TWI642340B - Manufacturing method of wiring board - Google Patents

Abstract

It is a method of manufacturing a wiring board that can realize fine wiring and can make electrical connection caused by a hole portion provided in an insulating layer more reliable. The manufacturing method of the wiring board (10) includes: engineering (A), which is a project to prepare a structure with an insulating layer (20) and a molecular bonding layer (30), and the insulating layer (20) has The first main surface (20a) and the second main surface (20b) opposite to the first main surface, the molecular bonding layer (30) is only provided on the first main surface, or is provided on the first On both the main surface and the second main surface; and project (B), which is a process to form a metal layer (42) bonded to the molecular bonding layer; and project (C), which is to perform laser irradiation and form a penetration The hole part (26) of the metal layer, the molecular bonding layer and the insulating layer; and the process (D) is the process of removing the slag treatment for the hole part; and the process (E) is the formation of the conductor layer ( 44) The project; and the project (F) is the project of forming the wiring layer (40).

Description

Manufacturing method of wiring board

The present invention relates to a method of manufacturing a wiring board.

In recent years, there has been an increasing demand for miniaturization and thinning of electronic equipment. Therefore, the wiring board used in the manufacture of electronic equipment is also required to further refine the wiring.

When the wiring layer is formed on the insulating layer, the following general technique is known: that is, the bonding force generated by utilizing the unevenness of the surface of the insulating layer formed by roughening the surface of the insulating layer , To join the wiring layer and the insulating layer to each other. However, when roughening is used to form irregularities on the surface of the insulating layer, it is difficult to form the wiring with good accuracy due to the presence of the irregularities. Therefore, further fine wiring Will become difficult.

In order to achieve further miniaturization of the wiring in the wiring board, a molecular bonding layer is formed on the surface of the insulating layer, and the molecular bonding layer is used to bond the wiring layer and the insulating layer with chemical adhesive force. The manufacturing method of the board is well known (refer to Non-Patent Document 1). As a molecular bonding agent for forming such a molecular bonding layer, it is well known to have various Compounds of various types (refer to Patent Document 1).

[Prior Technical Literature] [Patent Literature]

[Patent Document 1] International Publication No. 2012/043631

[Non-patent literature]

[Non-Patent Document 1] Journal of Electronic Installation Vol. 16 No. 6 (2013), 450 ~ 456

According to the method for manufacturing a flexible wiring board disclosed in Non-Patent Document 1, the insulating layer (polyimide film) is provided with holes, and then a molecular bonding layer is formed. Therefore, not only the inner wall of the hole, when the hole is a via hole, a molecular bonding layer is also formed on the surface of the wiring exposed from the hole. There is a possibility that the electrical connection made by the filled via formed later may not be established or the resistance may increase.

Therefore, the present invention is to provide a manufacturing method of a wiring board that can realize further fine wiring of wiring and can make electrical connection caused by a hole portion provided in an insulating layer more reliable, as purpose.

That is, the present invention provides the following inventions [1] to [7].

[1] A method of manufacturing a wiring board, characterized in that it includes: process (A), which is a process for preparing a structure having an insulating layer and a molecular bonding layer, the insulating layer having a first main surface And a second main surface facing the first main surface, the molecular bonding layer is provided only on the first main surface, or on both the first main surface and the second main surface Upper; and Project (B), which is a process for forming a metal layer joined to the molecular bonding layer; and Project (C), which is for laser irradiation to form a through metal layer, the molecular bonding layer, and the insulation The engineering of the hole part of the layer; and the engineering (D), which is the process of removing the slag treatment for the aforementioned hole; and the engineering (E), which is the engineering of forming the conductor layer; The project that forms the wiring layer.

[2] The method of manufacturing a wiring board according to [1], wherein the process (A) is a process for preparing a structure, the insulation layer is a hardened prepreg, and the molecular bonding layer is It is provided on both of the first main surface and the second main surface of the insulating layer.

[3] The method for manufacturing a wiring board according to [1], wherein the step (A) is a step for preparing a structure, the insulating layer is provided on a circuit board, and the molecular bonding layer is It is provided only on the first main surface opposite to the second main surface to which the circuit board is bonded.

〔4〕 Manufacture of wiring boards as described in any of [1] to [3] The method, wherein the process (A) is a process for preparing a structure further including a protective film bonded to the molecular bonding layer, and the process (B) is to peel the protective film and form a joint The engineering of the metal layer at the aforementioned molecular junction layer.

[5] The method for manufacturing a wiring board according to any one of [1] to [3], wherein the step (A) further includes a protective film provided at the molecular bonding layer The process, the process (B), is a process of peeling the protective film from the structure and forming a metal layer bonded to the molecular bonding layer.

[6] The method for manufacturing a wiring board as described in any one of [1] to [5], wherein, after the aforementioned process (D) and before the aforementioned process (E), it further includes: G) is a process of removing the metal layer, and the process (E) is a process of forming a conductor layer on the exposed molecular bonding layer and the hole.

[7] The method of manufacturing a wiring board as described in any one of [1] to [6], wherein the aforementioned process (B) is a process of forming a metal layer by an electroless plating process.

According to the method of manufacturing a wiring board according to the present invention, it is possible to provide a method that can achieve further fine wiring while maintaining good peel strength even without performing the roughening process as in the prior art. In addition, the electrical connection caused by the hole provided in the insulating layer can become a more reliable wiring board.

10‧‧‧Distribution board

20‧‧‧Insulation

20a‧‧‧1st main surface

20b‧‧‧ 2nd main surface

22‧‧‧hardened prepreg

24‧‧‧ circuit board

24a‧‧‧Electronic circuit

26‧‧‧Hole (through hole, guide hole)

30‧‧‧Molecular junction layer

40‧‧‧Wiring layer

42‧‧‧Metal layer

44‧‧‧Conductor layer

44a, 45a‧‧‧ Region 1

44b, 45b‧‧‧ Region 2

44c‧‧‧Region 3

45‧‧‧Electrolytic plating

45c‧‧‧Buried area

46‧‧‧First wiring layer

48‧‧‧Second wiring layer

50‧‧‧Wiring in through hole, filled via hole

60‧‧‧Structure

100‧‧‧Mask pattern

110‧‧‧Protection film

[FIG. 1] FIG. 1 is a schematic diagram showing a cut end surface of a wiring board cut by a cut line passing through a hole.

