KR102556112B1 - Adhesive film - Google Patents

Abstract

[Problem] Provision of an adhesive film or the like capable of forming an insulating layer that does not cause warpage, cracks, or the like when manufacturing a wiring board having a buried type wiring layer.
[Means for solving] (1) a step of preparing a base material with a wiring layer having a base material and a wiring layer formed on at least one surface of the base material; An adhesive film used in a wiring board manufacturing method including a step of forming an insulating layer by laminating on a substrate with a wiring layer so as to be embedded and curing by heat, (3) interlayer connection of the wiring layer, and (4) a step of removing the substrate. , The cured product obtained by thermally curing the thermosetting resin composition layer has an average linear thermal expansion coefficient of 16 ppm/°C or less, an elastic modulus of 12 GPa or less, and a breaking strength of 45 MPa or more.

Description

Adhesive film {ADHESIVE FILM}

The present invention relates to an adhesive film. It also 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 laminated is widely used, and it is known that the insulating layer is formed by curing a resin composition (for example, Patent Document 1 reference).

Japanese Unexamined Patent Publication No. 2015-82535

BACKGROUND OF THE INVENTION [0002] In recent years, light, thin, and miniaturization of electronic devices has been progressing. Accordingly, there is a demand for a flexible wiring board that can be bent and accommodated in an electronic device. Further, in order to enable further thinning of the wiring board, a wiring board having a buried type wiring layer is required.

As an insulating layer used in a wiring board having a buried wiring layer, a hard, highly filled inorganic filler is used to reduce the mismatch of the average coefficient of thermal expansion (Coefficient of Thermal Expansion: CTE, also referred to as coefficient of thermal expansion) between the wiring layer and components. material has been used. However, there was a problem that warpage would occur when manufacturing a wiring board provided with a buried type wiring layer.

Further, as an insulating layer used for a wiring board with an embedded wiring layer, use of a material in which a flexible resin is highly filled with an inorganic filler has been studied in order to lower the average linear thermal expansion coefficient, but a wiring board with an embedded wiring layer has been studied. There was a problem that cracks would occur during production.

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 cause warpage or cracking when manufacturing a wiring board having a buried type wiring layer, and 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 formed on at least one surface of the base material;

(2) Laminating an adhesive film containing a thermosetting resin composition layer on a base material with a wiring layer so that the wiring layer is embedded in the thermosetting resin composition layer, and thermally curing to form an insulating layer;

(3) a step of connecting the wiring layers between layers; and

(4) Step of removing substrate

An adhesive film used in a method for manufacturing a wiring board comprising:

The adhesive film includes a support and a thermosetting resin composition layer,

The cured product obtained by thermally curing the thermosetting resin composition layer has an average coefficient of linear thermal expansion at 30 ° C to 150 ° C of 16 ppm / ° C or less,

The cured product obtained by thermally curing the thermosetting resin composition layer has an elastic modulus at 25° C. of 12 GPa or less,

An adhesive film having a breaking strength at 25°C of a cured product obtained by thermally curing a layer of a thermosetting resin composition of 45 MPa or more.

[2] In [1], step (3) is at least one of a step of forming a via hole in the insulating layer and forming a conductor layer, and a step of polishing or grinding the insulating layer to expose the wiring layer process, adhesive film.

[3] An adhesive film used in the manufacture of a wiring board having an insulating layer and a buried wiring layer embedded in the insulating layer,

The adhesive film includes a support and a thermosetting resin composition layer,

The insulating layer is a cured product of a thermosetting resin composition layer,

The cured product of the thermosetting resin composition layer has an average coefficient of linear thermal expansion at 30 ° C to 150 ° C of 16 ppm / ° C or less,

The cured product of the thermosetting resin composition layer has an elastic modulus at 25° C. of 12 GPa or less,

An adhesive film having a breaking strength at 25°C of a cured product of a thermosetting resin composition layer of 45 MPa or more.

[4] The method of any one of [1] to [3], wherein the thermosetting resin composition layer is made of a thermosetting resin composition, and the thermosetting resin composition comprises: (a) an epoxy resin having an aromatic structure; (b) a glass transition temperature An adhesive film comprising a polymer resin at 25° C. or less or liquid at 25° C., (c) a curing agent, and (d) an inorganic filler.

[5] The component (b) according to [4] is a polyalkylene structure, a polyalkyleneoxy structure, a polybutadiene structure, a polyisoprene structure, a polyisobutylene structure, a polycarbonate structure, a poly(meth)acrylate structure. , And having at least one structure selected from the group consisting of polysiloxane structure, the adhesive film.

[6] The adhesive film according to [4] or [5], wherein the content of component (b) is 2% by mass to 13% by mass based on 100% by mass of the non-volatile component in the thermosetting resin composition.

[7] The adhesive film according to any one of [4] to [6], wherein component (d) is selected from silica or alumina.

[8] The adhesive film according to any one of [4] to [7], wherein the content of component (d) is 73% by mass or more based on 100% by mass of the non-volatile component in the thermosetting resin composition.

[9] The adhesive according to any one of [4] to [8], wherein the mixing ratio (mass ratio) of component (d) and component (b) (component (d)/component (b)) is 5 to 45. film.

[10] (1) A step of preparing a base material with a wiring layer having a base material and a wiring layer formed on at least one surface of the base material;

(2) Laminating the adhesive film according to any one of [1] to [9] on a base material with a wiring layer so that the wiring layer is embedded in the thermosetting resin composition layer, and thermally curing to form an insulating layer;

(3) a step of connecting the wiring layers between layers; and

(4) a step of removing the substrate;

A method for manufacturing a wiring board comprising:

[11] In [10], step (3) is at least one of a step of forming a via hole in the insulating layer and forming a conductor layer, and a step of polishing or grinding the insulating layer to expose the wiring layer fair man, how.

[12] The method according to [10] or [11], wherein step (3) is a step of forming a via hole in the insulating layer and forming a conductor layer, and is performed by laser irradiation.

[13] The method according to [12], including a step of performing a roughening treatment before forming the 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] A wiring board comprising an insulating layer that is a cured product of the thermosetting resin composition layer of the adhesive film according to any one of [1] to [9], and a buried wiring layer embedded in the insulating layer.

[17] The wiring board according to [16], which is a flexible wiring board.

[18] The wiring board according to [16] or [17], wherein the insulating layer has a thickness of 2 μm or more.

[19] A semiconductor device comprising 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 cause warpage or cracking when manufacturing a wiring board having a buried wiring layer, a method for manufacturing a wiring board using the same, a wiring board, and a semiconductor device are provided. can

1 is a schematic cross-sectional view for explaining a manufacturing process of a wiring board.
2 is a schematic cross-sectional view for explaining a manufacturing process of a wiring board.
3 is a schematic cross-sectional view for explaining a manufacturing process of a wiring board.
4 is a schematic cross-sectional view for explaining a manufacturing process of a wiring board.
5 is a schematic cross-sectional view for explaining a manufacturing process of a wiring board.
6 is a schematic cross-sectional view for explaining a manufacturing process of a wiring board.
7 is a schematic cross-sectional view for explaining a manufacturing process of a wiring board.
8 is a schematic cross-sectional view for explaining a manufacturing process of a wiring board.
9 is a schematic cross-sectional view for explaining a manufacturing process of a wiring board.
10 is a schematic cross-sectional view for explaining a manufacturing process of a wiring board.
11 is a schematic cross-sectional view for explaining a manufacturing process of a wiring board.
12 is a schematic cross-sectional view for explaining a manufacturing process of a wiring board.
13 is a schematic sectional view for explaining a manufacturing process of a wiring board.
14 is a schematic cross-sectional view for explaining a manufacturing process of a wiring board.
15 is a schematic cross-sectional view for explaining a manufacturing process of a wiring board.
16 is a schematic cross-sectional view for explaining a manufacturing process of a wiring board.
17 is a schematic cross-sectional view for explaining a manufacturing process of a wiring board.
18 is a schematic cross-sectional view for explaining a manufacturing process of a wiring board.
19 is a schematic cross-sectional view for explaining a manufacturing process of a wiring board.
20 is a schematic cross-sectional view for explaining a manufacturing process of a wiring board.
21 is a schematic cross-sectional view for explaining a manufacturing process of a wiring board.
22 is a schematic cross-sectional view for explaining the wiring board.
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, a method for manufacturing a wiring board, a wiring board, and a 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 formed on at least one surface of the base material, (2) an adhesive film containing a thermosetting resin composition layer, wherein the wiring layer is thermosetting A method for producing a wiring board including a step of laminating on a base material with a wiring layer so as to be embedded in a resin composition layer and forming an insulating layer by thermal curing, (3) a step of connecting the wiring layers between layers, and (4) a step of removing the base material. As an adhesive film used for, the adhesive film includes a support and a thermosetting resin composition layer, and a cured product obtained by thermally curing the thermosetting resin composition layer has an average linear thermal expansion coefficient of 16 ppm / ° C or less at 30 ° C to 150 ° C , The elastic modulus at 25 ° C. of a cured product obtained by thermally curing the thermosetting resin composition layer is 12 GPa or less, and the breaking strength at 25 ° C. (also referred to as “breaking strength”) of the cured product obtained by thermally curing the thermosetting resin composition layer is Characterized in that it is 45 MPa or more.

In addition, the adhesive film of the present invention is an adhesive film used for manufacturing a wiring board having an insulating layer and a buried wiring layer embedded in the insulating layer, wherein the adhesive film includes a support and a thermosetting resin composition layer, and the insulating layer is thermosetting. The cured product of the thermosetting resin composition layer has an average linear thermal expansion coefficient of 16 ppm/°C or less at 30° C. to 150° C., and the cured product of the thermosetting resin composition layer has an elastic modulus at 25° C. of 12 GPa or less. And, the cured product of the thermosetting resin composition layer is characterized in that the breaking strength at 25 ° C. is 45 MPa or more.

The adhesive film of the present invention includes a support and a thermosetting resin composition layer, and in one embodiment, the adhesive film includes a support and a thermosetting resin composition layer bonded to the support, and the thermosetting resin composition layer is thermosetting. It is composed of a 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 plastic material, metal foil, and release paper, and a film made of plastic material and metal foil are preferable.

When using a film made of a plastic material as the support, examples of the plastic material include polyethylene terephthalate (hereinafter sometimes abbreviated as "PET") and polyethylene naphthalate (hereinafter abbreviated as "PEN"). ), polyesters such as polycarbonate (hereinafter sometimes abbreviated as "PC"), acrylics such as polymethyl methacrylate (PMMA), cyclic polyolefins, triacetyl cellulose (TAC), polyether sulfide (PES) ), polyether ketone, polyimide and the like. Among these, polyethylene terephthalate and polyethylene naphthalate are preferable, and inexpensive polyethylene terephthalate is particularly preferable.

When using metal foil as a support body, as a metal foil, copper foil, aluminum foil, etc. are mentioned, for example, and copper foil is preferable. As the copper foil, foil made of a single metal of copper may be used, or foil made of an alloy of copper and another metal (eg, tin, chromium, silver, magnesium, nickel, zirconium, silicon, titanium, etc.) may be used. In addition, as the metal foil, one in which a plurality of metal foils are laminated may be used.

The support may be subjected to a mat treatment or a corona treatment to the surface to be bonded to the thermosetting resin composition layer.

Moreover, as a support body, you may use the support body with a release layer which has a release layer on the surface to be joined with a thermosetting resin composition layer. As a mold release agent used for the mold release layer of the support body with a mold release layer, 1 or more types of mold release agents chosen from the group which consists of alkyd resins, polyolefin resins, urethane resins, and silicone resins are mentioned, for example. A support with a release layer may use a commercial item, for example, "SK-1", "AL-5", "AL -7", Toray Co., Ltd. product "Lumiror T6AM", etc. are mentioned.

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. Moreover, when using a support body with a release layer, it is preferable that the thickness of the whole support body with a release layer is the said range.

<Thermosetting resin composition layer>

The adhesive film of the present invention includes a thermosetting resin composition layer, and the thermosetting resin composition layer is composed of the thermosetting resin composition. As will be described in detail later, when manufacturing a wiring board, the wiring layer is embedded in the thermosetting resin composition layer, thereby forming an embedded type wiring layer. The thermosetting resin composition (hereinafter also referred to as "resin composition") constituting the thermosetting resin composition layer is not particularly limited, and any cured product thereof 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 when forming an insulating layer of a wiring board can be used, and among these, an epoxy resin having an aromatic structure is preferable. In addition, from the viewpoint of lowering the elastic modulus and the average linear thermal expansion coefficient of the cured product of the thermosetting resin composition layer and suppressing the occurrence of warpage of the wiring board that can be produced using the adhesive film of the present invention, the thermosetting resin composition has a glass transition temperature includes a polymer resin that is 25° C. or less or liquid at 25° C., and an inorganic filler. Accordingly, in one embodiment, the thermosetting resin composition includes (a) an epoxy resin having an aromatic structure, (b) a polymer resin having a glass transition temperature of 25° C. or less or liquid at 25° C., (c) a curing agent, and (d) an inorganic resin. Contains filling material. The thermosetting resin composition may further contain additives such as (e) a curing accelerator, (f) a thermoplastic resin (except those corresponding to the component (b)), and (g) a flame retardant, if necessary.

