among the wiring layers depends on the design of the desired wiring board, but is preferably 100 μm or less, more preferably 80 μm or less, still more preferably 60 μm or less, still more preferably. Is 40 μm or less or 20 μm or less. The lower limit is not particularly limited, but is preferably 2 μm or more, and more preferably 5 μm or more. The thickness of the wiring layer other than the thickest wiring layer is the same as the thickness of the wiring layer in the first embodiment, and the preferable range is also the same.

In step (2), as shown by an example in FIG. 11, the adhesive film of the present invention is laminated on a base material with a wiring layer so that the wiring layer is embedded in the thermosetting resin composition layer, and heat is applied. This is a step of curing to form an insulating layer, which is the same as that of the first embodiment, and the preferable range is also the same.

The step (3) is a step of polishing or grinding the insulating layer to expose the wiring layer. Unlike the step (3) in the first embodiment, since the via hole is not formed, the cost of forming the via hole can be significantly reduced.

As described above, as the wiring layer in the second embodiment, as shown in FIG. 1, each wiring layer may have a uniform thickness, and as shown in FIG. 10, each wiring may be used. The layers 14 may have different thicknesses. In the step (3), it is not necessary to expose all the wiring layers, and for example, a part of the wiring layer 14 may be exposed as shown in FIG. 12 as an example.

The method for polishing or grinding the insulating layer is not particularly limited as long as the wiring layer can be exposed and the polishing or grinding surface is horizontal, and a conventionally known polishing method or grinding method can be applied, for example. , A chemical mechanical polishing method using a chemical mechanical polishing device, a mechanical polishing method such as a buff, a surface grinding method by rotating a grindstone, and the like.

After the step (3), if necessary, a smear removing step and a roughening treatment step may be performed as in the first embodiment. Further, if necessary, the conductor layer may be formed as in the above-mentioned step (3-2).

The step (4) is a step of removing the base material and forming the wiring board of the present invention as shown in FIG. 13 as an example. The method for removing the base material is not particularly limited. In one preferred embodiment, the base material is peeled off from the wiring board at the interface between the first and second metal layers, and the second metal layer is removed by etching with, for example, an aqueous solution of copper chloride.

3. 3. Third Embodiment In the first embodiment, a wiring board is manufactured from a base material with a wiring layer having a wiring layer on one surface, but in the third embodiment, a group with a wiring layer having wiring layers on both sides of the base material. It is the same as the first embodiment except that the wiring board is manufactured from the material. In each of the figures used in the following description, similar components may be indicated by the same reference numerals, and duplicate description may be omitted.

Step (1) is a step of preparing a base material with a wiring layer having a base material and wiring layers provided on both sides of the base material, as shown in FIG. 14 as an example. The method of forming the wiring layer 14 is the same as that of the first embodiment. The wiring layers provided on both sides of the base material may be formed at the same time to prepare the base material with the wiring layer, and after the one wiring layer is formed, the other may be formed. The wiring layer of the above may be formed and a base material with a wiring layer may be prepared. Further, each wiring layer may have the same pattern or may have a different pattern. Further, the thickness of each wiring layer may be different as shown in FIG.

In step (2), as shown by an example in FIG. 15, an adhesive film is applied to both sides of the base material with a wiring layer, and a group with a wiring layer is embedded so that the wiring layer is embedded in the thermosetting resin composition layer. This is a process of laminating each on a material and thermosetting it. The two adhesive films used may be the same adhesive film or different adhesive films.

In step (3), as shown in FIG. 16, laser irradiation is performed on both sides of the base material with a wiring layer from the thermosetting adhesive film side to form via holes in the thermosetting adhesive film. Is preferable. The via holes may be formed at the same time, or one via hole may be formed and then the other via hole may be formed.

Before forming the conductor layer, a step of roughening both surfaces of the base material with a wiring layer may be included, and the surfaces of the two insulating layers 21'are roughened. The roughening treatment may be performed at the same time, or one roughening treatment may be performed followed by the other roughening treatment.

After forming the via hole, a conductor layer is formed on both sides of the base material with a wiring layer. As an example shown in FIG. 17, the plating seed layer 41 is formed on the insulating layer 21'after the roughening treatment. After forming the plating seed layer 41, a mask pattern 50 for exposing a part of the plating seed layer 41 is formed as shown in FIG. 18, and as shown in FIG. 19, on the exposed plating seed layer 41. The electroplating layer 42 is formed in the above, and the via holes are also embedded by the electroplating treatment to form the filled via 61. As shown in FIG. 20, the mask pattern is removed to form the conductor layer 40. The details of the formation of the conductor layer 40 can be performed in the same manner as in the first embodiment. Further, the two conductor layers provided on both sides of the base material may be formed at the same time, or one conductor layer may be formed and then the other conductor layer may be formed.

The case where the step (3) in the third embodiment is a step of forming a via hole in the insulating layer and forming a conductor layer has been described, but instead, a step of polishing or grinding the insulating layer to expose the wiring layer is performed. You may go. Further, a step of forming a via hole in the insulating layer and forming a conductor layer is performed on one surface of the base material with a wiring layer, and the insulating layer is polished or ground on the other surface to form a wiring layer. The step of exposing may be performed.

The step (4) is a step of removing the base material and forming the wiring board of the present invention, as shown in FIG. 21 as an example. In the third embodiment, it is possible to manufacture two types of wiring boards at the same time.