[FIG. 2] FIG. 2 is a schematic diagram of a structure used in the manufacture of a wiring board.

[FIG. 3] FIG. 3 is a schematic diagram for explaining the manufacturing process of the wiring board.

[FIG. 4] FIG. 4 is a schematic diagram for explaining the manufacturing process of the wiring board.

[FIG. 5] FIG. 5 is a schematic diagram for explaining the manufacturing process of the wiring board.

[FIG. 6] FIG. 6 is a schematic diagram for explaining the manufacturing process of the wiring board.

[FIG. 7] FIG. 7 is a schematic diagram showing an end surface of a wiring board cut by a cutting line passing through a hole.

[FIG. 8] FIG. 8 is a schematic view of a structure used in the manufacture of a wiring board.

[FIG. 9] FIG. 9 is a schematic diagram for explaining the manufacturing process of the wiring board.

[FIG. 10] FIG. 10 is a schematic diagram for explaining the manufacturing process of the wiring board.

[Figure 11] Figure 11 is used for the manufacturing process of the wiring board Illustrated schematic.

[FIG. 12] FIG. 12 is a schematic diagram for explaining the manufacturing process of the wiring board.

[FIG. 13] FIG. 13 is a schematic diagram for explaining the manufacturing process of the wiring board.

The embodiments of the present invention will be described below with reference to the drawings. In addition, each drawing is only a rough display of the shape, size, and arrangement of constituent elements on the premise that the invention can be understood. The present invention is not limited by the contents described below, and it is possible to appropriately change each constituent element without departing from the gist of the present invention. In the drawings used in the following description, the same component elements are indicated by the same component symbols, and repeated descriptions may be omitted. In addition, the configuration of the embodiment of the present invention is not absolutely manufactured or used based on the configuration illustrated in the drawings.

The manufacturing method of the wiring board of the present invention includes: engineering (A), which is an engineering for preparing a structure having an insulating layer and a molecular bonding layer, the insulating layer having a first main surface and the first The second main surface facing the main surface, the molecular bonding layer is provided only on the first main surface, or on both the first main surface and the second main surface; and engineering ( B) is a process of forming a metal layer bonded to the molecular bonding layer; and process (C) is a laser irradiation to form a through metal layer, the molecular bonding layer and The project of the hole part of the aforementioned insulating layer; and the project (D), which is a process for removing the slag from the aforementioned hole part; and the project (E), which is the process of forming the conductor layer; and the project (F), It is a project to form a wiring layer.

In the following, the first embodiment of the present invention (the insulating layer is a wiring board as a core substrate) and the second embodiment (the insulating layer is a build-up wiring board as a build-up (BUILD-UP) insulating layer) The manufacturing method of the wiring board is explained separately.

1. The first embodiment 〔Distribution board〕

First, a configuration example of a wiring board manufactured by the method of manufacturing a wiring board according to the first embodiment of the present invention will be described with reference to FIG. 1. FIG. 1 is a schematic diagram of a wiring board cut by a cutting line passing through a hole.

As shown in FIG. 1, in general, the wiring board 10 of the first embodiment is provided with an insulating layer 20. The insulating layer 20 includes a first main surface 20a and a second main surface 20b facing the first main surface 20a.

The insulating layer 20 of the first embodiment is a hardened prepreg 22 that hardens the prepreg.

At the wiring board 10 of the first embodiment, the molecular bonding layer 30 is provided on both the first main surface 20a and the second main surface 20b. The molecular bonding layer 30 has the insulating layer 20 and the metal layer 42 formed by mutually different materials to be bonded by chemical bonding force Features.

Hereinafter, the structure in the process of manufacturing the wiring board 10 including the insulating layer 20, the molecular bonding layer 30, and the like may be simply referred to as a "structure".

At the molecular bonding layer 30 on both the first main surface 20a side and the second main surface 20b side, a metal layer 42 is provided. The material of the metal layer 42 is not particularly limited as long as it is resistant to desmear treatment in the process (D) described later. Examples of the material of the metal layer 42 include copper (Cu) and nickel (Ni). The thickness of the metal layer 42 is as long as it can prevent damage caused by the work performed after the process of forming the metal layer 42 for the molecular bonding layer 30, and can be prevented from flashing in the wiring formation process described later The removal process such as the flash etching process is removed, and the system is not particularly limited as long as this condition is satisfied. The thickness of the metal layer 42 is generally 0.1 μm to 5 μm, and more preferably 0.3 μm to 2 μm.

In addition, since the metal layer 42 is for the purpose of preventing damage to the molecular bonding layer 30 caused by the process performed after the process of forming the metal layer 42, after achieving this purpose, it can be Remove. Therefore, the wiring board 10 of the first embodiment also includes a type in which the metal layer 42 is not provided.

The wiring board 10 is provided with holes 26. The hole portion 26 of the first embodiment is the molecular bonding layer 30 and the first main surface penetrating both the insulating layer 20, the first main surface 20a side and the second main surface 20b side The through hole of the metal layer 42 on both the 20a side and the second main surface 20b side.

The wiring board 10 is provided with a wiring layer 40. The wiring board 10 of the first embodiment includes a first wiring layer 46 provided on the first main surface 20a side and a second wiring layer 48 provided on the second main surface 20b side.

The first wiring layer 46, when viewed from the thickness direction thereof, includes: a first region 42a that is a partial region on the side of the first main surface 20a in the metal layer 42, and a metal that is connected to the metal The first region 42a of the first region 42a of the layer 42 is the first region 44a of the partial region on the first main surface 20a side of the conductor layer 44 and the electrolytic plating layer that is joined to the first region 44a of the conductor layer 44 The first region 45a of the partial region on the first main surface 20a side of 45.