-(a) Epoxy resin having an aromatic structure-

An epoxy resin having an aromatic structure (hereinafter, simply referred to as "epoxy resin") is not particularly limited as long as it has an aromatic structure. An aromatic structure is a chemical structure generally defined as aromatic, and includes polycyclic aromatics and aromatic heterocycles. As the epoxy resin, for example, bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, bisphenol AF type epoxy resin, dicyclopentadiene type epoxy resin, trisphenol type epoxy resin, naphthol 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, bixylenol type epoxy resin, glycidyl amine type epoxy resin having an aromatic structure , A glycidyl ester type epoxy resin having an aromatic structure, a cresol novolac type epoxy resin, a biphenyl type epoxy resin, a linear aliphatic epoxy resin having an aromatic structure, an epoxy resin having a butadiene structure having an aromatic structure, an epoxy resin having an aromatic structure An alicyclic epoxy resin, a heterocyclic epoxy resin, a spiro ring-containing epoxy resin having an aromatic structure, a cyclohexanedimethanol type epoxy resin having an aromatic structure, a naphthylene ether type epoxy resin, a trimethylol type epoxy resin having an aromatic structure, an aromatic structure Tetraphenyl ethane type epoxy resin etc. which have are mentioned. An epoxy resin may be used individually by 1 type, and may be used in combination of 2 or more type. The component (a) is preferably at least one selected from the group consisting of bisphenol A type epoxy resins, bisphenol F type epoxy resins, and biphenyl type epoxy resins.

It is preferable that an epoxy resin contains the epoxy resin which has 2 or more epoxy groups in 1 molecule. When the non-volatile component of the epoxy resin is 100% by mass, it is preferable that at least 50% by mass or more is 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 being liquid at a temperature of 20°C (hereinafter referred to as "liquid epoxy resin"), and having three or more epoxy groups in one molecule and being in a solid state at a temperature of 20°C. It is preferable to contain an epoxy resin (henceforth "solid-state epoxy resin"). As the epoxy resin, a resin composition having excellent flexibility can be obtained by using a liquid epoxy resin and a solid epoxy resin together. Moreover, the breaking strength of the cured product of the resin composition is also improved.

As the liquid epoxy resin, 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, glycidyl amine type epoxy having an aromatic structure Resins, phenol novolak-type epoxy resins, alicyclic epoxy resins having an ester skeleton having an aromatic structure, cyclohexane dimethanol-type epoxy resins having an aromatic structure, and epoxy resins having a butadiene structure having an aromatic structure are preferred, and bisphenol A A type epoxy resin, a bisphenol F type epoxy resin, a bisphenol AF type epoxy resin, and a naphthalene type epoxy resin are more preferable, and a bisphenol A type epoxy resin and a bisphenol F type epoxy resin are still more preferable. As specific examples of the liquid epoxy resin, "HP4032", "HP4032D", "HP4032SS" (naphthalene type epoxy resin) manufactured by DIC Corporation, "828US" manufactured by Mitsubishi Chemical Corporation, "jER828EL" (bisphenol A type) Epoxy resin), “jER807” (bisphenol F-type epoxy resin), “jER152” (phenol novolak-type epoxy resin), “630”, “630LSD” (glycidyl amine-type epoxy resin), Nippon Steel Sumikin Chemical Co., Ltd. "ZX1059" (mixture of bisphenol A type epoxy resin and bisphenol F type epoxy resin), Nagase Chemtex Co., Ltd. "EX-721" (glycidyl ester type epoxy resin), (shares) ) "Celoxide 2021P" (alicyclic epoxy resin having an ester skeleton) manufactured by Daicel, "ZX1658" and "ZX1658GS" (liquid 1,4-glycidylcyclohexane) manufactured by Nippon Steel Chemical Co., Ltd. can be heard These may be used individually by 1 type, and may be used in combination of 2 or more type.

As the solid epoxy resin, a naphthalene type tetrafunctional epoxy resin, a cresol novolak type epoxy resin, a dicyclopentadiene type epoxy resin having an aromatic structure, a trisphenol type epoxy resin, a naphthol type epoxy resin, a biphenyl type epoxy resin, and a naphthylene ether. Type epoxy resins, anthracene type epoxy resins, bisphenol A type epoxy resins, tetraphenyl ethane type epoxy resins are preferred, and naphthalene type tetrafunctional epoxy resins, naphthol type epoxy resins, and biphenyl type epoxy resins and naphthylene ether type epoxy resins are preferred. is more preferable, and a naphthalene type tetrafunctional epoxy resin and a naphthylene ether type epoxy resin are still more preferable. Specific examples of the solid epoxy resin include "HP-4032H" (naphthalene type epoxy resin), "HP-4700", "HP-4710" (naphthalene type tetrafunctional epoxy resin), and "N-690" manufactured by DIC Co., Ltd. (cresol novolak type epoxy resin), "N-695" (cresol novolak type epoxy resin), "HP-7200" (dicyclopentadiene type epoxy resin), "HP-7200HH", "HP-7200H", "EXA7311", "EXA7311-G3", "EXA7311-G4", "EXA7311-G4S", "HP-6000" (naphthylene ether type epoxy resin), "EPPN-502H" manufactured by Nippon Kayaku Co., Ltd. ( trisphenol type epoxy resin), "NC7000L" (naphthol novolak type epoxy resin), "NC3000H", "NC3000", "NC3000L", "NC3100" (biphenyl type epoxy resin), Nippon Steel Sumikin Chemical Co., Ltd. ) "ESN475V" (naphthol type epoxy resin), "ESN485" (naphthol novolak type epoxy resin), "YX4000H", "YL6121" (biphenyl type epoxy resin), "YX4000HK" manufactured by Mitsubishi Chemical Corporation " (bixylenol type epoxy resin), "YX8800" (anthracene type epoxy resin), "PG-100" and "CG-500" manufactured by Osaka Gas Chemical Co., Ltd., "YL7800" manufactured by Mitsubishi Chemical Corporation (fluorene type epoxy resin), "jER1010" (solid bisphenol A type epoxy resin), "jER1031S" (tetraphenyl ethane type epoxy resin), "YL7760" (bisphenol AF type epoxy resin) manufactured by Mitsubishi Chemical Corporation etc. can be mentioned.

As the liquid epoxy resin, an aromatic epoxy resin having two or more epoxy groups in one molecule and being liquid at a temperature of 20°C is preferable. Epoxy resins are preferred. In addition, the aromatic epoxy resin as used in the present invention means an epoxy resin having an aromatic ring structure in its molecule.

As the epoxy resin, when a liquid epoxy resin and a solid epoxy resin are used together, their ratio (liquid epoxy resin:solid epoxy resin) is preferably in the range of 1:0.1 to 1:20 in terms of mass ratio. By setting the amount ratio of the liquid epoxy resin and the solid epoxy resin within this range, i) when used in the form of an adhesive film, appropriate adhesiveness can be formed, ii) when used in the form of an adhesive sheet, sufficient flexibility can be obtained, , handling is improved, and iii) a cured product having sufficient breaking strength can be obtained. From the viewpoint of the above effects of i) to iii), the amount ratio of the liquid epoxy resin to the solid epoxy resin (liquid epoxy resin:solid epoxy resin) is more preferably in the range of 1:0.3 to 1:10 in terms of mass ratio, and 1:0.6 to 1:9 is more preferred.

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 6% by mass, from the viewpoint of obtaining an insulating layer exhibiting good mechanical strength and insulation reliability. More than that. 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, and more preferably 40% by mass or less.

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

The epoxy equivalent of the epoxy resin is preferably 50 to 5000, more preferably 50 to 3000, even more preferably 80 to 2000, still more preferably 110 to 1000. By setting it as this range, the crosslinking density of hardened|cured material becomes sufficient and an insulating layer with small surface roughness can be formed. In addition, epoxy equivalent can be measured according to JIS K7236, and is the mass of resin containing an epoxy group of 1 equivalent.

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

- (b) Polymer resins with a glass transition temperature of 25 ° C or less or liquid at 25 ° C -

The thermosetting resin composition contains component (b). As the component (b), only a polymer resin having a glass transition temperature of 25°C or less may be used, or only a polymer resin that is liquid at 25°C may be used, and a polymer resin having a glass transition temperature of 25°C or less and a liquid polymer resin at 25°C may be used. You may use it combining a polymer resin. By including a flexible polymer resin such as component (b), the elastic modulus and thermal expansion coefficient of the cured product of the thermosetting resin composition layer can be reduced, and also the occurrence of warping of a wiring board that can be manufactured using the adhesive film of the present invention can be suppressed. there is.

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

It is preferable that component (b) has a functional group capable of reacting with 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 suitable embodiment, the functional group of component (b) is at least one functional group 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. Especially, as said 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 containing an epoxy group as a functional group, it is preferable that (b) component does not have an aromatic structure.

Component (b) is a polyalkylene structure, a polyalkyleneoxy structure, a polybutadiene structure, a polyisoprene structure, a polyisobutylene structure, a polycarbonate structure, a poly( It preferably has at least one structure selected from the group consisting of a meth)acrylate structure and a polysiloxane structure, and more preferably has at least one structure selected from the group consisting of a polybutadiene structure and a poly(meth)acrylate structure. In addition, "(meth)acrylate" refers to a methacrylate and an acrylate.

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

The polyalkyleneoxy structure is preferably a polyalkyleneoxy structure of 2 to 15 carbon atoms, more preferably a polyalkyleneoxy structure of 3 to 10 carbon atoms, more preferably a polyalkyleneoxy structure of 5 to 6 carbon atoms. It is a polyalkyleneoxy structure.

One suitable embodiment of component (b) is a butadiene resin. As the butadiene resin, a butadiene resin that is liquid at 25° C. or has a glass transition temperature of 25° C. or lower is preferable, and hydrogenated polybutadiene skeleton-containing resins (eg, hydrogenated polybutadiene skeleton-containing epoxy resins), hydroxy group-containing butadiene resins, phenolic A butadiene resin containing a hydroxyl group (resin having a polybutadiene structure and having a phenolic hydroxyl group), a butadiene resin containing a carboxyl group, a butadiene resin containing an acid anhydride group, a butadiene resin containing an epoxy group, a butadiene resin containing an isocyanate group, and a butadiene resin containing a urethane group. At least one resin selected from the group is more preferred, and a phenolic hydroxyl group-containing butadiene resin is still more preferred. Here, "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 in the side chain. Part or all of the polybutadiene structure may be hydrogenated. Here, "hydrogenated polybutadiene skeleton-containing resin" refers to a resin in which at least a part of the polybutadiene skeleton is hydrogenated, and it is not necessarily a resin in which the polybutadiene skeleton is completely hydrogenated.

The number average molecular weight (Mn) of the butadiene resin is preferably 1,000 to 100,000, more preferably 5,000 to 50,000, still more preferably 7,500 to 30,000, still more preferably 10,000 to 15,000. Here, the number average molecular weight (Mn) of the resin is a number average molecular weight in terms of polystyrene 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. In addition, a functional group equivalent is the number of grams of resin containing the functional group of 1 gram equivalent. For example, the epoxy group equivalent can be measured according to JIS K7236. The hydroxyl 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) manufactured by Cray Valley, "Ricon 130MA8", "Ricon 130MA13", "Ricon 130MA20", "Ricon 131MA5", "Ricon 131MA10", and "Ricon 131MA17". ", "Ricon 131MA20", "Ricon 184MA6" (polybutadiene containing an acid anhydride group), "JP-100" and "JP-200" (epoxidized polybutadiene) manufactured by Nippon Soda Co., Ltd., "GQ-1000" (hydroxyl group) , Carboxyl group-introduced polybutadiene), "G-1000", "G-2000", "G-3000" (both terminal hydroxyl polybutadiene), "GI-1000", "GI-2000", "GI-3000" ( Hydrogenated polybutadiene at both terminals), "PB3600" and "PB4700" (polybutadiene backbone epoxy resin) manufactured by Daicel, "EpoFriend A1005", "EpoFriend A1010" and "EpoFriend A1020" (styrene, butadiene and styrene block copolymer epoxide), "FCA-061L" (hydrogenated polybutadiene skeleton epoxy resin), "R-45EPT" (polybutadiene skeleton epoxy resin) manufactured by Nagase ChemteX Co., Ltd., and the like.

Furthermore, as another preferred embodiment of the component (b), a resin having an imide structure can also be used. As such component (b), a linear polyimide using a hydroxyl group-terminated polybutadiene, a diisocyanate compound, and a tetrabasic acid anhydride as raw materials (Polyi described in Japanese Unexamined Patent Publication No. 2006-37083 and International Publication No. 2008/153208) Mead) and the like. 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. The detail of the said polyimide resin can consider description of Unexamined-Japanese-Patent No. 2006-37083 and international publication 2008/153208, and this content is integrated in this specification.