[Wiring board]
The wiring board of the present invention is characterized by comprising an insulating layer which is a cured product of the thermosetting resin composition layer of the adhesive film of the present invention, and an embedded wiring layer embedded in the insulating layer. In addition, the description overlapping with the above-mentioned contents may be omitted.

The wiring board of the present invention can be manufactured, for example, by the method for manufacturing a wiring board of the present invention, which includes the steps (1) to (4) above. As shown in FIG. 9, the wiring board 1 of the present invention is laminated in the order of the embedded wiring layer 14 and the insulating layer 21'. The conductor layer 40 is provided on the surface of the insulating layer 21'that is not joined to the embedded wiring layer 14 (that is, on the surface opposite to the embedded wiring layer 14). The embedded wiring layer 14 is joined to the conductor layer 40 via a filled via 61.

The embedded wiring layer refers to a wiring layer (wiring layer 14) embedded in the insulating layer 21'as long as conductor connection with a component such as a semiconductor chip is possible. The embedded wiring layer is usually embedded in an insulating layer so that its protruding height is substantially 0 (zero), usually -1 μm to + 1 μm, on the surface opposite to the side on which the adhesive film is laminated. It has been.

The wiring board of the present invention may be a multilayer wiring board as shown in FIGS. 22 and 23. The thermosetting resin compositions constituting the thermosetting resin composition layer forming the insulating layer in the wiring board shown in FIGS. 22 and 23 may have the same composition but different compositions. May be good. Further, as shown in FIG. 22, the top diameter and the bottom diameter of the filled via 61 may be substantially the same, and as shown in FIG. 23, the top diameter of the filled via 61 is larger than the bottom diameter. May be good.

The wiring board manufactured by using the adhesive film of the present invention exhibits a characteristic that the occurrence of warpage is suppressed. The amount of warpage is preferably 1 cm or less. The lower limit is not particularly limited, but is 0.01 mm or more. The warp can be measured according to the method described in <Evaluation of warp> described later.

The wiring board manufactured by using the adhesive film of the present invention exhibits a characteristic that the occurrence of cracks is suppressed. The length of the crack is preferably less than 1 mm. The lower limit is not particularly limited, but is 0.01 mm or more. The crack can be measured according to the method described in <Evaluation of crack> described later.

[Semiconductor device]
The semiconductor device of the present invention is characterized by including the wiring board of the present invention. The semiconductor device of the present invention can be manufactured by using the wiring board of the present invention.

Examples of semiconductor devices include various semiconductor devices used in electrical products (for example, computers, mobile phones, digital cameras, televisions, etc.) and vehicles (for example, motorcycles, automobiles, trains, ships, aircraft, etc.).

The semiconductor device of the present invention can be manufactured by mounting a component (semiconductor chip) on a conductive portion of a printed wiring board. The "conduction point" is a "place for transmitting an electric signal in the printed wiring board", and the place may be a surface or an embedded place. Further, the semiconductor chip is not particularly limited as long as it is an electric circuit element made of a semiconductor.

The method for mounting the semiconductor chip in manufacturing the semiconductor device of the present invention is not particularly limited as long as the semiconductor chip functions effectively, but specifically, a wire bonding mounting method, a flip chip mounting method, and no bumps. Examples thereof include a mounting method using a build-up layer (BBUL), a mounting method using an anisotropic conductive film (ACF), and a mounting method using a non-conductive film (NCF). Here, the "mounting method using the bumpless build-up layer (BBUL)" means "a mounting method in which the semiconductor chip is directly embedded in the recess of the printed wiring board and the semiconductor chip is connected to the wiring on the printed wiring board". Is.

Hereinafter, the present invention will be specifically described with reference to Examples, but the present invention is not limited to these Examples. In the following description, "parts" and "%" mean "parts by mass" and "% by mass", respectively, unless otherwise specified.

<Preparation of evaluation board>
(1) Step of preparing a base material with a wiring layer having a base material and a wiring layer provided on at least one surface of the base material (1-1) Lamination of a dry film on a base material (core substrate) As a core substrate, a glass cloth base material epoxy resin double-sided copper-clad laminate (layer structure: Microsin MT-Ex copper foil (thickness 3 μm copper foil / thickness 18 μm carrier foil) manufactured by Mitsui Metal Mining Co., Ltd.) / Panasonic "R1515A" substrate manufactured by Mitsui Metal Mining Co., Ltd. (thickness 0.2 mm) / Microsin MT-Ex copper foil manufactured by Mitsui Metal Mining Co., Ltd. (carrier foil with a thickness of 18 μm / copper foil with a thickness of 3 μm)) 170 × 110 mm square Prepared. A dry film with a PET film (“ALPHO 20A263” manufactured by Nikko Materials Co., Ltd., dry film thickness 20 μm) is bonded to the copper foil on both sides of the laminated plate on the matte surface side of the 3 μm copper foil. As described above, the film was laminated using a batch type vacuum pressurizing laminator (2-stage build-up laminator "CVP700" manufactured by Nikko Materials Co., Ltd.). The dry film was laminated by depressurizing for 30 seconds to reduce the atmospheric pressure to 13 hPa or less, and then crimping at a temperature of 70 ° C. and a pressure of 0.1 MPa for 20 seconds.

(1-2) Formation of pattern A glass mask (photomask) in which the wiring pattern shown below is formed is placed on a PET film which is a protective layer of a dry film, and UV is used at an irradiation intensity of 150 mJ / cm2 by a UV lamp. Irradiated. After UV irradiation, the PET film of the dry film was peeled off, and a 1% sodium carbonate aqueous solution at 30 ° C. was sprayed at an injection pressure of 0.15 MPa for 30 seconds. Then, it was washed with water and the dry film was developed (pattern formation).