The second wiring layer 48, when viewed from the thickness direction thereof, includes: a second region 42b that is a partial region on the second main surface 20b side of the metal layer 42 and a metal that is The second region 42b of the second layer 42b of the layer 42 is the second region 44b of the partial region on the second main surface 20b side of the conductor layer 44 and the electrolytic plating layer which is joined to the second region 44b of the conductor layer 44 The second area 45b of the partial area of the second main surface 20b in 45.

In other words, the first wiring layer 46 is formed by laminating the first region 42a of the metal layer 42 and the first region 44a of the conductor layer 44 and the first region 45a of the electrolytic plating layer 45. In addition, the second wiring layer 48 is formed by combining the second region 42b of the metal layer 42 and the conductor layer 44 The second region 44b and the second region 45b of the electrolytic plating layer 45 are laminated to constitute.

In addition, the first wiring layer 46 and the second wiring layer 48 are not only linear wiring, but may include, for example, electrode pads (pads) on which external terminals can be mounted.

The hole 26 as a through hole has its inner wall covered by the third region 44c in the conductor layer 44 and is buried by the buried region 45c in the electrolytic plating layer 45 joined to the third region 44c In this way, the through-hole wiring 50 electrically connecting the first wiring layer 46 and the second wiring layer 48 is made.

The first region 44a, the second region 44b, and the third region 44c of the conductor layer 44 can also be integrally configured to be electrically connected. The first region 45a and the second region 45b of the electrolytic plating layer 45 And the third region 45c can also be integrally configured so as to be electrically connected.

[Manufacturing method of wiring board]

Hereinafter, a method of manufacturing a wiring board according to the first embodiment of the present invention will be described.

The process (A) of the manufacturing method of the wiring board of the present invention is a process for preparing a structure having an insulating layer and a molecular bonding layer, the insulating layer having a first main surface and facing the first main surface The second main surface, the molecular bonding layer, is only provided on the first main surface, or is provided on the first main surface and the second main surface On both sides.

<Engineering (A)>

2, the structure prepared in the process (A) of the first embodiment will be described. FIG. 2 is a schematic diagram of a structure used in the manufacture of a wiring board.

The process (A) of the first embodiment is a process for preparing a structure 60. The insulating layer 20 is a hardened prepreg, and the molecular bonding layer 30 is provided on the first main surface 20a of the insulating layer 20 and 2 On both sides of the main surface 20b.

As described above, the insulating layer 20 of the first embodiment is a hardened prepreg. Hereinafter, the hardened prepreg 22 serving as the insulating layer 20 will be described.

(Hardened prepreg)

The hardened prepreg 22 is a structure in which a sheet-shaped prepreg impregnated with a resin composition in a sheet-shaped fiber base material is hardened. The hardened prepreg 22 can be formed by using any suitable prepreg according to the application of the wiring board 10.

The hardened prepreg 22 and the flaky fiber base material that can be contained in the prepreg that is the material thereof are not particularly limited, and glass cloth, amide nonwoven fabric, liquid crystal polymer nonwoven fabric, etc. can be used The commonly used is the base material of flaky fibrous base material for prepreg. The thickness of the hardened prepreg 22 and the prepreg can be set based on the application of the wiring board 10 Suitable thickness. From the viewpoint of further thinning the wiring board 10, it is desirable to use a sheet-like fibrous base material having a thickness of 10 μm to 150 μm, and particularly to use a sheet-like fibrous base material having a thickness of 10 μm to 100 μm and a thickness of 10 μm A sheet-like fibrous base material of ~ 50 μm and a sheet-like fibrous base material of 10 μm to 30 μm in thickness are more ideal.

As a specific example of the glass cloth that can be used as a sheet-like fiber substrate, "STYLE 1027MS" (warp density 75 / 25mm, weft density 75 / 25mm, cloth weight 20g / m ² , thickness 19μm), `` STYLE 1037MS '' made by Asahi-Schwebel (Co., Ltd.) (warp density 70 / 25mm, weft density 73 / 25mm, cloth weight 24g / m ² , Thickness 28μm), (Co., Ltd.) Yousei Manufacturing Co., Ltd. "1078" (warp density 54 / 25mm, weft density 54 / 25mm, cloth weight 48g / m ² , thickness 43μm), (Co., Ltd.) Youze "1067NS" manufactured by the manufacturing company, "1037NS" manufactured by Youze Manufacturing Co., Ltd. (warp density 72 / 25mm, weft density 69 / 25mm, cloth weight 23g / m ² , thickness 21μm), (Co., Ltd.) Arisawa Seisakusho K.K. "1027NS" (warp density of 75 / 25mm, the weft yarn density of 75 / 25mm, fabric weight of 19.5g / m ^2, a thickness of 16μm), (Ltd.) Arisawa Seisakusho "1015NS" (warp density 95 threads / 25mm, weft thread density 95 threads / 25mm, cloth weight 17.5g / m ² , thickness 15μm), (Co., Ltd.) Youze "1000NS" manufactured by the manufacturing company (warp density 85/25 mm, weft density 85/25 mm, cloth weight 11 g / m ² , thickness 10 μm), etc. In addition, as a specific example of the liquid crystal polymer nonwoven fabric, "VECRUS" (weight per unit area: 6 g / m) produced by KURARAY's aromatic polyester nonwoven fabric manufactured by the melt blowing method (melt blowing) is cited. ² ~ 15g / m ² ) or "VECRY" etc.

(Resin composition)

The components of the resin composition that can be used in the formation of the prepreg and the content thereof are subject to the condition that the cured prepreg has sufficient hardness and insulation, and are not particularly limited.

Hereinafter, the details of the resin composition that can be used in the formation of the prepreg will be described. In addition, the content of the components of the resin composition is indicated as the amount when the total amount of nonvolatile components in the resin composition is 100% by mass.