A more preferable 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 100000, more preferably 10000 to 15000. Here, the number average molecular weight (Mn) of the resin is a number average molecular weight in terms of polystyrene 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 suitable embodiment of component (b) is an acrylic resin. As the acrylic resin, an acrylic resin having a glass transition temperature (Tg) of 25° C. or less is preferable, and is preferably an acrylic resin containing a hydroxyl group, an acrylic resin containing a phenolic hydroxyl group, an acrylic resin containing a carboxyl group, an acrylic resin containing an acid anhydride group, and an acrylic resin containing an epoxy group. , at least one resin selected from the group consisting of an isocyanate group-containing acrylic resin and a urethane group-containing acrylic resin is more preferred. Here, "acrylic resin" refers to resin containing a (meth)acrylate structure, and in these resins, the (meth)acrylate structure may be contained in the main chain or may be contained in 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 number average molecular weight in terms of polystyrene measured using GPC (gel permeation chromatography).

The functional group equivalent in case the acrylic resin has a functional group is preferably 1000 to 50000, more preferably 2500 to 30000.

Specific examples of the acrylic resin include Teisan Resin "SG-70L", "SG-708-6", "WS-023", "SG-700AS", and "SG-280TEA" (carboxyl group-containing acrylic acid esters) manufactured by Nagase ChemteX Co., Ltd. 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" (containing an epoxy group) Acrylic acid 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”” (hydroxyl group-containing acrylic acid ester copolymer) Polymer resin, hydroxyl value of 20 to 40 mgKOH/g, weight average molecular weight of 500,000 to 1.200,000, Tg of -37 to -32°C), "ME-2000" and "W-116.3" manufactured by Negami Kogyo Co., Ltd. (acrylic acid containing a carboxyl group) 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.

Also, one preferred embodiment of 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 carbonate resins containing a hydroxyl group, carbonate resins containing a phenolic hydroxyl group, carbonate resins containing a carboxyl group, carbonate resins containing an acid anhydride group, carbonate resins containing an epoxy group, and isocyanate group-containing resins. At least one resin selected from the group consisting of carbonate resins and urethane group-containing carbonate resins is preferred. Here, "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 in 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 preferred ranges are also the same.

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

In addition, a linear polyimide (PCT/JP2016/053609) made of a hydroxyl group-terminated polycarbonate, a diisocyanate compound, and a tetrabasic acid anhydride as raw materials can also be used. The content of the carbonate structure of the polyimide resin is preferably 60% by mass to 95% by mass, more preferably 75% by mass to 85% by mass. The detail of the said polyimide resin can consider description of PCT/JP2016/053609, and this content is integrated in this specification.

Further, more suitable embodiments of the component (b) are polysiloxane resins, alkylene resins, alkyleneoxy resins, isoprene resins, and isobutylene resins.

As a specific example of the polysiloxane resin, "SMP-2006", "SMP-2003PGMEA", "SMP-5005PGMEA" manufactured by Shin-Etsu Silicone Co., Ltd., amine-terminated polysiloxane, linear polyimide using tetrabasic acid anhydride as a raw material (International Publication No. 2010/ 053185) and the like.

Specific examples of the alkylene resin include "PTXG-1000" and "PTXG-1800" manufactured by Asahi Kasei Seni, and "YX-7180" manufactured by Mitsubishi Chemical Corporation (resin containing an alkylene structure having an ether bond). can be heard

Specific examples of the alkyleneoxy resin include "EXA-4850-150", "EXA-4816" and "EXA-4822" manufactured by DIC Corporation, "EP-4000", "EP-4003" and "EP-4010" manufactured by ADEKA. ”, and “EP-4011”, “BEO-60E” and “BPO-20E” manufactured by Shinnippon Rika Co., Ltd., and “YL7175” and “YL7410” manufactured by Mitsubishi Chemical Corporation.

As a specific example of isoprene resin, "KL-610" by the Kuraray company, "KL613", etc. are mentioned.

Specific examples of the isobutylene resin include "SIBSTAR-073T" (styrene-isobutylene-styrene triblock copolymer) and "SIBSTAR-042D" (styrene-isobutylene diblock copolymer) manufactured by Kaneka Corporation. there is.

Further, as more suitable embodiments of the component (b), acrylic rubber particles, polyamide fine particles, silicone particles and the like can be given. As a specific example of the acrylic rubber particles, a resin that exhibits rubber elasticity such as acrylonitrile butadiene rubber, butadiene rubber, acrylic rubber, etc. is subjected to chemical crosslinking treatment to make it insoluble and insoluble in organic solvents. Fine particles are exemplified, specifically, XER-91 (manufactured by Nippon Kosei Rubber Co., Ltd.), Staphyloid AC3355, AC3816, AC3832, AC4030, AC3364, IM101 (above, manufactured by Gantz Kasei Co., Ltd.), Pararoid EXL2655, EXL2602 (Above, manufactured by Kureha Chemical Industry Co., Ltd.), etc. are mentioned. As specific examples of the polyamide fine particles, any aliphatic polyamide such as nylon or even a flexible skeleton such as polyamideimide may be used. can be heard

From the viewpoint of improving the breaking strength, the component (b) is preferably highly compatible with components other than the component (b). That is, it is preferable that the component (b) is dispersed in the layer of the thermosetting resin composition. In addition, the component (b) may form a domain and be dispersed in the thermosetting resin composition layer. The average maximum diameter of the domains is preferably 15 μm or less, more preferably 10 μm or less, and even more preferably 5 μm or less, or not dispersed (average maximum diameter of the domains is 0 μm).

The average maximum diameter of the domains can be measured as follows. Cross-section observation of the thermosetting resin composition layer of the adhesive film heat-cured at 100°C for 30 minutes and then at 170°C for 30 minutes using a FIB-SEM composite device ("SMI3050SE" manufactured by SII Nanotechnology Co., Ltd.) did. Specifically, a cross section in a direction perpendicular to the surface of the adhesive film was cut by FIB (Focused Ion Beam) to obtain a cross-sectional SEM image (observation width 60 µm, observation magnification: 2,000 times). Cross-sectional SEM images of 5 randomly selected locations were observed, and the maximum diameters of 20 randomly selected domains (4 points/each cross section) were measured, and the average value was taken as the average maximum diameter. The maximum diameter refers to a diameter that becomes the largest among diameters of a domain.

The content of 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, still more preferably 11% by mass or less. The lower limit is preferably 2% by mass or more, more preferably 3% by mass or more, and even more preferably 4% by mass or more.

-(c) curing agent-

The curing agent is not particularly limited as long as it has a function of curing the epoxy resin, and examples thereof include phenol-based curing agents, naphthol-based curing agents, active ester-based curing agents, benzoxazine-based curing agents, cyanate ester-based curing agents, and carbodiimide-based curing agents. A curing agent etc. are mentioned. A curing agent may be used individually by 1 type, or may use 2 or more types together. Component (c) is preferably at least one selected from phenol-based curing agents, naphthol-based curing agents, active ester-based curing agents, and cyanate ester-based curing agents.

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

Specific examples of the phenol-based curing agent and the naphthol-based curing agent include "MEH-7700", "MEH-7810", and "MEH-7851" manufactured by Maywa Kasei Co., Ltd., and "NHN" manufactured by Nippon Kayaku Co., Ltd. ", "CBN", "GPH", "SN170", "SN180", "SN190", "SN475", "SN485", "SN495V", "SN375", "SN395" manufactured by Nippon Steel Sumikin Co., Ltd. "TD-2090", "LA-7052", "LA-7054", "LA-1356", "LA-3018-50P", "EXB-9500", "HPC-9500" manufactured by DIC Co., Ltd. etc. can be mentioned.

From the viewpoint of obtaining an insulating layer having excellent adhesion to the wiring layer, an active ester-based curing agent is also preferred. The active ester curing agent is not particularly limited, but in general, two ester groups with high reaction activity such as phenol esters, thiophenol esters, N-hydroxyamine esters, and esters of heterocyclic hydroxy compounds are used in one molecule. A compound having the above is preferably used. The active ester curing agent is preferably obtained by a condensation reaction of a carboxylic acid compound and/or a thiocarboxylic acid compound with a hydroxy compound and/or a thiol compound. In particular, from the viewpoint of improving heat resistance, an active ester-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, 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, and pyromellitic acid. Examples of the phenol compound or naphthol compound include hydroquinone, resorcinol, bisphenol A, bisphenol F, bisphenol S, phenolphthalein, methylated bisphenol A, methylated bisphenol F, methylated bisphenol S, phenol, o-cresol, m-cresol, p -Cresol, catechol, α-naphthol, β-naphthol, 1,5-dihydroxy naphthalene, 1,6-dihydroxy naphthalene, 2,6-dihydroxy naphthalene, dihydroxy benzophenone, trihydroxy Benzophenone, tetrahydroxy benzophenone, phloroglucine, benzenetriol, dicyclopentadiene type diphenol compounds, phenol novolaks, and the like. Here, "dicyclopentadiene-type diphenol compound" refers to a diphenol compound obtained by condensation of two molecules of phenol with one molecule of dicyclopentadiene.

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 acetylate of phenol novolac, and a benzoyl compound of phenol novolac. An active ester compound is preferable, and among 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" refers to a divalent structural unit composed of phenylene-dicyclopentylene-phenylene.

Commercially available active ester curing agents include "EXB9451", "EXB9460", "EXB9460S", "HPC-8000-65T" and "HPC-8000H-65TM" as active ester compounds containing a dicyclopentadiene type diphenol structure. "EXB-8000L-65TM" (manufactured by DIC Corporation), "EXB9416-70BK" (manufactured by DIC Corporation) as an active ester compound containing a naphthalene structure, active ester containing acetylated phenol novolac "DC808" (manufactured by Mitsubishi Chemical Corporation) as a compound, "YLH1026" (manufactured by Mitsubishi Chemical Corporation) as an active ester compound containing a benzoylate of phenol novolac, active ester as an acetylated product of phenol novolac "DC808" (Mitsubishi Chemical Co., Ltd.) as a curing agent, "YLH1026" (Mitsubishi Chemical Co., Ltd.), "YLH1030" (Mitsubishi Chemical Co., Ltd. ) manufacture), "YLH1048" (made by Mitsubishi Chemical Corporation), etc. are mentioned.

As a specific example of a benzoxazine system hardening|curing agent, "HFB2006M" by Showa Kobunshi Co., Ltd., "P-d" by Shikoku Kasei Kogyo Co., Ltd., and "F-a" are mentioned.

Examples of the cyanate ester curing agent include bisphenol A dicyanate, polyphenol cyanate, oligo(3-methylene-1,5-phenylene cyanate), 4,4'-methylene bis(2,6-dimethyl phenyl cyanate), 4,4'-ethylidenediphenyl dicyanate, hexafluoro bisphenol A dicyanate, 2,2-bis(4-cyanate)phenylpropane, 1,1-bis(4-cyanate) nate phenylmethane), bis(4-cyanate-3,5-dimethylphenyl)methane, 1,3-bis(4-cyanate phenyl-1-(methylethylidene)benzene, bis(4-cyanate phenyl) ) Bifunctional cyanate resins such as thioether and bis(4-cyanate phenyl) ether, polyfunctional cyanate resins derived from phenol novolacs and cresol novolacs, and prepolymers in which these cyanate resins are partially triazated Specific examples of the cyanate ester curing agent include "PT30" and "PT60" (all phenol novolak type polyfunctional cyanate ester resins) manufactured by Lonza Japan Co., Ltd., "BA230" and "BA230S75" (a prepolymer obtained by triazation of part or all of bisphenol A dicyanate to form a trimer); and the like.

As a specific example of a carbodiimide type hardening|curing agent, "V-03" of Nisshinbo Chemical Co., Ltd. product, "V-07", etc. are mentioned.

The ratio between the epoxy resin and the curing agent is preferably in the range of 1:0.01 to 1:2, preferably 1:0.015 to 1:1.5, in the ratio of [the total number of epoxy groups in the epoxy resin]:[the total number of reactive groups in the curing agent]. is more preferred, and 1:0.02 to 1:1 is still more preferred. Here, the reactive group of the curing agent is an active hydroxyl group, an active ester group, or the like, and varies depending on the type of the curing agent. In addition, the total number of epoxy groups of an epoxy resin is a value obtained by dividing the solid content mass of each epoxy resin by the epoxy equivalent with respect to all epoxy resins, and the total number of reactive groups of the curing agent is the total number of reactive groups of the curing agent. It is the sum of the values divided by , for all curing agents. By making the quantity ratio of an epoxy resin and a hardening|curing agent into this range, the heat resistance of the hardened|cured material of a thermosetting resin composition improves more.