Wiring pattern of glass mask:
Comb tooth patterns (wiring length 15 mm, 16 lines) with L / S = 15 μm / 15 μm, that is, a wiring pitch of 30 μm are formed at 10 mm intervals.

(1-3) Formation of Wiring Layer After the dry film was developed, electrolytic copper plating was performed to a thickness of 15 μm to form a wiring layer. Next, a 3% sodium hydroxide solution at 50 ° C. was spray-treated at an injection pressure of 0.2 MPa, the dry film was peeled off, washed with water, and dried at 150 ° C. for 30 minutes.

(2) A step of laminating an adhesive film on a base material with a wiring layer and heat-curing to form an insulating layer so that the wiring layer is embedded in a thermosetting resin composition layer (2-1) Laminating of an adhesive film The protective film of the adhesive film (167 mm × 107 mm) produced in Examples and Comparative Examples was peeled off, and a batch type vacuum pressure laminator (2-stage build-up laminator "CVP700" manufactured by Nikko Materials Co., Ltd.) was used. Using, the thermosetting resin composition layer was embedded and laminated on both sides of the wiring layer so as to be bonded to the wiring layer. Lamination was carried out by reducing the pressure for 30 seconds to reduce the atmospheric pressure to 13 hPa or less, and then crimping at 110 ° C. and a pressure of 0.74 MPa for 30 seconds. Next, the laminated adhesive film was heat-pressed at 110 ° C. and a pressure of 0.5 MPa for 60 seconds under atmospheric pressure to smooth it.

(2-2) Thermosetting of Thermosetting Resin Composition Layer After laminating the adhesive film, the support (PET film) is peeled off, and the thermosetting resin is prepared at 100 ° C. for 30 minutes and then at 170 ° C. for 30 minutes. The composition layer was thermoset to form insulating layers on both sides of the wiring layer.

(3) Step of forming a via hole in the insulating layer A laser is irradiated from above the insulating layer from above the insulating layer using a _{CO 2 laser machine "605GTWIII (-P)" manufactured by Mitsubishi Electric Corporation.} A via hole having a top diameter (75 μm) was formed in the insulating layer directly above the 150 μm square wiring layer, which is the land of the comb-tooth wiring pattern. The laser irradiation conditions were a mask diameter of 2.5 mm, a pulse width of 16 μs, an energy of 0.36 mJ / shot, a number of shots of 3, and a burst mode (10 kHz).

(3-1) Step of roughening treatment A desmear treatment was performed on a structure provided with via holes. As the desmear treatment, the following wet desmear treatment was carried out.

Wet desmear treatment:
The circuit board provided with the via hole was placed in a swelling solution (“Swelling Dip Securigant P” manufactured by Atotech Japan Co., Ltd., an aqueous solution of diethylene glycol monobutyl ether and sodium hydroxide) at 60 ° C. for 5 minutes, and then an oxidizing agent solution ( "Concentrate Compact CP" manufactured by Atotech Japan Co., Ltd., an aqueous solution with a potassium permanganate concentration of about 6% and a sodium hydroxide concentration of about 4%) at 80 ° C. for 10 minutes, and finally a neutralizing solution (Atotech Japan Co., Ltd.) ), "Reduction Solution Securigant P", aqueous sulfuric acid solution) at 40 ° C. for 5 minutes, and then dried at 80 ° C. for 15 minutes.

(3-2) Step of forming a conductor layer (3-2-1) Electrolytic plating step In order to form a conductor layer on the surface of the evaluation substrate, a plating step including the following steps 1 to 6 (Atotech Japan Co., Ltd.) A conductor layer was formed by performing a copper plating step) using a chemical solution made in Japan.

1. 1. Alkaline cleaning (cleaning of the surface of the insulating layer with via holes and charge adjustment)
Product name: Cleaning was performed at 60 ° C. for 5 minutes using Cleaning Cleaner Security 902 (trade name).
2. Soft etching (cleaning inside the via hole)
Treatment was carried out at 30 ° C. for 1 minute using an aqueous sodium sulfate-acidic peroxodisulfate solution.
3. 3. Predip (Adjustment of charge on the surface of the insulating layer for Pd application)
Pre. Treatment was performed at room temperature for 1 minute using Dip Neoganth B (trade name).
4. Add activator (give Pd to the surface of the insulating layer)
Treatment was performed at 35 ° C. for 5 minutes using Activator Neoganth 834 (trade name).
5. Reduction (Reduction of Pd applied to the insulating layer)
Reducer Neoganth WA (trade name) and Reducer Acceralator 810 mod. Using a mixed solution with (trade name), the treatment was carried out at 30 ° C. for 5 minutes.
6. Electroless copper plating process (Cu is deposited on the surface of the insulating layer (Pd surface))
A mixture of Basic Solution Printganth MSK-DK (trade name), Copper solution Printganth MSK (trade name), Stabilizer Printganth MSK-DK (trade name), and Reducer Cu (trade name) at 35 ° C. Treated for 20 minutes. The thickness of the formed electroless copper plating layer was 0.8 μm.