As a component of the resin composition that can be used as the material of the prepreg, that is, the material of the hardened prepreg 22, it can also include inorganic fillers, epoxy resins, hardeners, organic fillers, Hardening accelerator, thermoplastic resin, flame retardant, etc. Here, each of the aforementioned components that can be included in the resin composition will be described separately.

-Inorganic filler-

The resin composition can suppress the occurrence of problems such as chipping and circuit deformation caused by the difference in thermal expansion rate due to the reduction in thermal expansion rate after curing, and the excessive reduction in melt viscosity. From a viewpoint, it is desirable to include an inorganic filler.

The material of the inorganic filler is not particularly limited. For example, it may include silicon oxide, aluminum oxide, glass, cordierite, silicon oxide, barium carbonate, zinc oxide, hydrotalcite, diaspore, and magnesium hydroxide. , Aluminum nitride, manganese nitride, strontium carbonate, zirconia, barium zirconate titanate, zirconium phosphate, zirconium tungstate, barium sulfate, talc, clay, mica powder, aluminum hydroxide, magnesium hydroxide, calcium carbonate, magnesium carbonate , Magnesium oxide, boron nitride, aluminum borate, barium titanate, strontium titanate, calcium titanate, magnesium titanate, bismuth titanate, titanium oxide, barium zirconate and calcium zirconate. Among these, amorphous silicon oxide, fused silicon oxide, crystalline silicon oxide, synthetic silicon oxide, hollow silicon oxide, and other silicon oxides are ideal. Furthermore, as the silicon oxide, spherical silica is ideal. The inorganic filler can be used as one kind alone, or two or more kinds can be used in combination. The spherical (fused) silica sold on the market includes, for example, "SOC1", "SOC2", "SOC4", "SOC5", and "SOC6" manufactured by ADMATECHS (Co., Ltd.).

From the viewpoint of improving the fluidity of the resin composition, the average particle diameter of the inorganic filler is preferably in the range of 0.01 μm to 4 μm, and more preferably in the range of 0.05 μm to 2.5 μm, and The range of 0.1μm ~ 1.5μm is more ideal, and the range of 0.3μm ~ 1.0μm is more ideal. The average particle diameter of the inorganic filler can be measured by laser diffraction and scattering based on Mie scattering theory. Specifically, the particle size distribution of the inorganic filler can be made on a volume basis by a laser diffraction scattering type particle size distribution measuring device, and then the median diameter can be measured as the average particle size. In this case, it is appropriate to use the inorganic filler to make a division in water by ultrasound Scattered measurement samples. As a laser diffraction scattering type particle size distribution measuring device, "LA-500" manufactured by HORIBA, Ltd. (Co., Ltd.) can be used.

Inorganic fillers, from the viewpoint of improving moisture resistance and dispersibility, are based on aminosilane coupling agents, epoxy silane coupling agents, mercaptosilane coupling agents, silane coupling agents, organic silazane compounds It is desirable to perform treatment with one or more surface treatment agents such as titanate-based coupling agents. Examples of commercially available products of such surface treatment agents include “KBM403” (3-glycidoxypropyltrimethoxysilane) manufactured by Shin-Etsu Chemical Co., Ltd., and “KBM803” manufactured by Shin-Etsu Chemical Co., Ltd. "(3-mercaptopropyltrimethoxysilane), Shin-Etsu Chemical Co., Ltd." KBE903 "(3-aminopropyltriethoxysilane), Shin-Etsu Chemical Co., Ltd." KBM573 "(N- (Phenyl-3-aminopropyltrimethoxysilane), Shin-Etsu Chemical Industry Co., Ltd. "SZ-31" (hexamethyldisilazane), etc.

The inorganic filler after the surface treatment with the surface treatment agent can be washed with a solvent (for example, methyl ethyl ketone (MEK)). The carbon content is measured. Specifically, as a solvent, a sufficient amount of MEK is added to the inorganic filler that has been surface-treated with the surface-treating agent, and ultrasonic washing is performed at 25 ° C. for 5 minutes. Next, the supernatant liquid is removed, and the non-volatile components (solid content) are dried. Thereafter, the carbon amount per unit surface area of the inorganic filler can be measured using a carbon analyzer. As a carbon analyzer, "EMIA-320V" manufactured by HORIBA, Ltd. (Co., Ltd.) can be used.

The amount of carbon per unit surface area of the inorganic filler is preferably 0.02 mg / m ² or more, and more preferably 0.1 mg / m ² or more from the viewpoint of improving the dispersibility of the inorganic filler. , It is more ideal to be 0.2mg / m ² or more. On the other hand, from the viewpoint of suppressing the increase in melt viscosity, the amount of carbon per unit surface area of the inorganic filler is preferably 1 mg / m ² or less, and 0.8 mg / m ² or less For more ideal, it is more ideal to be 0.5 mg / m ² or less.

-Organic filler-

From the viewpoint of improving the adhesion with the layer formed by the electroplating process, the resin composition is preferably composed of an organic filler. Examples of organic fillers include rubber particles. As the rubber particles that are organic fillers, for example, rubber particles that are not dissolved in an organic solvent described below and are not compatible with an epoxy resin, a curing agent, a thermoplastic resin, etc. described later. Such rubber particles are generally prepared by increasing the molecular weight of the components of the rubber particles to the extent that they will not dissolve in organic solvents or resins, and making them in the form of particles.

Examples of the rubber particles that are organic fillers include core-shell rubber particles, cross-linked acrylonitrile butadiene rubber particles, cross-linked styrene butadiene rubber particles, and acrylic rubber particles. The core-shell rubber particles are rubber particles having a core layer and a shell layer. For example, the shell layer of the outer layer is composed of a glassy polymer and the inner layer The core layer is a two-layer structure composed of a rubbery polymer, or the outer shell layer is composed of a glassy polymer, the middle layer is composed of a rubbery polymer, and the inner layer of the core layer is composed of a glassy Rubber particles of three-layer structure composed of polymers. The glass-like polymer layer is composed of, for example, methyl methacrylate copolymer and the like, and the rubber-like polymer layer is composed of, for example, butyl acrylate copolymer (butyl rubber) and the like. Examples of usable rubber particles include "STAPHYROID AC3816N" manufactured by GANZ (Co., Ltd.). The rubber particle system may be used alone or in combination of two or more.