In one embodiment, the thermosetting resin composition contains the above-described (a) epoxy resin and (c) curing agent. 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 liquid epoxy resin:solid epoxy resin is preferably 1:0.1 to 1:20, more preferably 1:0.3 to 1:0.3). 1:10, more preferably 1:0.6 to 1:9), (c) at least one selected from the group consisting of a phenol-based curing agent, a naphthol-based curing agent, an active ester-based curing agent, and a cyanate-based curing agent as a curing agent It is preferable to include each.

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, still more preferably 20% by mass or less. In addition, 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, and examples thereof include silica, alumina, glass, cordierite, silicon oxide, barium sulfate, barium carbonate, talc, clay, mica powder, zinc oxide, hydrotalcite, boehmite, Aluminum hydroxide, magnesium hydroxide, calcium carbonate, magnesium carbonate, magnesium oxide, boron nitride, aluminum nitride, manganese nitride, aluminum borate, strontium carbonate, strontium titanate, calcium titanate, magnesium titanate, bismuth titanate, titanium oxide, zirconium oxide, barium titanate , barium zirconate titanate, barium zirconate, calcium zirconate, zirconium phosphate, and zirconium tungstate phosphate. Among these, silica or alumina is suitable, and silica is particularly suitable. Moreover, as a silica, spherical silica is preferable. An inorganic filler may be used individually by 1 type, and may be used in combination of 2 or more types.

The average particle size of the inorganic filler is preferably 2 μm or less, more preferably 1 μm or less, even more preferably 0.8 μm or less, and still more preferably 0.6 μm or less, from the viewpoint of good embedding properties. The lower limit of the average particle diameter is not particularly limited, but is preferably 0.01 μm or more, more preferably 0.05 μm or more, still more preferably 0.1 μm or more. Examples of commercially available inorganic fillers having such an average particle diameter include "YC100C", "YA050C", "YA050C-MJE", "YA010C" manufactured by Adomatex Co., Ltd., and "YA010C" manufactured by Denki Kagaku Kogyo Co., Ltd. UFP-30", "Silent NSS-3N", "Silent NSS-4N", "Silent NSS-5N" manufactured by Tokuyama Co., Ltd. "SOC4", "SOC2", "SOC1" manufactured by Adomatex Co., Ltd. "AHP300" manufactured by Nippon Keikinzoku Co., Ltd., "Aluna beads (registered trademark) CB" manufactured by Showa Denko Co., Ltd. (for example, "CB-P05", "CB-A30S"), Denka Co., Ltd. Manufacture "DAW-03", "DAW-45", "DAW-05", "ASFP-20" etc. are mentioned.

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

From the viewpoint of improving moisture resistance and dispersibility, inorganic fillers include aminosilane coupling agents, epoxysilane coupling agents, mercaptosilane coupling agents, silane coupling agents, alkoxysilane compounds, organosilazane compounds, and titanate coupling agents. It is preferable to be treated with one or more types of surface treatment agents such as ring agents. As a commercial item of a surface treatment agent, Shin-Etsu Chemical Co., Ltd. product "KBM403" (3-glycidoxypropyltrimethoxysilane), Shin-Etsu Chemical Co., Ltd. product "KBM803" (3-mercapto propyltrimethoxysilane), Shin-Etsu Chemical Co., Ltd. "KBE903" (3-aminopropyltriethoxysilane), Shin-Etsu Chemical Chemical Co., Ltd. "KBM573" (N-phenyl-3-aminopropyl trimethoxysilane) methoxysilane), Shin-Etsu Chemical Co., Ltd. "SZ-31" (hexamethyldisilazane), Shin-Etsu Chemical Chemical Co., Ltd. "KBM103" (phenyltrimethoxysilane), Shin-Etsu Chemical Chemical ( Note) Manufacture "KBM-4803" (long chain epoxy type silane coupling agent) etc. are mentioned.

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 with a low thermal expansion coefficient. The upper limit of the content of the inorganic filler in the thermosetting resin composition is preferably 90% by mass or less, and more preferably 85% by mass or less, from the viewpoint of mechanical strength of the insulating layer, particularly elongation.

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

-(e) Curing accelerator-

Examples of the curing accelerator include phosphorus curing accelerators, amine curing accelerators, imidazole curing accelerators, guanidine curing accelerators, and metal curing accelerators. , Metal-based hardening accelerators are preferable, and amine-based hardening accelerators, imidazole-based hardening accelerators, and metal-based hardening accelerators are more preferable. A hardening accelerator may be used individually by 1 type, and may be used in combination of 2 or more type.

Examples of the phosphorus curing accelerator include triphenylphosphine, phosphonium borate compounds, tetraphenylphosphonium tetraphenylborate, n-butylphosphonium tetraphenylborate, tetrabutylphosphonium decanoate, and (4-methylphenyl)triphenylphos. Phonium thiocyanate, tetraphenylphosphonium thiocyanate, butyl triphenylphosphonium thiocyanate, etc. are mentioned, and triphenylphosphine and tetrabutylphosphonium decanoate are preferable.

Examples of the amine curing accelerator include trialkylamines such as triethylamine and tributylamine, 4-dimethylaminopyridine, benzyldimethylamine, 2,4,6-tris(dimethylaminomethyl)phenol, 1,8- Diazabicyclo(5,4,0)-undecene etc. are mentioned, 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, and 2-ethyl-4-methyl. Imidazole, 1,2-dimethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 1-benzyl-2-methyl Midazole, 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 ] Imidazole compounds such as benzimidazole, 1-dodecyl-2-methyl-3-benzimidazolium chloride, 2-methylimidazoline, and 2-phenylimidazolin, and adducts of imidazole compounds and epoxy resins A sieve is used, and 2-ethyl-4-methylimidazole and 1-benzyl-2-phenylimidazole are preferable.

As an imidazole type hardening accelerator, you may use a commercial item, for example, Mitsubishi Chemical Corporation product "P200-H50" etc. are mentioned.

Examples of the guanidine-based curing accelerator include dicyandiamide, 1-methylguanidine, 1-ethylguanidine, 1-cyclohexylguanidine, 1-phenylguanidine, 1-(o-tolyl)guanidine, dimethylguanidine, diphenylguanidine, Trimethylguanidine, tetramethylguanidine, pentamethylguanidine, 1,5,7-triazabicyclo[4.4.0]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-allylbiguanide, 1-phenylbiguanide, 1-(o-tolyl)biguanide and the like, dicyandiamide, 1 ,5,7-triazabicyclo[4.4.0]deca-5-ene is preferred.

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

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 resins (except those corresponding to component (b))-

Examples of the thermoplastic resin are preferably phenoxy resins, polyvinyl acetal resins, polyimide resins, polyamideimide resins, polysulfone resins, polyether sulfone resins, and polyphenylene ether resins, and more preferably phenoxy resins. . A thermoplastic resin may be used individually by 1 type, or may be used in combination of 2 or more types.

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

Examples of the phenoxy resin include bisphenol A skeleton, bisphenol F skeleton, bisphenol S skeleton, bisphenol acetophenone skeleton, novolac skeleton, biphenyl skeleton, fluorene skeleton, dicyclopentadiene skeleton, norbornene skeleton, and naphthalene skeleton. , an anthracene skeleton, an adamantane skeleton, a terpene skeleton, and a phenoxy resin having at least one skeleton selected from the group consisting of a trimethylcyclohexane skeleton. Any functional group, such as a phenolic hydroxyl group and an epoxy group, may be sufficient as the terminal of a phenoxy resin. A phenoxy resin may be used individually by 1 type, and may be used in combination of 2 or more types. As specific examples of the phenoxy resin, "1256" and "4250" (both bisphenol A skeleton-containing phenoxy resins) manufactured by Mitsubishi Chemical Corporation, "YX8100" (bisphenol S skeleton-containing phenoxy resin), and "YX6954" (bisphenol acetophenone skeleton-containing phenoxy resin), in addition, "FX280" and "FX293" manufactured by Nippon Steel Sumikin Chemical Co., Ltd., "YX6954BH30" manufactured by Mitsubishi Chemical Corporation, " YX7553", "YX7553BH30", "YL7769BH30", "YL6794", "YL7213", "YL7290", "YL7482", etc. are mentioned.

As polyvinyl acetal resin, polyvinyl formal resin and polyvinyl butyral resin are mentioned, for example, and polyvinyl butyral resin is preferable. Specific examples of the polyvinyl acetal resin include, for example, "Telenium Butyral 4000-2", "Telenium Butyral 5000-A", "Telenium Butyral 6000-C" and "Telenium Butyral 6000-C" manufactured by Denki Chemical Co., Ltd. Ral 6000-EP", Sekisui Kagaku Kogyo Co., Ltd.'s SRECK BH series, BX series (e.g. BX-5Z), KS series (e.g. KS-1), BL series, BM series, etc. can be heard

As a specific example of the polyimide resin, "Ricacoat SN20" and "Ricacoat PN20" manufactured by Shinnippon Rica Co., Ltd. are exemplified.

Specific examples of the polyamideimide resin include "Viromax HR1NN" and "Viromax HR16NN" manufactured by Toyobo Seki Co., Ltd.

As a specific example of polyether sulfone resin, "PES5003P" of Tsumitomo Chemical Co., Ltd. product etc. are mentioned.

As a specific example of polysulfone resin, Solvay Advanced Polymers Co., Ltd. product polysulfone "P1700", "P3500", etc. are mentioned.

As a specific example of polyphenylene ether resin, Mitsubishi Gas Chemical Co., Ltd. product oligophenylene ether styrene resin "OPE-2St 1200" etc. are mentioned.

Among these, as a thermoplastic resin, a phenoxy resin and a polyvinyl acetal resin are preferable. Accordingly, in one suitable embodiment, the thermoplastic resin includes at least one 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% by mass to 40% by mass. %am.

-(g) flame retardant-

Examples of the flame retardant include organophosphorus flame retardants, organic nitrogen-containing phosphorus compounds, nitrogen compounds, silicon flame retardants, metal hydroxides, and the like. A flame retardant may be used individually by 1 type, or may use 2 or more types together.

As a flame retardant, you may use a commercial item, For example, "HCA-HQ" by Sanko Co., Ltd., "PX-200" by Daihachi Chemical Co., Ltd., etc. are mentioned.

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, still more preferably 0.5% by mass to 20% by mass. It is 10 mass %.

-Other Ingredients-

The thermoplastic resin composition may further contain other additives as needed, and examples of these other additives include organometallic compounds such as organic copper compounds, organic zinc compounds and organic cobalt compounds, thickeners, antifoaming agents, and leveling agents. , adhesion imparting agents, and 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 its outermost surface.

<Method of manufacturing adhesive film>

The manufacturing method of the adhesive film is not particularly limited as long as it includes a support and a thermosetting resin composition layer bonded to the support. An adhesive film can be produced, for example, by preparing a resin varnish obtained by dissolving a resin composition in an organic solvent, applying the resin varnish on a support using a die coater or the like, and further drying to form a resin composition layer. .

Examples of the organic solvent include ketones such as acetone, methyl ethyl ketone (MEK) and cyclohexanone, ethyl acetate, butyl acetate, cellosolve acetate, propylene glycol monomethyl ether acetate, and carbitol acetate. Acetate esters, carbitols such as cellosolve and butyl carbitol; aromatic hydrocarbons such as toluene and xylene; amide solvents such as dimethylformamide, dimethylacetamide (DMAc) and N-methylpyrrolidone; and the like. An organic solvent may be used individually by 1 type, and may be used in combination of 2 or more types.

Drying may be performed by a known method such as heating or hot air spraying. Drying conditions are not particularly limited, but drying is performed so that the content of the organic solvent in the thermosetting resin composition layer 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 using a resin varnish containing 30% by mass to 60% by mass of the organic solvent, the thermosetting resin composition is dried at 50°C to 150°C for 3 minutes to 15 minutes. layers can be formed.

In the adhesive film, a protective film conforming to the support may be further laminated on the surface of the thermosetting resin composition layer not bonded to the support (ie, 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, adhesion of dust and the like to the surface of the thermosetting resin composition layer and scratches can be prevented. The adhesive film can be wound up in a roll shape and stored. When the adhesive film has a protective film, it becomes usable by peeling off the protective film.

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

As the plastic material, for example, polyester such as polyethylene terephthalate (hereinafter sometimes abbreviated as "PET") and polyethylene naphthalate (hereinafter sometimes abbreviated as "PEN"), polyethylene, polypropylene, etc. polyolefin, polycarbonate (hereinafter sometimes abbreviated as "PC"), acrylic such as polymethyl methacrylate (PMMA), cyclic polyolefin, triacetyl cellulose (TAC), polyether sulfide (PES), polyether A ketone, a polyimide, etc. are mentioned. Among them, polyethylene terephthalate, polyethylene naphthalate, and polypropylene are preferred, and inexpensive polyethylene terephthalate is particularly preferred.