(3-2-2) Electroplating Step Next, using a chemical solution manufactured by Atotech Japan Co., Ltd., an electrolytic copper plating step was performed under the condition that the via hole was filled with copper. After that, as a resist pattern for patterning by etching, a land pattern having a diameter of 150 μm corresponding to the via hole is formed (the portion without the via connection is also formed on the entire surface at a pitch of 600 μm), and this land pattern is used to form the surface of the insulating layer. A conductor layer having a conductor pattern with a thickness of 15 μm was formed on the surface. Next, the annealing treatment was performed at 190 ° C. for 90 minutes.

(4) Step of removing the base material After adhering a PET film with an adhesive (thickness 50 μm) to the entire surface of the base material with a wiring layer on which a conductor layer is formed, the micro-thin MT-Ex copper foil of the core substrate is used. A cutter blade was inserted into the interface between a copper foil having a thickness of 3 μm and a carrier foil having a thickness of 18 μm, and the core substrate was peeled off and separated. Next, the surface on which the conductor layer was formed was protected by a PET film with an adhesive, and a 3 μm copper foil was etched and removed with an aqueous solution of copper chloride, washed with water, and then dried at 110 ° C. for 30 minutes. Then, the PET film with an adhesive was peeled off to prepare a wiring board in which an L / S = 15/15 μm comb tooth pattern was embedded on one side. The obtained wiring board is referred to as "evaluation board A".

<Evaluation of warpage>
Of the four sides of the evaluation board A, it is fixed to the SUS plate with an adhesive tape (product name: Kapton adhesive tape, manufactured by Teraoka Seisakusho Co., Ltd.) with a width of 107 mm, and the warp value is obtained by obtaining the height of the highest point from the SUS plate. Asked. This operation was repeated 4 times, and the case where the average value was less than 1 cm and the magnitude of the warp was "◯" and the case where the average value was 1 cm or more was "x".

<Evaluation of cracks>
The presence or absence of resin cracks on the four sides of the evaluation substrate A was visually observed with an optical microscope. Those without resin cracks (length 1 mm or more) were designated as "○", and those without resin cracks were designated as "x" (n = 4).

<Measurement of average linear thermal expansion coefficient (coefficient of thermal expansion)>
The untreated surface of the release PET film ("501010" manufactured by Lintec Co., Ltd., thickness 38 μm, 240 mm square) is a glass cloth base material epoxy resin double-sided copper-clad laminate ("R5715ES" manufactured by Matsushita Electric Works Co., Ltd., thickness. It was placed on a glass cloth-based epoxy resin double-sided copper-clad laminate so as to be in contact with (0.7 mm, 255 mm square), and the four sides of the release film were fixed with polyimide adhesive tape (width 10 mm).

Each adhesive film (167 × 107 mm square) produced in Examples and Comparative Examples has a thermosetting resin composition using a batch type vacuum pressure laminator (2-stage build-up laminator CVP700 manufactured by Nikko Materials Co., Ltd.). The material layer was laminated in the center so as to be in contact with the release surface of the release PET film. The laminating treatment was carried out by reducing the pressure for 30 seconds to reduce the atmospheric pressure to 13 hPa or less, and then crimping at 100 ° C. and a pressure of 0.74 MPa for 30 seconds.

Then, the support was peeled off, and the thermosetting resin composition layer was heat-cured under the curing conditions of 190 ° C. for 90 minutes.

After thermosetting, the polyimide adhesive tape was peeled off, and the thermosetting resin composition layer was removed from the glass cloth base material epoxy resin double-sided copper-clad laminate. Further, the release PET film was peeled off from the thermosetting resin composition layer to obtain a sheet-like cured product. The sheet-shaped cured product is referred to as an evaluation cured product. The obtained cured product is cut into test pieces having a width of 5 mm and a length of 15 mm, and thermomechanical analysis is performed by a tensile weight method using a thermomechanical analyzer (“Thermo Plus TMA8310” manufactured by Rigaku Co., Ltd.). It was. Specifically, after the test piece was attached to the thermomechanical analyzer, the measurement was carried out twice in succession under the measurement conditions of a load of 1 g and a heating rate of 5 ° C./min. Then, in the second measurement, the average linear thermal expansion coefficient (α1; ppm / ° C.) in the plane direction in the range of 30 ° C. to 150 ° C. was calculated. This operation was performed three times, and the average value is shown in the table.

<Measurement of elastic modulus and breaking strength>
The cured product for evaluation was cut into a dumbbell-shaped No. 1 shape to obtain a test piece. The test piece was subjected to tensile strength measurement using a tensile tester "RTC-1250A" manufactured by Orientec, and the elastic modulus and breaking strength at 25 ° C. were determined. The measurement was carried out in accordance with JIS K7127. This operation was performed three times, and the average value is shown in the table.

<Measurement of average maximum diameter of domain>
The FIB-SEM composite device (“SMI3050SE” manufactured by SII Nanotechnology Co., Ltd.) was applied to the thermosetting resin composition layer of the adhesive film that was thermally cured at 100 ° C. for 30 minutes and then at 170 ° C. for 30 minutes. A cross section in a direction perpendicular to the surface of the thermosetting adhesive film was carved out by the FIB (focused ion beam) in the above, and a cross section SEM image (observation width 60 μm, observation magnification 2,000 times) was obtained. The cross-sectional SEM images of 5 randomly selected points were observed, and the maximum diameters of 20 arbitrarily selected domains (4 points / each cut surface) were measured, and the average value was taken as the average maximum diameter. Those having an average maximum diameter of 15 μm or less were designated as “◯”, and those having an average maximum diameter of more than 15 μm were designated as “x”.