The average particle size of rubber particles as an organic filler is more preferably in the range of 0.005 μm to 1 μm, and more preferably in the range of 0.2 μm to 0.6 μm. The average particle size of the rubber particles can be measured using the dynamic light scattering method. For example, it is possible to uniformly disperse rubber particles in an appropriate organic solvent by ultrasonic waves, etc., and use a thick particle size analyzer ("FPAR-1000" manufactured by Otsuka Electronics Co., Ltd.) to obtain quality The particle size distribution of the rubber particles was made on the basis of reference, and the median diameter was used as the average particle size to measure.

-Epoxy resin-

Examples of the epoxy resin include bisphenol A epoxy resin, bisphenol F epoxy resin, bisphenol S epoxy resin, bisphenol AF epoxy resin, and dicyclopentadiene epoxy resin. , Phenolic epoxy resin, naphthol novolak epoxy resin, phenol novolak epoxy resin, tert-butyl-catechol epoxy resin, naphthalene epoxy resin, naphthol epoxy resin, Anthracene ring Oxygen resin, epoxypropylamine epoxy resin, epoxypropyl ester epoxy resin, cresol novolac epoxy resin, biphenyl epoxy resin, linear aliphatic epoxy resin, with bis Epoxy resin with olefin structure, alicyclic epoxy resin, heterocyclic epoxy resin, epoxy resin containing spiro ring, cyclohexane dimethanol type epoxy resin, naphthyl ether type epoxy resin and trihydroxy Methyl epoxy resin, etc. One type of epoxy resin may be used alone, or two or more types may be used in combination.

The epoxy resin is preferably an epoxy resin having two or more epoxy groups in one molecule. When the non-volatile component of the epoxy resin is set to 100% by mass, it is desirable that at least 50% by mass or more is an epoxy resin having two or more epoxy groups in one molecule. Among them, there are epoxy resins containing two or more epoxy groups in one molecule and being liquid at a temperature of 20 ° C (hereinafter, referred to as “liquid epoxy resins”) and in It is desirable to have three or more epoxy groups in one molecule and to be a solid epoxy resin at a temperature of 20 ° C (hereinafter, referred to as “solid epoxy resin”). As the epoxy resin, by using a liquid epoxy resin and a solid epoxy resin together, it is possible to impart excellent flexibility.

Examples of the liquid epoxy resin include bisphenol A epoxy resin, bisphenol F epoxy resin, phenol novolac epoxy resin, bifunctional aliphatic epoxy resin, and naphthalene epoxy resin. Ideally, it is a bisphenol A epoxy resin, a bisphenol F epoxy resin, or a naphthalene epoxy resin. Specific examples of the liquid epoxy resin include "HP4032", "HP4032D", and "HP4032SS" manufactured by DIC (Co., Ltd.) (Naphthalene type epoxy resin), "jER828EL", "jER1007" (bisphenol A type epoxy resin) manufactured by Mitsubishi Chemical Corporation, "jER807" (bisphenol F type epoxy resin), "jER152" (Phenolic novolac epoxy resin), "ZX1059" (mixture of bisphenol A epoxy resin and bisphenol F epoxy resin) manufactured by Nippon Steel Chemical Co., Ltd., "YL7410" (2 Functional aliphatic epoxy resin), etc. These systems may be used alone or in combination of two or more.

Examples of the solid epoxy resin include crystalline bifunctional epoxy resin, tetrafunctional naphthalene epoxy resin, cresol novolac epoxy resin, dicyclopentadiene epoxy resin, and phenol epoxy resin. Resin, naphthol novolac epoxy resin, biphenyl epoxy resin, naphthyl ether epoxy resin. Specific examples of the solid epoxy resin include "HP-4700", "HP-4710" (4-functional naphthalene epoxy resin) manufactured by DIC (Co., Ltd.), and "N-690" (formaldehyde (Phenol novolac epoxy resin), `` N-695 '' (cresol novolac epoxy resin), `` HP-7200 '' (dicyclopentadiene epoxy resin), `` EXA7311 '', `` EXA7311-G3 "," HP-6000 "(naphthyl ether type epoxy resin)," EPPN-502H "(shenphenol epoxy resin) manufactured by Nippon Kayaku Co., Ltd.," NC7000L "(naphthol novolac type) Epoxy resin), "NC3000", "NC3000H", "NC3000L", "NC3100" (biphenyl type epoxy resin), "ESN475" (naphthol novolak type ring made by Nippon Steel Chemical Co., Ltd.) Oxygen resin), "ESN485" (naphthol novolac epoxy resin), "YX4000H", "YL6121" manufactured by Mitsubishi Chemical Corporation. (Biphenyl type epoxy resin), "YX4000HK" (bixylenol type epoxy resin) which is a crystalline 2-functional epoxy resin, etc.

As an epoxy resin, when a liquid epoxy resin and a solid epoxy resin are used together, the ratio of these amounts (liquid epoxy resin: solid epoxy resin) is preferably a mass ratio It becomes the range of 1: 0.1 ~ 1: 4. By setting the ratio of the amount of the liquid epoxy resin and the solid epoxy resin to such a range, it is possible to obtain effects such as that a hardened body having sufficient breaking strength can be obtained. From the viewpoint of obtaining such an effect, the ratio of the amount of liquid epoxy resin to solid epoxy resin (liquid epoxy resin: solid epoxy resin) is more preferably, which is 1: 0.3 by mass ratio. The range of ~ 1: 3.5 is more ideal, it becomes the range of 1: 0.6 ~ 1: 3, especially ideal, it becomes the range of 1: 0.8 ~ 1: 2.5.