Moreover, as a protective film, you may use the support body with a release layer which has a release layer on the surface to be bonded with a thermosetting resin composition layer. As a mold release agent used for the mold release layer of the support body with a mold release layer, 1 or more types of mold release agents chosen from the group which consists of alkyd resins, polyolefin resins, urethane resins, and silicone resins are mentioned, for example. A support with a release layer may use a commercial item, for example, "SK-1", "AL-5", "AL -7", Toray Co., Ltd. product "Lumiror T6AM", etc. are mentioned.

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. Moreover, when using a support body with a release layer, it is preferable that the thickness of the whole support body with a release layer is the said range.

The thermosetting resin composition layer in the present invention exhibits good embedding properties. When laminating on a base material with a wiring layer, the thermosetting resin composition layer can be laminated on the wiring layer in a void-free state.

In the adhesive film of the present invention, a cured product obtained by thermally curing the thermosetting resin composition layer (for example, a cured product obtained by curing at 190° C. for 90 minutes (thermosetting resin composition layer after thermal curing)) has a range of 30 to 150 It shows a good average coefficient of linear thermal expansion at °C. That is, an insulating layer exhibiting a good average linear thermal expansion coefficient is formed. The cured product obtained by curing the thermosetting resin composition layer has an average linear thermal expansion coefficient at 30°C to 150°C of 16 ppm/°C or less, preferably 15 ppm/°C or less, more preferably 14 ppm/°C or less, 13 ppm/°C or less. am. 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 the average linear thermal expansion coefficient (coefficient of thermal expansion)> described later.

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

In the adhesive film of the present invention, the cured product obtained by thermally curing the thermosetting resin composition layer (for example, the cured product obtained by curing at 190 ° C. for 90 minutes (thermosetting resin composition layer after thermal curing)) has good breaking strength ( 25° C.). That is, an insulating layer exhibiting good breaking strength is formed. The breaking strength at 25°C of the thermosetting resin composition layer after curing is 45 MPa or more, preferably 50 MPa or more, and more preferably 60 MPa or more. Although it does not specifically limit about an upper limit, It is 500 Mpa or less. The method for measuring the breaking strength can be measured according to the method described in <Measurement of elastic modulus and breaking strength> described later.

Since the adhesive film of the present invention includes a thermosetting resin composition layer that provides a cured product showing good results in average coefficient of linear thermal expansion at 30 ° C to 150 ° C, modulus of elasticity at 25 ° C, and breaking strength at 25 ° C, the present invention In the wiring board manufactured using the adhesive film of the invention, occurrence of warping and cracking is suppressed. Therefore, the adhesive film of the present invention can be suitably used for forming an insulating layer of a printed wiring board having a buried wiring layer, and can be more suitably used for forming an interlayer insulating layer of a printed wiring board.

[Method of manufacturing wiring board]

The manufacturing method of the 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 formed on at least one surface of the base material;

(2) 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 thermally curing to form an insulating layer;

(3) a step of connecting the wiring layers between layers; and

(4) It is characterized by including a step of removing the substrate.

Step (3) is not particularly limited as long as wiring layers can be connected between layers, but at least any of a step of forming a via hole in an insulating layer and forming a conductor layer, and a step of polishing or grinding the insulating layer to expose the wiring layer It is preferable that it is one process.

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

1. First Embodiment

<Process (1)>

Step (1) is a step of preparing a base material with a wiring layer having a base material and a wiring layer formed 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 parts of the base material 11 on both sides of the base material 11, respectively, and one side The wiring layer 14 is provided on the surface of the second metal layer 13 opposite to the surface of the substrate 11 side.

In detail of step (1), a dry film (photosensitive resist film) is laminated on a substrate, and a patterned dry film is formed by exposing and developing under predetermined conditions using a photomask. After using the developed pattern dry film as a plating mask and forming a wiring layer by an electroplating method, the pattern dry film is peeled off.

Materials used for the first and second metal layers are 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, and more preferably copper, from the viewpoints of cost, etching, ease of peeling, and the like.

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

The dry film is not particularly limited as long as it is a photosensitive dry film made of a photoresist composition, and dry films such as novolak resin and acrylic resin can be used, for example. A dry film may use a commercial item, for example, Nikko Materials Co., Ltd. product "ALPHO 20A263" which is a dry film with a PET film can be used. The dry film may be laminated on one side of the substrate, or may be laminated on both sides of the substrate as in the second embodiment described later.

Lamination conditions of the base material and the dry film are the same as those for laminating the adhesive film in step (2) to be 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 photo mask 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 (ie, the pitch is 40 μm or less), more preferably 18/18 μm or less ( Pitch 36 μm or less), more preferably 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, more preferably 1/1 μm or more. The pitch need not 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 wiring layer can be formed by a plating method using a dry film having a desired pattern formed thereon as a plating mask.

The conductor material used for the wiring layer is not particularly limited. In a suitable embodiment, the wiring layer includes one or more metals selected from the group consisting of gold, platinum, palladium, silver, copper, aluminum, cobalt, chromium, zinc, nickel, titanium, tungsten, iron, tin and indium. . The wiring layer may be a single metal layer or an alloy layer, and the alloy layer is, for example, an alloy of two or more types of metals selected from the above groups (eg, nickel-chromium alloy, copper-nickel alloy, and copper-titanium alloy). can be formed. 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-nickel alloy, copper An alloy layer of a titanium alloy is preferred, 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 preferred, and a single metal layer of copper is still 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. Peeling of the dry film can be performed using, for example, an alkaline stripping solution such as a sodium hydroxide solution. If necessary, unnecessary wiring patterns may be removed by etching or the like to form desired wiring patterns. The pitch of the wiring layers 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 thermally curing to form an insulating layer. Since the thermosetting resin composition layer in the present invention exhibits good embedding properties, when it is laminated on a base material with a wiring layer, it can be laminated in a void-free state. As an example shown in FIG. 2, the wiring layer 14 of the base material with a 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, and the adhesive film ( The thermosetting resin composition layer 21 of 20) is thermally cured. The adhesive film 20 is formed by laminating a thermosetting resin composition layer 21 and a support 22 in that order.

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

Lamination of the wiring layer and the adhesive film can be performed by, for example, heat-pressing the adhesive film to the wiring layer from the support body 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 (such as a SUS head plate) or a metal roll (SUS roll). In addition, it is preferable to press the heat-compressed member not directly onto the adhesive film, but through an elastic material such as heat-resistant rubber so that the adhesive film sufficiently follows the irregularities on the surface of the wiring layer.

Lamination of the wiring layer and the adhesive film may be performed by a vacuum lamination method after removing the protective film of the adhesive film. In the vacuum lamination method, the heat compression temperature is preferably in the range of 60°C to 160°C, more preferably 80°C to 140°C, and the heat compression pressure is preferably 0.098 MPa to 1.77 MPa, more preferably It is in the range of 0.29 MPa to 1.47 MPa, and the heat pressing time is preferably in the range of 20 seconds to 400 seconds, and more preferably in the range of 30 seconds to 300 seconds. Lamination is preferably carried out under reduced pressure conditions of 13 hPa or less.

Lamination can be performed with a commercially available vacuum laminator. Commercially available vacuum laminators include, for example, a vacuum pressurized laminator manufactured by Nikko Materials Co., Ltd., a vacuum pressurized laminator manufactured by Makey Sesakusho Co., Ltd., and a vacuum applicator manufactured by Nichigo Morton Co., Ltd. .

After lamination, the laminated adhesive film may be subjected to a smoothing treatment under normal pressure (under atmospheric pressure), for example, by pressing the hot-pressing member from the support body side. The press conditions for the smoothing treatment can be the same conditions as the thermal compression conditions for the above laminate. The smoothing process can be performed with a commercially available laminator. In addition, you may perform lamination|stacking and a smoothing process continuously using the said commercially available vacuum laminator.

After the thermosetting resin composition layer is laminated on the substrate with a wiring layer so as to bury the wiring layer, the thermosetting resin composition layer is thermally cured to form an insulating layer. Conditions for thermal curing of the thermosetting resin composition layer are not particularly limited, and conditions usually employed when forming an insulating layer of a wiring board may be used.

For example, the thermal curing conditions of the thermosetting resin composition layer vary depending on the type of the thermosetting resin composition, etc., but the curing temperature is in the range of 120°C to 240°C (preferably in the range of 150°C to 220°C, more preferably 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).

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

The support of the adhesive film may be peeled off after laminating the adhesive film on the substrate with a wiring layer and curing by heat, or may be peeled off before laminating the adhesive film on the substrate with a wiring layer. Moreover, you may peel a support body before a roughening process process mentioned later.

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

<Process (3)>

Step (3) in the first embodiment is a step of forming a via hole in the insulating layer and forming a conductor layer. Hereinafter, 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)") will be described separately. do.

-Process (3-1)-

Formation of the via hole is not particularly limited, but laser irradiation, etching, mechanical drilling, etc. may be cited, and it is preferably performed by laser irradiation. In detail, as an example shown in FIG. 3 , in step (3), after the support 22 is peeled off, laser irradiation is performed from the surface side of the adhesive film 20, and the support 22 and the insulating layer ( 21') to form a via hole 31 exposing the wiring layer 14.

This laser irradiation can be performed using any suitable laser processing machine using a carbon dioxide gas laser, a YAG laser, an excimer laser, or the like as a light source. As a laser processing machine that can be used, for example, a CO ₂ laser processing machine “LC-2k212/2C” manufactured by Via Mechanics Co., Ltd., 605GTWIII(-P) manufactured by Mitsubishi Electric Corporation, and Matsushita Yosetsu Systems Co., Ltd. ) manufacturing laser processing machine.

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

The shape of the via hole, that is, the shape of the outline of the opening when viewed in the stretching direction is not particularly limited, but is generally circular (substantially circular). Hereinafter, when referring to the “diameter” of a via hole, it refers to the diameter (diameter) of the outline of the opening when viewed from the stretching direction. In this specification, the top diameter r1 refers to the diameter of the via hole's insulating layer 21' side outline, and the bottom diameter r2 refers to the via hole's outline diameter on the wiring layer 14 side (FIG. 3, see Figure 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 an example in FIG. 3 , the via hole 31 may be formed such that r1 is larger than r2, and as shown in an example in FIG. 4 , the top diameter r1 of the via hole is The via hole 31 may be formed so as to be equal to the bottom diameter r2.

In this way, filling of via holes is improved, generation of voids can be suppressed, and as a result, reliability of electrical connection by filled vias described later can be improved.

After via hole formation, a so-called desmear process, which is a smear removal process in the via hole, may be performed. When the step (3-2) described later is performed by a plating step, for example, a wet desmear treatment may be performed on the via hole, and when the step (3-2) is performed by a sputtering step You may perform a dry desmear process, such as a plasma treatment process, for example. In addition, the desmear process may also serve as a roughening process.

You may include the process of performing a roughening process before a process (3-2). The roughening treatment is performed on the via hole and the adhesive sheet, and the procedures and conditions of the roughening treatment are not particularly limited. can Plasma treatment is exemplified as an example of dry roughening treatment, and examples of 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.

In the wet roughening process, the insulation layer 21' can be roughened by performing, for example, a swelling process with a swelling liquid, a roughening process with an oxidizing agent, and a neutralization process with a neutralization liquid in this order. Although it does not specifically limit as a swelling liquid, An alkali solution, surfactant solution, etc. are mentioned, Preferably it is an alkali solution, As said alkali solution, a sodium hydroxide solution and a potassium hydroxide solution are more preferable. Examples of commercially available swelling solutions include "Swelling Deep Securiganth P" and "Swelling Deep Securiganth SBU" manufactured by Atotech Japan Co., Ltd.

The swelling treatment with the swelling solution is not particularly limited, but can be performed by, for example, immersing the insulating layer 21' in a swelling solution at 30°C to 90°C for 1 minute to 20 minutes. From the viewpoint of suppressing 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 solution at 40°C to 80°C for 5 seconds to 15 minutes. Although it is not specifically limited as an oxidizing agent, For example, the alkaline permanganate solution which melt|dissolved potassium permanganate or sodium permanganate in the aqueous solution of sodium hydroxide is mentioned. The roughening treatment with an oxidizing agent such as an alkaline permanganic acid solution is preferably performed by immersing the insulating layer 21' in an oxidizing agent solution heated to 60°C to 80°C for 10 minutes to 30 minutes. In addition, the concentration of permanganate in the alkaline permanganic acid solution is preferably 5% by mass to 10% by mass. Examples of commercially available oxidizing agents include alkaline permanganic acid solutions such as Concentrate Compact P and Dosing Solution Securiganth P manufactured by Atotech Japan Co., Ltd. Moreover, as a neutralization liquid, an acidic aqueous solution is preferable, and as a commercial item, Reduction Solution Securiganth P of Atotech Japan Co., Ltd. product is mentioned, for example.