<Example 1>
Biphenyl type epoxy resin ("ZX1059" manufactured by Nippon Steel Chemical Co., Ltd., 1: 1 mixture of bisphenol A type and bisphenol F type, epoxy equivalent 169), 5 parts, biphenyl type epoxy resin (manufactured by Nippon Kayaku Co., Ltd.) "NC3000L", epoxy equivalent 269) 10 parts, naphthalene type tetrafunctional epoxy resin ("HP-4710" manufactured by DIC Co., Ltd., epoxy equivalent 163) 15 parts, naphthalene type epoxy resin ("EXA7311-G4" manufactured by DIC Co., Ltd. , Epoxy equivalent 213) 15 parts, Polybutadiene skeleton-containing epoxy resin (“PB3600” manufactured by Daicel Co., Ltd., number average molecular weight Mn: 5900 g / mol, epoxy equivalent 190) 20 parts, methyl ethyl ketone (MEK) 15 parts, cyclohexanone 15 parts Was dissolved by heating with stirring. The melted product is cooled to room temperature, and then there, a triazine-containing phenol novolac resin (“LA-7554” manufactured by DIC Co., Ltd., hydroxyl group equivalent 125, nitrogen content about 12% by weight, solid content 60% by weight MEK). 10 parts of solution), 25 parts of naphthol-based curing agent (“HPC-9500” manufactured by DIC Co., Ltd., MEK solution having a hydroxyl group equivalent of 153 and a solid content of 60% by weight), curing accelerator (manufactured by Shikoku Kasei Kogyo Co., Ltd., “ 1B2PZ ”, 1-benzyl-2-phenylimidazole, MEK solution with a solid content of 3% by mass) and 1 part, and a phenylaminosilane-based coupling agent (“KBM573” manufactured by Shin-Etsu Chemical Industry Co., Ltd.) were surface-treated. 260 parts of spherical silica (average particle size 0.5 μm, "SOC2" manufactured by Admatex Co., Ltd.) is mixed, uniformly dispersed with a high-speed rotating mixer, and filtered through a cartridge filter ("SHP050" manufactured by ROKITECHNO). , Resin varnish 1 was prepared.

Next, the resin varnish 1 was uniformly applied onto a polyethylene terephthalate film (Lumirror "T6AM" manufactured by Toray Co., Ltd., thickness 38 μm) so that the thickness of the thermosetting resin composition layer after drying was 80 μm. After drying at ~ 120 ° C. (average 100 ° C.) for 6 minutes, the rough surface of the protective film (polypropylene film, "Alfan MA-430" manufactured by Oji Ftex Co., Ltd., thickness 20 μm) is subjected to a thermosetting resin composition. An adhesive film 1 was produced by laminating them so as to be bonded to a physical layer.

The FIB-SEM composite device (“SMI3050SE” manufactured by SII Nanotechnology Co., Ltd.) was applied to the thermosetting resin composition layer of the adhesive film 1 which was thermally cured at 100 ° C. for 30 minutes and then at 170 ° C. for 30 minutes. ) Was used to observe the cross section, and it was found that the component (b) was not clearly dispersed in the domain, and was compatible with or close to the component other than the component (b).

<Example 2>
Biphenyl type epoxy resin ("ZX1059" manufactured by Nippon Steel Chemical Co., Ltd., 1: 1 mixture of bisphenol A type and bisphenol F type, epoxy equivalent 169), 5 parts, biphenyl type epoxy resin (manufactured by Nippon Kayaku Co., Ltd.) "NC3000L", epoxy equivalent 269) 10 parts, naphthalene type tetrafunctional epoxy resin ("HP-4710" manufactured by DIC Co., Ltd., epoxy equivalent 163) 15 parts, naphthalene type epoxy resin ("EXA7311-G4S" manufactured by DIC Co., Ltd. , Epoxy equivalent 187) 15 parts, epoxy group-containing acrylic acid ester copolymer (“SG-80H” manufactured by Nagase ChemteX Corporation, number average molecular weight Mn: 350,000 g / mol, epoxy value 0.07 eq / kg, solid content 110 parts of 18 mass% MEK solution) was dissolved by heating in 10 parts of methyl ethyl ketone (MEK) and 10 parts of cyclohexanone with stirring. The heat-dissolved product is cooled to room temperature, and a triazine skeleton-containing phenol-based curing agent (DIC Co., Ltd. "LA-3018-50P", hydroxyl group equivalent of about 151, 2-methoxypropanol solution having a solid content of 50%) is added thereto. 20 parts, naphthol-based curing agent ("HPC-9500" manufactured by DIC Co., Ltd., MEK solution having a hydroxyl group equivalent of 153 and a solid content of 60% by weight) 25 parts, curing accelerator (manufactured by Shikoku Kasei Kogyo Co., Ltd., "1B2PZ" , 1-benzyl-2-phenylimidazole, MEK solution with a solid content of 3% by mass), and spherical silica surface-treated with a phenylaminosilane-based coupling agent (manufactured by Shin-Etsu Chemical Industry Co., Ltd., "KBM573"). (Average particle size 1 μm, “SOC4” manufactured by Admatex Co., Ltd.) 360 parts, mixed, uniformly dispersed with a high-speed rotating mixer, filtered with a cartridge filter (“SHP100” manufactured by ROKITECHNO), and resin varnish 2 Was prepared, and the adhesive film 2 was prepared in the same manner as in Example 1.