The content of the epoxy resin in the resin composition is preferably 3% by mass to 50% by mass, more preferably 5% by mass to 45% by mass, and 5% by mass to 40% by mass. It is more ideal, and it is particularly ideal to become 7% by mass to 35% by mass.

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

The epoxy equivalent of the epoxy resin is more preferably in the range of 50-3000, more preferably in the range of 80-2000, and more preferably in the range of 110-1000. By setting to such a range, it is possible to obtain Hardened body with cross-link density. In addition, the epoxy equivalent can be measured according to the method normalized as JIS K7236. Here, the epoxy equivalent refers to the mass of epoxy resin containing 1 equivalent of epoxy group.

-hardener-

The curing agent is not particularly limited as long as it has the function of curing the epoxy resin, but examples thereof include phenolic curing agents, naphthol curing agents, active ester curing agents, and benzo Oxazine hardener, cyanate ester hardener, carbodiimide hardener. One type of hardener may be used alone, or two or more types may be used in combination.

Examples of the phenol-based hardener and naphthol-based hardener include a phenol-based hardener having a novolak structure, a naphthol-based hardener having a novolak structure, a nitrogen-containing phenol-based hardener, and a triazine skeleton The cresol hardener and the phenol hardener containing triazine skeleton.

As specific examples of the phenol-based hardener and the naphthol-based hardener, for example, Minghe Chemical ("MEH-7700", "MEH-7810", "MEH-7851" manufactured by Co., Ltd., Nippon Kayaku, etc.) (Co., Ltd.) "NHN", "CBN", "GPH", Dongdu Chemical (Co., Ltd.) "SN170", "SN180", "SN190", "SN475", "SN485", "SN495" "," SN375 "," SN395 "," LA7052 "," LA7054 "," LA3018 "made by DIC (Co., Ltd.), etc.

Although it is not particularly limited as an active ester hardener, it is generally In particular, compounds having two or more reactive ester groups such as phenol esters, thiophenol esters, N-hydroxylamine esters, and esters of heterocyclic hydroxy compounds in one molecule can be preferably used. The active ester-based hardener is preferably a hardener obtained by condensation reaction of a carboxylic acid compound and / or thiocarboxylic acid compound with a hydroxy compound and / or thiol compound. In particular, from the viewpoint of improving heat resistance, the active ester hardener obtained from the carboxylic acid compound and the hydroxy compound is ideal, and the active ester obtained from the carboxylic acid compound and the phenol compound and / or naphthol compound is also used The system hardener is more ideal. 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, phenolphthalin (phenolphthalin), methylated bisphenol A, and methylated bisphenol. Phenol F, methylated bisphenol S, phenol, o-cresol, m-cresol, p-cresol, catechol, α-naphthol, β-naphthol, 1,5-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, dihydroxydiphenyl ketone, trihydroxydiphenyl ketone, tetrahydroxydiphenyl ketone, 1,3,5-pyrogallol, pyrogallol , Dicyclopentadiene type bisphenol compounds, phenol novolac, etc.

Specific examples of the active ester-based hardener include active ester compounds containing a dicyclopentadiene-type diphenol condensation structure, active ester compounds containing a naphthalene structure, and active ester compounds containing phenol novolac acetyl compounds. An active ester compound containing phenol novolac benzoyl compounds.

A commercially available product as an active ester hardener, for example, as an active ester compound containing a dicyclopentadiene-type diphenol condensation structure, Examples include "EXB9451", "EXB9460", "EXB9460S", and "HPC-8000-65T" manufactured by DIC (Co., Ltd.). As active ester compounds containing a naphthalene structure, DIC (Co., Ltd.) The "EXB9416-70BK" manufactured as an active ester compound containing phenol novolac acetoacetate includes the "DC808" manufactured by Mitsubishi Chemical (Co., Ltd.) as a benzoate compound containing phenol novolac. Examples of the active ester compound include "YLH1026" manufactured by Mitsubishi Chemical Corporation.

As specific examples of the benzoxazine-based hardener, for example, "HFB2006M" manufactured by Showa Polymer Co., Ltd., "Pd" and "Fa" manufactured by Shikoku Chemical Industry Co., Ltd. .

Examples of the cyanate-based curing agent include bisphenol A dicyanate, polyphenol cyanate (oligo (3-methylene-1,5-phenylene cyanate), 4,4 '-Methylene bis (2,6-xylyl cyanate), 4,4'-ethylene diphenyl dicyanate, hexafluorobisphenol A dicyanate, 2,2-bis (4-cyanate) phenylpropane, 1,1-bis (4-cyanate phenylmethane), bis (4-cyanate-3,5-xylyl) methane, 1,3-bis (4-cyanate phenyl-1- (methylethylene)) benzene, bis (4-cyanate phenyl) sulfide, and bis (4-cyanate phenyl) ether and other two functions Multifunctional cyanate resin derived from cyanate resin, phenol novolak, cresol novolak, etc. These cyanate ester resins are a part of triazineized prepolymer, etc. As cyanate ester hardener Specific examples include "PT30" and "PT60" (both are phenolic novolak type polyfunctional cyanate resins) manufactured by Lonza Japan Co., Ltd., "BA230" (a part or all of bisphenol A dicyanate is a tripolymerized prepolymer) and the like.

Specific examples of the carbodiimide-based hardener include "V-03" and "V-07" manufactured by Nisshinbo CHEMICAL (Co., Ltd.).

The ratio of the amount of epoxy resin to hardener is based on the ratio of "total number of epoxy groups in epoxy resin": "total number of reactive groups in hardener", which is 1: 0.2 ~ 1: The range of 2 is ideal, and the range of 1: 0.3 ~ 1: 1.5 is more ideal, and the range of 1: 0.4 ~ 1: 1 is more ideal. Here, the reactive groups of the hardener are active hydroxyl groups, active ester groups, etc., and are different depending on the type of hardener. In addition, the total number of epoxy groups in epoxy resins is the value obtained by dividing the mass of the non-volatile components of each epoxy resin by the epoxy equivalent for all epoxy resins. The total number of reactive groups of the hardener is the total value of the mass of the non-volatile components of each hardener divided by the equivalent of the reactive group for all hardeners. When the amount ratio between the epoxy resin and the hardener is within this range, the heat resistance when the hardened body is formed will be further improved.