The treatment with the neutralization solution can be performed by immersing the treated surface subjected to the roughening treatment with the oxidizing agent solution in a neutralization solution at 30°C to 80°C for 5 minutes to 30 minutes. From the standpoint of workability and the like, a method in which the object subjected to the roughening treatment with the oxidizing agent solution is immersed in a neutralization solution at 40°C to 70°C for 5 minutes to 20 minutes is preferable.

-Process (3-2)-

The conductor material constituting the conductor layer is not particularly limited. In a suitable embodiment, it can form with the same material as the conductor material used for a wiring pattern, and it is preferable to use copper as a material.

The conductor layer may have a single-layer structure or a multi-layer structure in which two or more single metal layers or alloy layers made of different types of metals or alloys are laminated. When the conductor layer has a multilayer 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 a nickel/chromium alloy.

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

The conductor layer can be formed by any suitable conventionally known method such as plating, sputtering, or vapor deposition, and it is preferable to form the conductor layer by plating. In a suitable embodiment, a conductor layer having a desired wiring pattern can be formed by plating the surface of the insulating layer by a conventionally known technique such as a semi-additive method or a full additive method. 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. Subsequently, a mask pattern exposing a part of the plating seed layer corresponding to a desired wiring pattern is formed on the formed plating seed layer. An electroplating layer is formed on the exposed plating seed layer by electroplating, and then the mask pattern is removed. Thereafter, 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 bonded to the exposed surface of the insulating layer 21' is formed. First, cleaning of the surface of the insulating layer 21' and alkali cleaning for charge adjustment are performed. Next, a soft etching process is performed to clean the inside of the via hole 31 . Specifically, it may be treated under arbitrary suitable conditions using an etchant such as sulfuric acid acidic sodium peroxodisulfate aqueous solution. Subsequently, a pre-dip process for adjusting the electric charge on the surface of the insulating layer 21' is performed to impart Pd (palladium) to the surface of the insulating layer 21'. Next, Pd as an activator is applied to the surface, and Pd applied to the insulating layer 21' is reduced. Next, a plating seed layer 41 is formed by depositing copper (Cu) on the surface of the insulating layer 21'. At this time, the plating seed layer 41 is formed to cover the inside of the via hole 31 , that is, the sidewall and the wiring layer 14 exposed from the via hole 31 .

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

As a dry film which can be used in process (3-2), it is the same as the said dry film, and the preferable range is also the same.

As an example shown in FIG. 7 , an electroplating layer 42 is formed by electrolytic plating under the condition that the via hole 31 is filled on the exposed plating seed layer 41, and the via hole is electroplated. filled by , to form the filled via 61 .

As an example shown in FIG. 8 , the patterned conductor layer 40 is formed by stripping and removing the mask pattern, followed by flash etching under any suitable conditions to remove only the exposed plating seed layer 41 .

The conductor layer may include not only linear wires, but also electrode pads (lands) on which external terminals may be mounted. In addition, the conductor layer may be constituted only by electrode pads.

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

<Process (4)>

Step (4) is a step of forming the wiring board of the present invention by removing the substrate as shown in an example in FIG. 9 . The method for removing the substrate is not particularly limited. In one preferred embodiment, the substrate is separated from the wiring board at the interface between the first and second metal layers, and the second metal layer is etched away with, for example, an aqueous copper chloride solution.

If necessary, the substrate may be peeled off in a state where the conductor layer 40 is protected with a protective film. The above protective film is the same as the protective film used for the adhesive film, and the preferred range is also the same.

According to the manufacturing method of the present invention, a wiring board in which the wiring layer 14 is buried in the insulating layer 21' can be manufactured. 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 steps (2) to (3) may be repeated to form a multilayer wiring board. When manufacturing a multilayer wiring board, at least one adhesive film of the present invention may be used. In the case where a plurality of steps (3) are performed, a step of polishing or grinding the insulating layer and exposing the wiring layer may be performed in addition to the steps of forming via holes in the insulating layer and forming the conductor layer. Flexible means that the wiring board can be bent at least once without generating cracks or changes in resistance value.

2. Second Embodiment

In the first embodiment, 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) polishes or grinds the insulating layer to form a wiring layer Except for the step of exposing, it is the same as in the first embodiment. In each drawing used in the following description, the same reference numerals are assigned to the same components, and overlapping descriptions may be omitted.

Step (1) is a step of preparing a base material with a wiring layer having a base material and a wiring layer formed on both surfaces of the base material. The formation method of the wiring layer 14 is the same as that of the first embodiment. In step (1) in the second embodiment, as an example shown in FIG. 10 , it is preferable that the thicknesses of the respective wiring layers 14 in the second embodiment are different.

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

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 thermally curing it to form an insulating layer, as shown in FIG. 11 as an example. , the same as in the first embodiment, and the preferred range is also the same.

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

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

The polishing method or grinding method of 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, chemical mechanical polishing. A chemical mechanical polishing method by method, a mechanical polishing method such as buffing, a surface grinding method by rotating a grindstone, and the like are exemplified.

You may perform the process of performing a smear removal method and a roughening process after process (3) similarly to 1st Embodiment as needed after process (3). Moreover, you may form a conductor layer like said process (3-2) as needed.

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

3. Third Embodiment

In the first embodiment, a wiring board was manufactured from a base material with a wiring layer having a wiring layer on one surface, but in the third embodiment, the wiring board was manufactured from a base material with a wiring layer having a wiring layer on both sides of the base material. do. In each figure used for the following description, the same code|symbol is attached|subjected about the same component, and overlapping description may be abbreviate|omitted.

As an example shown in FIG. 14, process (1) is a process of preparing the base material with a wiring layer which has a base material and the wiring layer formed on both surfaces of the said base material. The method of forming the wiring layer 14 is the same as in the first embodiment, and the wiring layers formed on both sides of the base material may be formed simultaneously to prepare a base material with a wiring layer, or after forming one wiring layer, the other wiring layer is formed to form the base material with a wiring layer. You may also prepare In addition, each wiring layer may have the same pattern or a different pattern. Further, the thickness of each wiring layer may be different as shown in FIG. 10 .

Step (2), as shown in an example in FIG. 15, on both sides of the base material with a wiring layer, an adhesive film is laminated on the base material with a wiring layer so that the wiring layer is embedded in the thermosetting resin composition layer, respectively. It is a step of thermally curing. The two adhesive films to be used may be the same adhesive film or different adhesive films.

As shown in an example in FIG. 16, in step (3), laser irradiation is performed from the thermally cured adhesive film side to both surfaces of the base material with a wiring layer, and via holes are preferably formed in the thermally cured adhesive film. . The via hole may be formed simultaneously, or the other via hole may be formed after forming one via hole.

Before forming a conductor layer, you may include the process of roughening with respect to both surfaces of a base material with a wiring layer, and the surface of two insulating layers 21' is roughened. The roughening treatment may be performed simultaneously, or after one roughening treatment, the other roughening treatment may be performed.

After via hole formation, a conductor layer is formed on both surfaces of the base material with a wiring layer. As an example shown in Fig. 17, a plating seed layer 41 is formed on the insulating layer 21' after the roughening treatment. After forming the plating seed layer 41, as shown in an example in FIG. 18, a mask pattern 50 exposing a part of the plating seed layer 41 is formed, and as shown in an example in FIG. 19, An electric field plating layer 42 is formed on the exposed plating seed layer 41, and filled vias 61 are formed by filling via holes with an electric field plating process. As an example shown in FIG. 20 , the mask pattern is removed and the conductor layer 40 is formed. Details of the formation of the conductor layer 40 can be performed in the same manner as in the first embodiment. In addition, the two conductor layers formed on both sides of the base material may be formed simultaneously, or after forming one conductor layer, the other conductor layer may be formed.

Although 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, the step of polishing or grinding the insulating layer and exposing the wiring layer instead You may do it. Alternatively, on one side of the base material with a wiring layer, a step of forming a via hole in an insulating layer and forming a conductor layer may be performed, and on the other side, a step of polishing or grinding the insulating layer to expose the wiring layer may be performed. .

Step (4) is a step of removing the substrate and forming the wiring board of the present invention, as shown in Fig. 21 as an example. In the third embodiment, it becomes possible to simultaneously manufacture two types of wiring boards.

[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 a buried wiring layer embedded in the insulating layer. In addition, description overlapping with the above content may be omitted.

The wiring board of the present invention can be manufactured by the manufacturing method of the wiring board of the present invention including, for example, the steps (1) to (4) above. As an example shown in Fig. 9, in the wiring board 1 of the present invention, a buried wiring layer 14 and an insulating layer 21' are laminated in that order. A conductor layer 40 is provided on the surface of the insulating layer 21' that is not bonded to the buried wiring layer 14 (ie, on the surface opposite to the buried wiring layer 14). The buried wiring layer 14 is bonded to the conductor layer 40 via a filled via 61 .

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

The wiring board of the present invention may be a multilayer wiring board as shown in Figs. 22 and 23 as an example. The thermosetting resin composition constituting the thermosetting resin composition layer forming the insulating layer in the wiring board shown as an example in FIGS. 22 and 23 may have the same composition or a different composition. 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 the bottom diameter. It may be larger than the diameter.

A wiring board manufactured using the adhesive film of the present invention exhibits a characteristic that occurrence of warpage is suppressed. The size of the warp is preferably 1 cm or less. Although it does not specifically limit about a lower limit, It is 0.01 mm or more. The measurement of warpage can be measured according to the method described in <Evaluation of warpage> described later.

A wiring board manufactured using the adhesive film of the present invention exhibits a characteristic that generation of cracks is suppressed. The length of the crack is preferably less than 1 mm. Although it does not specifically limit about a lower limit, It is 0.01 mm or more. The measurement of cracks can be performed according to the method described in <Evaluation of cracks> 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 using the wiring board of the present invention.

Examples of semiconductor devices include various semiconductor devices provided for electric appliances (eg, computers, mobile phones, digital cameras, TVs, etc.) and vehicles (eg, motorcycles, automobiles, electric cars, ships, aircraft, etc.) can

The semiconductor device of the present invention can be manufactured by mounting a component (semiconductor chip) at a conducting location on a printed wiring board. A "conduction point" is a "point where electric signals are transmitted on a printed wiring board", and the place may be a surface or a buried location. In addition, the semiconductor chip is not particularly limited as long as it is an electric circuit element made of a semiconductor as a material.

The semiconductor chip mounting method in manufacturing the semiconductor device of the present invention is not particularly limited as long as the semiconductor chip functions effectively, but specifically includes a wire bonding mounting method, a flip chip mounting method, and a bumpless mounting method. A packaging method using a build-up layer (BBUL), a packaging method using an anisotropic conductive film (ACF), a packaging method using a non-conductive film (NCF), and the like are exemplified. Here, the "mounting method using a bumpless build-up layer (BBUL)" refers to a "mounting method in which a semiconductor chip is directly embedded in a concave portion of a printed wiring board and the semiconductor chip and wiring on the printed wiring board are connected."

[Example]

Hereinafter, the present invention will be specifically described by examples, but the present invention is not limited to these examples. In addition, in the following description, "part" and "%" mean "part by mass" and "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 formed on at least one surface of the base material

(1-1) Lamination of dry film to substrate (core substrate)

As the core substrate, a glass cloth base epoxy resin double-sided copper clad laminate (layer configuration: Mitsui Kinzoku Kogyo Co., Ltd. Microcyn MT-Ex copper foil (3 μm-thick copper foil/18 μm-thick carrier foil)/manufactured by Panasonic Co., Ltd.) "R1515A" substrate (thickness: 0.2 mm)/Mitsui Kinzoku Kogyo Co., Ltd. Microcyn MT-Ex copper foil (carrier foil with a thickness of 18 μm/copper foil with a thickness of 3 μm) 170 × 110 mm square was prepared. A dry film with PET film (“ALPHO 20A263” manufactured by Nikko Materials Co., Ltd., dry film thickness: 20 μm) is applied to both surfaces of the 3 μm copper foil on the mat surface side of the laminated board in a batchwise manner so that the dry film is bonded to the copper foil. It laminated|stacked using the vacuum pressure laminator (2-stage build-up laminator "CVP700" manufactured by Nikko Materials Co., Ltd.). Lamination|stacking of the dry film was performed by pressure-reducing for 30 second and pressure-reducing to 13 hPa or less, and then crimping|compression-bonding for 20 second at the temperature of 70 degreeC, and the pressure of 0.1 MPa.

(1-2) Pattern formation

A glass mask (photomask) having a wiring pattern shown below was placed on a PET film serving as a protective layer of a dry film, and UV irradiation was performed with a UV lamp at an irradiation intensity of 150 mJ/cm 2 . After UV irradiation, the PET film of the dry film was peeled off, and a 30°C 1% sodium carbonate aqueous solution was sprayed for 30 seconds at a spraying pressure of 0.15 MPa. Then, it washed with water and developed (pattern formation) of the dry film.

Wiring pattern of glass mask:

L/S = 15 μm/15 μm, that is, a comb pattern (wiring length 15 mm, 16 lines) with a wiring pitch of 30 μm is formed at intervals of 10 mm.