The FIB-SEM composite device (“SMI3050SE” manufactured by SII Nanotechnology Co., Ltd.) was applied to the thermosetting resin composition layer of the adhesive film 2 which was thermally cured at 100 ° C. for 30 minutes and then at 170 ° C. for 30 minutes. ) Was used to observe the cross section, and it was found that the component (b) was not clearly dispersed in the domain, and was compatible with or close to the component other than the component (b).

<Example 3>
80 parts of polymer resin A manufactured as shown below, bisphenol type epoxy resin (“ZX1059” manufactured by Nippon Steel Chemical Co., Ltd., 1: 1 mixture of bisphenol A type and bisphenol F type, epoxy equivalent 169) 3 18 parts of dicyclopentadiene type epoxy resin (“HP-7200” manufactured by DIC Co., Ltd., epoxy equivalent 260), 18 parts of naphthalene type tetrafunctional epoxy resin (“HP-4710” manufactured by DIC Co., Ltd., epoxy equivalent 163) 3 Parts were dissolved by heating in 10 parts of methyl ethyl ketone (MEK) and 10 parts of cyclohexanone with stirring. The heat-dissolved product is cooled to room temperature, and 5 parts of a naphthol-based curing agent (“HPC-9500” manufactured by DIC Co., Ltd., MEK solution having a hydroxyl group equivalent of 153 and a solid content of 60% by weight) and an active ester compound ( "HPC-8000-65T" manufactured by DIC Co., Ltd., 2 parts of a toluene solution having a weight average molecular weight of about 2700 and an active group equivalent of about 223 and a non-volatile content of 65% by mass), a curing accelerator (4-dimethylaminopyridine (DMAP)) , MEK solution with a solid content of 5% by mass), curing accelerator (manufactured by Shikoku Kasei Kogyo Co., Ltd., "1B2PZ", 1-benzyl-2-phenylimidazole, MEK solution with a solid content of 3% by mass), 2 parts, And 300 parts of spherical silica (average particle size 1 μm, “SOC4” manufactured by Admatex Co., Ltd.) surface-treated with a phenylaminosilane-based coupling agent (“KBM573” manufactured by Shin-Etsu Chemical Industry Co., Ltd.) are mixed. A resin varnish 3 was prepared by uniformly dispersing with a high-speed rotating mixer and filtering with a cartridge filter (“SHP100” manufactured by ROKITECHNO), and an adhesive film 3 was prepared in the same manner as in Example 1.

The FIB-SEM composite device (“SMI3050SE” manufactured by SII Nanotechnology Co., Ltd.) was applied to the thermosetting resin composition layer of the adhesive film 3 which was thermally cured at 100 ° C. for 30 minutes and then at 170 ° C. for 30 minutes. ) Was used to observe the cross section, and it was found that the component (b) was not clearly dispersed in the domain, and was compatible with or close to the component other than the component (b).

[Manufacturing of polymer resin A]
G-3000 (bifunctional hydroxyl group-terminated polybutadiene, number average molecular weight = 5047 (GPC method), hydroxyl group equivalent = 1798 g / eq., Solid content 100% by mass: manufactured by Nippon Soda Co., Ltd.) 50 g in a reaction vessel. 23.5 g of Ipsol 150 (aromatic hydrocarbon mixed solvent: manufactured by Idemitsu Petrochemical Co., Ltd.) and 0.005 g of dibutyltin laurate were mixed and uniformly dissolved. When the temperature became uniform, the temperature was raised to 50 ° C., and 4.8 g of toluene-2,4-diisocyanate (isocyanate group equivalent = 87.08 g / eq.) Was added with further stirring, and the reaction was carried out for about 3 hours. Next, the reaction product is cooled to room temperature, and then 8.96 g of benzophenone tetracarboxylic dianhydride (acid anhydride equivalent = 161.1 g / eq.), 0.07 g of triethylenediamine, and ethyldiglycol are added to the reaction product. 40.4 g of acetate (manufactured by Daicel Co., Ltd.) was added, the temperature was raised to 130 ° C. with stirring, and the reaction was carried out for about 4 hours. The disappearance of the NCO peak of ^{2250 cm -1} was confirmed from FT-IR. The confirmation of the disappearance of the NCO peak was regarded as the end point of the reaction, and the reaction product was cooled to room temperature and then filtered through a 100-mesh filter cloth to obtain a polymer resin A having an imide structure, a urethane structure, and a polybutadiene structure.
Viscosity: 7.5 Pa · s (25 ° C, E-type viscometer)
Acid value: 16.9 mgKOH / g
Solid content: 50% by mass
Number average molecular weight: 13723
Glass transition temperature: -10 ° C
Content of polybutadiene structural part: 50 / (50 + 4.8 + 8.96) x 100 = 78.4% by mass