Regarding the content of the hardener, the ratio between the total number of epoxy groups in the epoxy resin and the total number of reactive groups in the hardener is preferably in the range of 1: 0.2 ~ 1: 2, and more ideally The range of 1: 0.3 ~ 1: 1.5, and the ideal range is 1: 0.4 ~ 1: 1.

The resin composition is preferably a mixture of liquid epoxy resin and solid epoxy resin (liquid epoxy resin) The mass ratio of resin to solid epoxy resin is ideally in the range of 1: 0.1 ~ 1: 4, more preferably in the range of 1: 0.3 ~ 1: 3.5, and as 1: The range of 0.6 ~ 1: 3 is more ideal, and the range of 1: 0.8 ~ 1: 2.5 is particularly ideal), and as the hardener, it includes from phenolic hardener, naphthol hardener, active ester One or more selected from the group consisting of hardeners and cyanate ester hardeners (preferably, one or more selected from the group consisting of phenol hardeners and naphthol hardeners) More preferably, it is one or more selected from the group consisting of a phenol novolak resin containing a triazine skeleton and a naphthol-based hardener, and more preferably, it is a phenol novolak containing a triazine skeleton Hardener for varnish resin).

-Thermoplastic resin-

Examples of the thermoplastic resins include phenoxy resins, acrylic resins, polyvinyl acetal resins, polyimide resins, polyamidoamide resins, polyether sulfonate resins, and polysulfonate resins. The thermoplastic resin system may be used alone or in combination of two or more.

The weight average molecular weight of the thermoplastic resin in terms of polystyrene is preferably in the range of 8000 to 70,000, more preferably in the range of 10,000 to 60,000, and more preferably in the range of 20,000 to 60,000. . The weight average molecular weight in terms of polystyrene of the thermoplastic resin is measured by gel permeation chromatography (GPC) method. Specifically, the polystyrene-equivalent weight average molecular weight of the thermoplastic resin can be used as a measuring device (made by Shimadzu Corporation) The produced "LC-9A / RID-6A], and used as the column" Shodex K-800P / K-804L / K-804L "manufactured by Showa Denko (Co., Ltd.), and used chloroform as the mobile phase Etc., and measured at a column temperature of 40 ° C, and then calculated using the standard curve of standard polystyrene.

Examples of the phenoxy resin include a bisphenol A skeleton, a bisphenol F skeleton, a bisphenol S skeleton, a bisphenol acetophenone skeleton, a novolac skeleton, a biphenyl skeleton, a stilbene skeleton, and a dicyclopentadiene skeleton. , One or more phenoxy resins selected from the group consisting of norbornene skeleton, naphthalene skeleton, anthracene skeleton, adamantane skeleton, terpene skeleton, and trimethylcyclohexane skeleton. The terminal of the phenoxy resin may be a functional group of any of phenolic hydroacid group, epoxy group and the like. One type of phenoxy resin can be used alone, or two or more types can be used in combination. Specific examples of the phenoxy resin include "1256" and "4250" (both phenoxy resins containing a bisphenol A skeleton) and "YX8100" (containing a bisphenol S skeleton) manufactured by Mitsubishi Chemical Corporation. Phenoxy resin), and "YX6954" (containing bisphenol acetophenone skeleton phenoxy resin), in addition to, can also be listed "FX280" and "FX293" made by Toto Chemical Co., Ltd., Mitsubishi Chemical (Co., Ltd.) "YL7553", "YL6794", "YL7213", "YL7290", "YL7482", etc.

As the acrylic resin, from the viewpoint of further reducing the thermal expansion coefficient and the elastic modulus, the functional group-containing acrylic resin is preferable, and the epoxy group-containing acrylic resin having a glass transition temperature of 25 ° C. or lower is more preferable.

Number average molecular weight of acrylic resin containing functional groups (Mn), the ideal system is 10000 ~ 1000000, and the more ideal system is 30,000 ~ 900000.

The functional group equivalent of the acrylic resin containing functional groups is more preferably 1,000 to 50,000, and more preferably 2,500 to 30,000.

As the epoxy group-containing acrylic resin having a glass transition temperature of 25 ° C or lower, an epoxy group-containing acrylate copolymer resin having a glass transition temperature of 25 ° C or lower is ideal. Specific examples thereof include NAGASECHEMTEX ( "SG-80H" (Epoxy-containing acrylate copolymer resin (number average molecular weight Mn: 350,000g / mol, epoxy value 0.07eq / kg, glass transition temperature 11 ° C)), NAGASECHEMTEX ( "SG-P3" (epoxy group-containing acrylate copolymer resin (number-average molecular weight Mn: 850,000 g / mol, epoxy value 0.21 eq / kg, glass transition temperature 12 ° C)) manufactured by Co., Ltd.).

Specific examples of the polyvinyl acetal resin include electrochemical butyraldehyde "4000-2", "5000-A", "6000-C", and "6000-EP" manufactured by the Electric Chemical Industry Co., Ltd. ", S-LEC BH series, BX series," KS-1 "and other KS series, BL series, BM series, etc. manufactured by Sekisui Chemical Industry Co., Ltd.

As specific examples of the polyimide resin, "RIKACOAT SN20" and "RIKACOAT PN20" manufactured by New Japan Physical and Chemical Co., Ltd. can be cited. In addition, as a specific example of the polyimide resin, a linear polyimide obtained by reacting a bifunctional hydroxyl-terminated polybutadiene, a diisocyanate compound, and a tetrabasic acid anhydrous (in Polyimide tree described in Japanese Patent Laid-Open No. 2006-37083 Fat), polyimide containing polysiloxane skeleton (polyimide resin described in JP 2002-12667 and JP 2000-319386, etc.) and other modified polyimides .