(1-3) Formation of wiring layer

After development of the dry film, electrolytic copper plating was performed to a thickness of 15 µm to form a wiring layer. Subsequently, a 50°C 3% sodium hydroxide solution was sprayed at a spray pressure of 0.2 MPa, and the dry film was peeled off, then washed with water and dried at 150°C for 30 minutes.

(2) Step of laminating an adhesive film on a base material with a wiring layer and thermally curing it to form an insulating layer so that the wiring layer is embedded in the thermosetting resin composition layer

(2-1) Lamination of adhesive film

The protective film of the protective film (167 mm × 107 mm) of the adhesive film produced in Examples and Comparative Examples was peeled off, using a batch-type vacuum pressure laminator (2-stage build-up laminator “CVP700” manufactured by Nikko Materials Co., Ltd.) , and 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. The lamination was carried out by reducing the pressure for 30 seconds to reduce the atmospheric pressure to 13 hPa or less, and then compressing at 110°C and a pressure of 0.74 MPa for 30 seconds. Then, the laminated adhesive film was hot pressed for 60 seconds at 110 DEG C under atmospheric pressure at a pressure of 0.5 MPa to smooth it.

(2-2) Thermal curing of the thermosetting resin composition layer

After lamination of the adhesive film, the support (PET film) was peeled off, and the thermosetting resin composition layer was thermally cured at 100°C for 30 minutes and then at 170°C for 30 minutes to form insulating layers on both sides of the wiring layer.

(3) Process of forming via holes in the insulating layer

A 150 μm square wiring layer serving as a land of a comb wiring pattern by irradiating a laser from the top of the insulating layer using a CO ₂ laser processing machine “605GTWIII(-P)” manufactured by Mitsubishi Denki Co., Ltd. A via hole having a top diameter (75 μm) was formed in the insulating layer immediately above. 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, and a number of shots of 3, which were performed in burst mode (10 kHz).

(3-1) Process of roughening

Desmear treatment was performed on the structure in which via holes were formed. In addition, as a desmear process, the following wet desmear process was implemented.

Wet desmear treatment:

The circuit board on which via holes were formed was placed in a swelling solution (“Swelling Deep Securigans P” manufactured by Atotech Japan Co., Ltd., an aqueous solution of diethylene glycol monobutyl ether and sodium hydroxide) at 60° C. for 5 minutes, followed by an oxidizing agent solution ( "Concentrate Compact CP" manufactured by Atotech Japan Co., Ltd., an aqueous solution of potassium permanganate concentration of about 6% and sodium hydroxide concentration of about 4%) at 80 ° C. for 10 minutes, and finally a neutralization solution (manufactured by Atotech Japan Co., Ltd. It was immersed in "Reduction Solution Securiganth P", sulfuric acid aqueous 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) Electroless plating process

In order to form a conductor layer on the surface of the evaluation substrate, a plating process (copper plating process using a chemical solution manufactured by Atotech Japan Co., Ltd.) including the following steps 1 to 6 was performed to form the conductor layer.

1. Alkaline cleaning (cleaning and charge adjustment of the surface of the insulating layer where via holes are formed)

Product name: Cleaning Cleaner Securiganth 902 (trade name) was used for cleaning at 60° C. for 5 minutes.

2. Soft Etching (Cleaning in Via Holes)

It was treated at 30° C. for 1 minute using a sulfuric acid acidic sodium peroxodisulfate aqueous solution.

3. Pre-dip (adjustment of electric charge on the surface of the insulating layer for Pd application)

Pre. Using Dip Neoganth B (trade name), it was treated at room temperature for 1 minute.

4. Activator application (application of Pd to the surface of the insulating layer)

Using Activator Neoganth 834 (trade name), it was treated at 35°C for 5 minutes.

5. Reduction (reduction of Pd applied to the insulating layer)

Using a mixture of Reducer Neoganth WA (trade name) and Reducer Acceralator 810 mod. (trade name), treatment was performed at 30° C. for 5 minutes.

6. Electroless copper plating process (precipitating Cu on the surface of the insulating layer (Pd surface))

Using 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), treatment was performed at 35° C. for 20 minutes. The thickness of the electroless copper plating layer formed was 0.8 μm.

(3-2-2) Electrolytic plating process

Subsequently, an electrolytic copper plating process was performed using a liquid chemical manufactured by Atotech Japan Co., Ltd. under the condition that copper was filled in the via hole. 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 (a portion without via connection is also formed on the entire surface at a pitch of 600 μm), and insulation is performed using the land pattern A conductor layer having a conductor pattern with a thickness of 15 μm was formed on the surface of the layer. Next, an annealing treatment was performed at 190°C for 90 minutes.

(4) Step of removing substrate

After bonding a PET film (thickness: 50 μm) with an adhesive to the entire surface of the base material with a wiring layer on which a conductor layer is formed, a cutter blade is placed at the interface between the 3 μm-thick copper foil of Microcyn MT-Ex copper foil and the 18-μm-thick carrier foil of the core substrate. was inserted to peel and separate the core substrate. Subsequently, the 3 μm copper foil was etched away with an aqueous copper chloride solution while the surface on which the conductor layer was formed was protected with a PET film with an adhesive, washed with water, and then dried at 110° C. for 30 minutes. After that, the PET film with the adhesive was peeled off, and a wiring board in which a L/S = 15/15 μm comb pattern was embedded on one side was produced. The obtained wiring board is referred to as "evaluation board A".

<Evaluation of warpage>

Among the four sides of the evaluation board A, it was fixed to a SUS plate with an adhesive tape (product name Kapton adhesive tape, manufactured by Teraoka Sesakusho Co., Ltd.) with a width of 107 mm, and the value of warpage was obtained by determining the height of the highest point on the SUS plate. saved This operation was repeated 4 times, and the average value was set as "○" when the size of the warpage was less than 1 cm, and as "x" when it was 1 cm or more.

<Evaluation of crack>

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

<Measurement of Average Coefficient of Linear Thermal Expansion (Coefficient of Thermal Expansion)>

The untreated side of the release PET film (“501010” manufactured by Lintec Co., Ltd., 38 μm thick, 240 mm square) is a glass cloth-based epoxy resin double-sided copper-clad laminate (“R5715ES” manufactured by Matsushita Denko Co., Ltd., 0.7 mm thick, 255 mm square) It was installed on a glass cloth-based epoxy resin double-sided copper-clad laminate, 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 was placed using a batch-type vacuum pressure laminator (2-stage build-up laminator CVP700 manufactured by Nichigo Morton Co., Ltd.), and the thermosetting resin composition layer was formed into a release PET film. Laminate was processed in the center to contact the release surface of the The lamination process was performed by compressing the pressure at 100° C. and a pressure of 0.74 MPa for 30 seconds after reducing the pressure for 30 seconds and reducing the atmospheric pressure to 13 hPa or less.

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

After thermal curing, the polyimide adhesive tape was peeled off, and the thermosetting resin composition layer was separated from the glass cloth-based epoxy 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. A sheet-like cured product is referred to as a cured product for evaluation. The obtained cured product was cut into test pieces having a width of 5 mm and a length of 15 mm, and thermomechanical analysis was performed by a tensile weighting method using a thermomechanical analyzer (“Thermo Plus TMA8310” manufactured by Rigaku Co., Ltd.). Specifically, after the test piece was attached to the thermomechanical analyzer, it was measured twice continuously under the measurement conditions of a load of 1 g and a heating rate of 5°C/min. And in the second measurement, the average coefficient of linear thermal expansion (α1; ppm/°C) in the planar direction in the range from 30°C to 150°C was calculated. This operation was performed 3 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 tensile strength of the test piece was measured using a tensile tester "RTC-1250A" manufactured by Orientec Co., Ltd., and the elastic modulus and breaking strength at 25°C were determined. The measurement was performed according to JIS K7127. This operation was performed 3 times and the average value is shown in the table.

<Measurement of average maximum diameter of domains>

For the thermosetting resin composition layer of the adhesive film heat-cured under conditions of 100 ° C. for 30 minutes and then 170 ° C. for 30 minutes, FIB (focused ion beam) to obtain a cross-sectional SEM image (observation width: 60 μm, observation magnification: 2,000 times) by cutting a cross section in a direction perpendicular to the surface of the adhesive film heat-cured. Cross-sectional SEM images of 5 randomly selected locations were observed, and the maximum diameters of 20 randomly selected domains (4 points/each cross section) were measured, and the average value was taken as the average maximum diameter. Those with an average maximum diameter of 15 µm or less were designated as "○", and those with an average maximum diameter of more than 15 µm were designated as "x".

<Example 1>

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.) Manufacture "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 (manufactured by DIC Corporation "EXA7311- G4", epoxy equivalent 213) 15 parts, polybutadiene backbone-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) It was heat-dissolved stirring 15 parts and 15 parts of cyclohexanone. The heat-dissolved solution was cooled to room temperature, and thereto, a triazine-containing phenolic novolac resin ("LA-7054" manufactured by DIC Co., Ltd., hydroxyl equivalent 125, nitrogen content of about 12% by weight, MEK solution having a solid content of 60% by weight) 10 parts, naphthol curing agent ("HPC-9500" manufactured by DIC Co., Ltd., hydroxyl equivalent 153, MEK solution having a solid content of 60% by weight) 25 parts, curing accelerator ("1B2PZ" manufactured by Shikoku Kasei Kogyo Co., Ltd., 1 Spherical silica (average Resin varnish 1 was prepared by mixing 260 parts of particle diameter 0.5 μm, “SOC2” manufactured by Adomatex Co., Ltd.), uniformly dispersing with a high-speed rotary mixer, and filtering with a cartridge filter (“SHP050” manufactured by ROKITECHNO).

Next, on a polyethylene terephthalate film (Lumiror "T6AM" manufactured by Tore Co., Ltd., thickness 38 μm), resin varnish 1 was uniformly applied so that the thickness of the thermosetting resin composition layer after drying was 80 μm, and the temperature was 80 to 120 ° C. ( After drying at an average temperature of 100 ° C.) for 6 minutes, the rough surface of the protective film (polypropylene film, “Alpan MA-430” manufactured by Oji Aftex Co., Ltd., thickness 20 μm) is bonded to the thermosetting resin composition layer It was bonded together to produce adhesive film 1.

Observation of the cross section of the thermosetting resin composition layer of adhesive film 1 heat-cured at 100°C for 30 minutes and then at 170°C for 30 minutes using a FIB-SEM composite device ("SMI3050SE" manufactured by SII Nano Technology Co., Ltd.) As a result, it was found that the component (b) was compatible with or close to components other than component (b) without showing any apparent dispersion in the domain shape.

<Example 2>

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.) Manufacture "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 (manufactured by DIC Corporation "EXA7311- G4S", epoxy equivalent 187) 15 parts, epoxy group-containing acrylic acid ester copolymer ("SG-80H" manufactured by Nagase Chemtex Co., Ltd. Number average molecular weight (Mn): 350000 g/mol, epoxy value 0.07 eq/kg, solid content 18 mass 110 parts of MEK solution) was heated and dissolved in 10 parts of methyl ethyl ketone (MEK) and 10 parts of cyclohexanone while stirring. The heat-dissolved solution was cooled to room temperature, and thereto, a triazine skeleton-containing phenolic curing agent ("LA-3018-50P" manufactured by DIC Corporation, 2-methoxypropanol solution with a hydroxyl equivalent of about 151 and a solid content of 50%) 20 Part, naphthol curing agent ("HPC-9500" manufactured by DIC Co., Ltd., hydroxyl equivalent 153, MEK solution having a solid content of 60% by weight) 25 parts, curing accelerator ("1B2PZ" manufactured by Shikoku Kasei Kogyo Co., Ltd.), 1- Spherical silica (average particle A diameter of 1 μm, 360 parts of “SOC4” manufactured by Adomatex Co., Ltd.) were mixed, uniformly dispersed with a high-speed rotary mixer, and filtered with a cartridge filter (“SHP100” manufactured by ROKITECHNO) to prepare resin varnish 2, Example 1 In the same manner as above, adhesive film 2 was produced.

A cross-section of the thermosetting resin composition layer of adhesive film 2 heat-cured under conditions of 100°C for 30 minutes and then 170°C for 30 minutes using a FIB-SEM composite device ("SMI3050SE" manufactured by SII Nano Technology Co., Ltd.) As a result of observation, it was found that the component (b) was compatible with or close to components other than the component (b), with no apparent dispersion in the domain shape.