<Comparative example 1>
Biphenyl type epoxy resin ("ZX1059" manufactured by Nippon Steel Chemical Co., Ltd., 1: 1 mixture of bisphenol A type and bisphenol F type, epoxy equivalent 169), 5 parts, biphenyl type epoxy resin (manufactured by Nippon Kayaku Co., Ltd.) "NC3000L", epoxy equivalent 269) 10 parts, naphthalene type tetrafunctional epoxy resin ("HP-4710" manufactured by DIC Co., Ltd., epoxy equivalent 163) 15 parts, naphthalene type epoxy resin ("EXA7311-G4S" manufactured by DIC Co., Ltd. , Epoxy equivalent 187) 15 parts were dissolved by heating in 10 parts of methyl ethyl ketone (MEK) and 10 parts of cyclohexanone with stirring. The melted product is cooled to room temperature, and then there, a triazine-containing phenol novolac resin (“LA-7854” manufactured by DIC Co., Ltd., hydroxyl group equivalent 125, nitrogen content about 12% by weight, solid content 60% by weight MEK). 10 parts of solution), 25 parts of naphthol-based curing agent (“HPC-9500” manufactured by DIC Co., Ltd., MEK solution having a hydroxyl group equivalent of 153 and a solid content of 60% by weight), curing accelerator (manufactured by Shikoku Kasei Kogyo Co., Ltd., “ 1B2PZ ”, 1-benzyl-2-phenylimidazole, MEK solution having a solid content of 3% by mass), and a phenylaminosilane-based coupling agent (“KBM573” manufactured by Shin-Etsu Chemical Industry Co., Ltd.). 200 parts of spherical silica (average particle size 0.5 μm, "SOC2" manufactured by Admatex Co., Ltd.) is mixed, uniformly dispersed with a high-speed rotating mixer, and filtered with a cartridge filter ("SHP050" manufactured by ROKITECHNO). , A resin varnish 4 was prepared, and an adhesive film 4 was prepared in the same manner as in Example 1.

<Comparative example 2>
80 parts of polymer resin A, bisphenol type epoxy resin ("ZX1059" manufactured by Nippon Steel Chemical Co., Ltd., 1: 1 mixture of bisphenol A type and bisphenol F type, epoxy equivalent 169), 5 parts, biphenyl type epoxy resin (Nippon Kayaku Co., Ltd. "NC3000L", epoxy equivalent 269) was dissolved by heating in 6 parts of methyl ethyl ketone (MEK) and 6 parts of cyclohexanone with stirring. The heat-dissolved product is cooled to room temperature, and the active ester compound (“HPC-8000-65T” manufactured by DIC Co., Ltd.) has a weight average molecular weight of about 2700 and an active group equivalent of about 223, and has a non-volatile content of 65% by mass. 2 parts of toluene solution), 1 part of curing accelerator (4-dimethylaminopyridine (DMAP), MEK solution with 5% by mass of solid content), curing accelerator (manufactured by Shikoku Kasei Kogyo Co., Ltd., "1B2PZ", 1-benzyl -2-Phenylimidazole, 2 parts of MEK solution with a solid content of 3% by mass), and spherical silica (average particle size) surface-treated with a phenylaminosilane-based coupling agent (manufactured by Shin-Etsu Chemical Industry Co., Ltd., "KBM573"). 1 μm, 250 parts of “SOC4” manufactured by Admatex Co., Ltd.) were mixed, uniformly dispersed with a high-speed rotary mixer, and filtered with a cartridge filter (“SHP100” manufactured by ROKITECHNO) to prepare a resin varnish 5. The adhesive film 5 was produced in the same manner as in Example 1.

When the cross section of the thermosetting resin composition layer of the thermosetting adhesive film 5 was observed in the same manner as in the adhesive film 3, the average maximum diameter exceeded 15 μm as shown in FIG. 24.

<Comparative example 3>
Biphenyl type epoxy resin ("ZX1059" manufactured by Nippon Steel Chemical Co., Ltd., 1: 1 mixture of bisphenol A type and bisphenol F type, epoxy equivalent 169), 7 parts, biphenyl type epoxy resin (manufactured by Nippon Kayaku Co., Ltd.) "NC3000L", epoxy equivalent 269) 10 parts, naphthalene type tetrafunctional epoxy resin ("HP-4710" manufactured by DIC Co., Ltd., epoxy equivalent 163) 15 parts, naphthalene type epoxy resin ("EXA7311-G4" manufactured by DIC Co., Ltd. , Epoxy equivalent 213) 15 parts, Polybutadiene skeleton-containing epoxy resin (“PB3600” manufactured by Daicel Co., Ltd., number average molecular weight Mn: 5900 g / mol, epoxy equivalent 190) 5 parts, methyl ethyl ketone (MEK) 10 parts, cyclohexanone 10 parts Was dissolved by heating with stirring. The heat-dissolved product is cooled to room temperature, and a triazine skeleton-containing phenol-based curing agent (DIC Co., Ltd. "LA-3018-50P", hydroxyl group equivalent of about 151, 2-methoxypropanol solution having a solid content of 50%) is added thereto. 20 parts, naphthol-based curing agent ("HPC-9500" manufactured by DIC Co., Ltd., MEK solution having a hydroxyl group equivalent of 153 and a solid content of 60% by weight) 25 parts, curing accelerator (manufactured by Shikoku Kasei Kogyo Co., Ltd., "1B2PZ" , 1-benzyl-2-phenylimidazole, MEK solution with a solid content of 3% by mass), and spherical silica surface-treated with a phenylaminosilane-based coupling agent (manufactured by Shinetsu Chemical Industry Co., Ltd., "KBM573"). (Average particle size 0.5 μm, “SOC2” manufactured by Admatex Co., Ltd.) 200 parts, mixed, uniformly dispersed with a high-speed rotating mixer, filtered with a cartridge filter (“SHP050” manufactured by ROKITECHNO), and resin. A varnish 6 was prepared, and an adhesive film 6 was prepared in the same manner as in Example 1.