<Example 3>

80 parts of polymer resin A prepared as follows, 3 parts of 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), 18 parts of dicyclopentadiene type epoxy resin ("HP-7200" manufactured by DIC Corporation, epoxy equivalent 260), 3 parts of naphthalene type tetrafunctional epoxy resin ("HP-4710" manufactured by DIC Corporation, epoxy equivalent 163) The mixture was heated and dissolved in 10 parts of methyl ethyl ketone (MEK) and 10 parts of cyclohexanone while stirring. The heated and dissolved solution was cooled to room temperature, and thereto, 5 parts of a naphthol-based curing agent ("HPC-9500" manufactured by DIC Co., Ltd., MEK solution having a hydroxyl equivalent of 153 and a solid content of 60% by weight), an active ester compound (DIC Co., Ltd.) Production "HPC-8000-65T", weight average molecular weight of about 2700, active group equivalent of about 223, non-volatile matter 65 mass% toluene solution) 2 parts, curing accelerator (4-dimethylaminopyridine (DMAP), solid content of 5 mass% MEK solution) 1 part, curing accelerator ("1B2PZ" manufactured by Shikoku Kasei Kogyo Co., Ltd., 1-benzyl-2-phenylimidazole, MEK solution having a solid content of 3% by mass) 2 parts, and a phenylaminosilane-based couple 300 parts of spherical silica (average particle diameter: 1 μm, “SOC4” manufactured by Adomatex Co., Ltd.) surface-treated with a ring agent (“KBM573” manufactured by Shin-Etsu Chemical Co., Ltd.) was mixed and uniformly mixed with a high-speed rotary mixer It was dispersed and filtered with a cartridge filter (“SHP100” manufactured by ROKITECHNO) to prepare resin varnish 3, and adhesive film 3 was prepared in the same manner as in Example 1.

A cross-section of the thermosetting resin composition layer of adhesive film 3, which was cured at 100°C for 30 minutes and then at 170°C for 30 minutes, using an FIB-SEM composite device ("SMI3050SE" manufactured by SII Nano Technology Co., Ltd.) As a result of observation, it was found that the component (b) was compatible with or close to components other than the component (b), with no apparent dispersion in the domain shape.

[Preparation of polymer resin A]

In a reaction vessel, 50 g of G-3000 (bifunctional hydroxyl group terminal polybutadiene, number average molecular weight = 5047 (GPC method), hydroxyl group equivalent = 1798 g/eq., 100% by mass of solid content: manufactured by Nippon Soda Co., Ltd.) 23.5 g of Ipsol 150 (aromatic hydrocarbon-based mixed solvent: manufactured by Idemitsu Sekiyu Chemical Co., Ltd.) and 0.005 g of dibutyltin laurate were mixed and uniformly dissolved. When it 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 while further stirring, followed by reaction for about 3 hours. Then, after cooling this reaction product to room temperature, 8.96 g of benzophenone tetracarboxylic dianhydride (acid anhydride equivalent: 161.1 g/eq), 0.07 g of triethylenediamine, and ethyldiglycol acetate (Co., Ltd.) 40.4 g of Daicel) was added, and the temperature was raised to 130°C while stirring, followed by reaction for about 4 hours. Disappearance of the NCO peak at 2250 cm ^-1 was confirmed by FT-IR. 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 filtered through a 100-mesh filter cloth to obtain a polymer resin A having an imide structure, a urethane structure, and a butadiene structure.

Viscosity: 7.5 Pa s (25°C, E-type viscometer)

Acid value: 16.9mgKOH/g

Solid content: 50% by mass

Number average molecular weight: 13723

Glass Transition Temperature: -10℃

Content of polybutadiene structural part: 50/(50+4.8+8.96) × 100 = 78.4% by mass

<Comparative Example 1>

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.) Manufacture "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 (manufactured by DIC Corporation "EXA7311- G4S”, epoxy equivalent 187) 15 parts were heated and dissolved in 10 parts of methyl ethyl ketone (MEK) and 10 parts of cyclohexanone while stirring. The heat-dissolved solution was cooled to room temperature, and thereto, a triazine-containing phenolic novolac resin ("LA-7054" manufactured by DIC Co., Ltd., hydroxyl equivalent 125, nitrogen content of about 12% by weight, MEK solution having a solid content of 60% by weight) 10 parts, naphthol-based curing agent ("HPC-9500" manufactured by DIC Co., Ltd., hydroxyl equivalent 153, MEK solution having a solid content of 60% by weight) 25 parts, curing accelerator ("1B2PZ" manufactured by Shikoku Kasei Kogyo Co., Ltd., 1 Spherical silica (average 200 parts of particle diameter 0.5 μm, "SOC2" manufactured by Adomatex Co., Ltd.) were mixed, uniformly dispersed with a high-speed rotary mixer, and filtered with a cartridge filter ("SHP050" manufactured by ROKITECHNO) to prepare resin varnish 4, Example Adhesive film 4 was produced in the same manner as in 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. product "NC3000L", epoxy equivalent 269) 10 parts were heat-dissolved, stirring in 6 parts of methyl ethyl ketone (MEK) and 6 parts of cyclohexanone. The heated and dissolved solution was cooled to room temperature, and thereto, an active ester compound ("HPC-8000-65T" manufactured by DIC Co., Ltd., a toluene solution having a weight average molecular weight of about 2700 and an active group equivalent of about 223 and a nonvolatile content of 65% by mass) 2 parts, curing accelerator (4-dimethylaminopyridine (DMAP), MEK solution with a solid content of 5% by mass) 1 part, curing accelerator ("1B2PZ" manufactured by Shikoku Kasei Kogyo Co., Ltd., 1-benzyl-2-phenyl is spherical silica (average particle diameter of 1 μm, ) 250 parts of "SOC4" manufactured by Adomatex) were mixed, uniformly dispersed with a high-speed rotary mixer, and filtered with a cartridge filter ("SHP100" manufactured by ROKITECHNO) to prepare resin varnish 5, and in the same manner as in Example 1, an adhesive film 5 was produced.

Similar to adhesive film 3, a cross-section of the thermosetting resin composition layer of adhesive film 5, which was heat-cured, was observed. As shown in FIG. 24, the average maximum diameter exceeded 15 μm.

<Comparative Example 3>

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) 7 parts, biphenyl type epoxy resin (Nippon Kayaku Co., Ltd.) Manufacture "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 (manufactured by DIC Corporation "EXA7311- G4", epoxy equivalent 213) 15 parts, polybutadiene backbone-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) It was heated and dissolved while stirring with 10 parts and 10 parts of cyclohexanone. The heat-dissolved solution was cooled to room temperature, and thereto, 20 parts of a triazine skeleton-containing phenolic curing agent (DIC Corporation "LA-3018-50P", hydroxyl equivalent of about 151, 2-methoxypropanol solution with a solid content of 50%) , Naphthol-based curing agent ("HPC-9500" manufactured by DIC Co., Ltd., hydroxyl equivalent 153, MEK solution having a solid content of 60% by weight) 25 parts, curing accelerator ("1B2PZ" manufactured by Shikoku Kasei Kogyo Co., Ltd., 1-benzyl Spherical silica (average particle diameter) surface-treated with 2 parts of -2-phenylimidazole, MEK solution with a solid content of 3 mass%) and a phenylaminosilane coupling agent ("KBM573" manufactured by Shin-Etsu Chemical Co., Ltd.) 0.5 μm, 200 parts of “SOC2” manufactured by Adomatex Co., Ltd.) were mixed, uniformly dispersed with a high-speed rotary mixer, and filtered with a cartridge filter (“SHP050” manufactured by ROKITECHNO) to prepare a resin varnish 6, and Example 1 and In the same way, adhesive film 6 was prepared.

[Table 1]

<Examples 4 to 6>

In Examples 1 to 3, component (d) was surface-treated with a phenylaminosilane-based coupling agent ("KBM573" manufactured by Shin-Etsu Chemical Co., Ltd.) (average particle diameter: 3 µm, Denka Co., Ltd.) manufactured "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 matters. These adhesive films were capable of forming an insulating layer with sufficiently small warpage and no occurrence of cracks or the like when manufacturing a wiring board having a buried type wiring layer. In Examples 4 to 6, the average coefficient of linear thermal expansion, modulus of elasticity, strength at break, and average maximum diameter of the domains also gave good results similar to Examples 1 to 3.

1: wiring board
10: substrate with wiring layer
11: substrate (core substrate)
12: first metal layer
13: second metal layer
14: wiring layer (buried wiring layer)
20: adhesive film
21: thermosetting resin composition layer
21 ': insulating layer
22: support
23: protective film
31: via hole
40: conductor layer
41: plating seed layer
42: electric field plating layer
50: mask pattern
61: field via

Claims (19)

(1) a step of preparing a base material with a wiring layer having a base material and a wiring layer formed on at least one surface of the base material;
(2) Laminating an adhesive film containing a thermosetting resin composition layer on a base material with a wiring layer so that the wiring layer is embedded in the thermosetting resin composition layer, and thermally curing to form an insulating layer;
(3) a step of connecting the wiring layers between layers; and
(4) Step of removing substrate
An adhesive film used in a method for manufacturing a wiring board comprising:
The adhesive film includes a support and a thermosetting resin composition layer,
The thermosetting resin composition layer includes (a) an epoxy resin having an aromatic structure;
(a) The epoxy resin having an aromatic structure includes a liquid epoxy resin and a solid epoxy resin,
The cured product obtained by thermally curing the thermosetting resin composition layer has an average coefficient of linear thermal expansion at 30 ° C to 150 ° C of 0.1 ppm / ° C or more and 16 ppm / ° C or less,
The cured product obtained by thermally curing the thermosetting resin composition layer has an elastic modulus at 25°C of 0.1 GPa or more and 12 GPa or less,
An adhesive film having a breaking strength at 25°C of a cured product obtained by thermally curing a layer of a thermosetting resin composition of 45 MPa or more and 500 Mpa or less. The method according to claim 1, wherein the step (3) is at least one of a step of forming a via hole in the insulating layer and forming a conductor layer, and a step of polishing or grinding the insulating layer to expose the wiring layer, adhesive film. An adhesive film used in the manufacture of a wiring board having an insulating layer and a buried wiring layer embedded in the insulating layer, comprising:
The adhesive film includes a support and a thermosetting resin composition layer,
The insulating layer is a cured product of a thermosetting resin composition layer,
The thermosetting resin composition layer includes (a) an epoxy resin having an aromatic structure;
(a) The epoxy resin having an aromatic structure includes a liquid epoxy resin and a solid epoxy resin,
The cured product of the thermosetting resin composition layer has an average coefficient of linear thermal expansion at 30 ° C to 150 ° C of 0.1 ppm / ° C or more and 16 ppm / ° C or less,
The cured product of the thermosetting resin composition layer has an elastic modulus at 25°C of 0.1 GPa or more and 12 GPa or less,
The adhesive film whose breaking strength at 25 degreeC of the cured product of a thermosetting resin composition layer is 45 Mpa or more and 500 Mpa or less. The thermosetting resin composition according to any one of claims 1 to 3, wherein the thermosetting resin composition layer is made of a thermosetting resin composition, (a) an epoxy resin having an aromatic structure, (b) a glass transition temperature of -15 An adhesive film comprising a polymer resin that is liquefied at 25° C. or higher or 25° C., (c) a curing agent, and (d) an inorganic filler. The method of claim 4, wherein the component (b) is 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. An adhesive film having at least one structure selected from the group consisting of structures. The adhesive film according to claim 4, wherein the content of the component (b) is 2% by mass to 13% by mass based on 100% by mass of the non-volatile component in the thermosetting resin composition. The adhesive film according to claim 4, wherein component (d) is selected from silica or alumina. The adhesive film according to claim 4, wherein the content of component (d) is 73% by mass or more based on 100% by mass of the non-volatile component in the thermosetting resin composition. The adhesive film according to claim 4, wherein the mixing ratio (mass ratio) of component (d) and component (b) (component (d)/component (b)) is 5 to 45. (1) a step of preparing a base material with a wiring layer having a base material and a wiring layer formed on at least one surface of the base material;
(2) Laminating the adhesive film according to any one of claims 1 to 3 on a base material with a wiring layer so that the wiring layer is embedded in the thermosetting resin composition layer, and thermally curing to form an insulating layer;
(3) a step of connecting the wiring layers between layers; and
(4) a step of removing the substrate;
A method for manufacturing a wiring board comprising: The method according to claim 10, wherein the step (3) is at least one of a step of forming a via hole in the insulating layer and forming a conductor layer, and a step of polishing or grinding the insulating layer to expose the wiring layer, method. The method according to claim 10, wherein the step (3) is a step of forming a via hole in the insulating layer and forming a conductor layer, and is performed by laser irradiation. The method according to claim 12, comprising a step of performing a roughening treatment before forming the conductor layer. 11. The method according to claim 10, wherein the wiring board is a flexible wiring board. The method according to claim 10, wherein the minimum pitch of the wiring pattern is 40 μm or less. A wiring board comprising: an insulating layer that is a cured product of the thermosetting resin composition layer of the adhesive film according to any one of claims 1 to 3; and a buried wiring layer embedded in the insulating layer. The wiring board according to claim 16, which is a flexible wiring board. The wiring board according to claim 16, wherein the insulating layer has a thickness of 2 μm or more and 100 μm or less. A semiconductor device comprising the wiring board according to claim 16.

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