<Examples 4 to 6>
In Examples 1 to 3, each component (d) was surface-treated with a phenylaminosilane-based coupling agent (manufactured by Shinetsu Chemical Industry Co., Ltd., “KBM573”) (average particle size 3 μm, manufactured by Denka Co., Ltd.” It was replaced with DAW-03 "). A resin composition and an adhesive film were produced in the same manner as in Examples 1 to 3 except for the above items. These adhesive films had sufficiently small warpage when manufacturing a wiring board provided with an embedded wiring layer, and could form an insulating layer in which cracks and the like did not occur. Further, in Examples 4 to 6, the average coefficient of linear thermal expansion, elastic modulus, breaking strength, and average maximum diameter of the domain were also good results as in Examples 1 to 3.

1 Wiring board 10 Base material with wiring layer 11 Base material (core substrate)
12 1st metal layer 13 2nd metal layer 14 Wiring layer (embedded wiring layer)
20 Adhesive film 21 Thermosetting resin composition layer 21'Insulation layer 22 Support 23 Protective film 31 Via hole 40 Conductor layer 41 Plating seed layer 42 Electroplating layer 50 Mask pattern 61 Field via

Claims (20)

(1) A step of preparing a base material with a wiring layer having a base material and a wiring layer provided on at least one surface of the base material.
(2) An adhesive film containing a thermosetting resin composition layer is laminated on a base material with a wiring layer so that the wiring layer is embedded in the thermosetting resin composition layer, and is thermally cured to form an insulating layer. Process,
(3) Steps of connecting wiring layers between layers, and (4) Steps of removing a base material,
An adhesive film used in the manufacturing method of wiring boards, including
The adhesive film contains a support and a thermosetting resin composition layer.
The average linear thermal expansion coefficient of the cured product obtained by thermally curing the thermosetting resin composition layer at 30 ° C. to 150 ° C. is 16 ppm / ° C. or less.
The elastic modulus of the cured product obtained by thermosetting the thermosetting resin composition layer at 25 ° C. is 12 GPa or less.
An adhesive film having a breaking strength at 25 ° C. of a cured product obtained by thermosetting the thermosetting resin composition layer at 25 MPa or more. The first aspect of claim 1, wherein the step (3) is at least one of a step of forming a via hole in the insulating layer to form a conductor layer and a step of polishing or grinding the insulating layer to expose the wiring layer. Adhesive film. The thermosetting resin composition layer comprises a thermosetting resin composition, and the thermosetting resin composition is (a) an epoxy resin having an aromatic structure, and (b) a glass transition temperature of 25 ° C. or lower or 25 ° C. The adhesive film according to claim 1 or 2 , which comprises a liquid polymer resin, (c) a curing agent, and (d) an inorganic filler. (B) One or more components selected from the group consisting of a polyalkylene structure, a polyalkyleneoxy structure, a polybutadiene structure, a polyisoprene structure, a polyisobutylene structure, a polycarbonate structure, a poly (meth) acrylate structure, and a polysiloxane structure. The adhesive film according to claim 3 , which has a structure. (B) The component is a resin having an imide structure, an acrylic resin, a butadiene resin having a number average molecular weight (Mn) of 7500 or more, a carbonate resin, a polysiloxane resin, an alkylene resin, an alkyleneoxy resin, an isoprene resin, an isobutylene resin, and an acrylic rubber. The adhesive film according to claim 3 or 4, which is one or more selected from the group consisting of particles, polyamide particles, and silicone particles. The invention according to any one of claims 3 to 5, wherein the component (b) is a resin having a functional group (excluding an epoxy group) or a resin containing an epoxy group and having no aromatic structure. Adhesive film. The content of the component (b) is 2% by mass to 13% by mass when the non-volatile component in the thermosetting resin composition is 100% by mass, according to any one of claims 3 to 6. Adhesive film. (D) The adhesive film according to any one of claims 3 to 7 , wherein the component is selected from silica or alumina. The adhesive film according to any one of claims 3 to 8 , wherein the content of the component (d) is 73% by mass or more when the non-volatile component in the thermosetting resin composition is 100% by mass. The adhesion according to any one of claims 3 to 9 , wherein the mixing ratio (mass ratio) of the component (d) and the component (b) is (component (d) / component (b)) 5 to 45. the film. (1) A step of preparing a base material with a wiring layer having a base material and a wiring layer provided on at least one surface of the base material.
(2) The adhesive film according to any one of claims 1 to 10 is laminated on a base material with a wiring layer and thermosetting so that the wiring layer is embedded in the thermosetting resin composition layer. The process of forming an insulating layer,
(3) The process of connecting the wiring layers between layers and
(4) Step of removing the base material,
A method of manufacturing a wiring board, including. 11. The step (3) is at least one of a step of forming a via hole in the insulating layer to form a conductor layer and a step of polishing or grinding the insulating layer to expose the wiring layer, according to claim 11 . the method of. The method according to claim 11 or 12 , wherein the step (3) is a step of forming a via hole in the insulating layer and forming a conductor layer, which is performed by laser irradiation. 13. The method of claim 13, comprising a step of roughening before forming the conductor layer. The method according to any one of claims 11 to 14 , wherein the wiring board is a flexible wiring board. The method according to any one of claims 11 to 15 , wherein the minimum pitch of the wiring pattern is 40 μm or less. A wiring board comprising an insulating layer which is a cured product of the thermosetting resin composition layer of the adhesive film according to any one of claims 1 to 10 and an embedded wiring layer embedded in the insulating layer. The wiring board according to claim 17 , which is a flexible wiring board. The wiring board according to claim 17 or 18 , wherein the thickness of the insulating layer is 2 μm or more. A semiconductor device comprising the wiring board according to any one of claims 17 to 19.

Images