As specific examples of the polyimide amide imide resin, "VYLOMAX HR11NN" and "VYLOMAX HR16NN" manufactured by Toyobo Co., Ltd. can be cited. In addition, as a specific example of the polyimide amide imide resin, there may also be listed polysiloxane amide-containing polyimide amide imide "KS9100", "KS9300", etc. manufactured by Hitachi Chemical Industry Co., Ltd. Denatured polyamide amide imide.

As a specific example of the polyether resin, "PES5003P" manufactured by Sumitomo Chemical Co., Ltd., etc. may be mentioned.

As specific examples of the poly-resin resin, poly-resins "P1700" and "P3500" manufactured by SOLVAY ADVANCED POLYMERS (Co., Ltd.) can be cited.

The content of the thermoplastic resin in the resin composition is preferably 0.1% by mass to 20% by mass. By setting the content of the thermoplastic resin within such a range, the viscosity of the resin composition becomes moderate, and a resin composition layer having a uniform thickness and bulk properties can be formed.

-Hardening accelerator-

Examples of curing accelerators include phosphorus-based curing accelerators, amine-based curing accelerators, imidazole-based curing accelerators, and guanidine-based curing accelerators.

Examples of the phosphorus-based hardening accelerator include triphenylphosphine, phosphonium borate compounds, tetraphenylphosphonium tetraphenylborate, n-butylphosphonium tetraphenylborate, and tetrabutylphosphonium decanoate. Acid salt, (4-tolyl) triphenylphosphonium thiocyanate, tetraphenylphosphonium thiocyanate, butyl triphenylphosphonium thiocyanate, etc.

Examples of the amine-based hardening accelerator include trialkylamines such as triethylamine and tributylamine, 4-dimethylaminepyridine (DMAP), benzyldimethylamine, 2,4,6- Ginseng (dimethylaminomethyl) phenol, 1,8-diazabicyclo (5,4,0) -undecene, etc.

Examples of the imidazole hardening accelerator include 2-methylimidazole, 2-undecylimidazole, 2-heptadecylimidazole, 1,2-dimethylimidazole, and 2-ethyl-4-methylimidazole. , 2-phenylimidazole, 2-phenyl-4-methylimidazole, 1-benzyl-2-methylimidazole, 1-benzyl-2-phenylimidazole, 1-cyanoethyl-2-methyl Imidazole, 1-cyanoethyl-2-undecylimidazole, 1-cyanoethyl-2-ethyl-4-methylimidazole, 1-cyanoethyl-2-phenylimidazole, 1-cyanoethyl- 2-undecylimidazole salt trimellitate, 1-cyanoethyl-2-phenylimidazole salt trimellitate, 2,4-diamino-6- [2'-methylimidazolyl- (1 ')]-ethyl-s-triazine, 2,4-diamino-6- [2'-undecylimidazolyl- (1')]-ethyl-s-triazine, 2, 4-Diamino-6- [2'-ethyl-4'-methylimidazolyl- (1 ')]-ethyl-s-triazine, 2,4-diamino-6- [2' -Methylimidazolyl- (1 ')]-ethyl-s-triazine isocyanurate adduct, 2-phenylimidazole isocyanurate adduct, 2-phenyl-4,5- Dihydroxymethylimidazole, 2-phenyl-4-methyl-5-hydroxymethylimidazole, 2,3-dihydro-1H-pyrrolo [1,2-a] benzimidazole, 1-dodecyl 2-methyl-3-benzyl imidazole chloride Was 2-imidazoline, 2-phenyl Imidazole compounds such as imidazoline and adducts of imidazole compounds and epoxy resins.

Examples of the guanidine hardening accelerator include dicyandiamide, 1-methylguanidine, 1-ethylguanidine, 1-cyclohexylguanidine, 1-phenylguanidine, and 1- (o- Group) guanidine, dimethylguanidine, diphenylguanidine, trimethylguanidine, tetramethylguanidine, pentamethylguanidine, 1,5,7-triazabicyclo [4.4.0] dec-5-ene, 7-methyl-1,5,7-triazabicyclo [4.4.0] dec-5-ene, 1-methyl biguanide, 1-ethyl biguanide, 1-n-butyl biguanide, 1-n- Octadecyl biguanide, 1,1-dimethyl biguanide, 1,1-diethyl biguanide, 1-cyclohexyl biguanide, 1-allyl biguanide, 1-phenyl biguanide, 1- (o- Base) Biguanide and so on.

The hardening accelerator can be used as one kind alone or in combination of two or more kinds. The content of the hardening accelerator in the resin composition is used within the range of 0.05% by mass to 3% by mass when the total amount of the nonvolatile components of the epoxy resin and the hardener is 100% by mass Ideal.

-Flame retardant-

Examples of flame retardants include organic phosphorus flame retardants, organic nitrogen-containing phosphorus compounds, nitrogen compounds, silicone flame retardants, and metal hydroxides. As an example of a flame retardant that can be used, "HCA-HQ-HST" manufactured by Sanko Co., Ltd. can be cited. The flame retardant system can be used alone or two or more types can be used in combination. The content of the flame retardant in the resin composition layer is not particularly limited, but it is preferably within a range of 0.5% by mass to 10% by mass, and within a range of 1% by mass to 9% by mass The range is more ideal, and the range of 1.5% to 8% by mass is more ideal.

-Other additives-

The resin composition may be added with other additives for the purpose of adjusting the characteristics of the resin composition or its hardened body according to needs. Examples of such other additives include organic copper compounds and organic compounds. Organometallic compounds such as zinc compounds and organic cobalt compounds, and resin additives such as tackifiers, defoamers, leveling agents, adhesion imparting agents, and coloring agents.

(Formation of hardened prepreg)

First, the formation process of the hardened prepreg is explained. The prepreg can be produced by a well-known method such as hot-melt method or solvent method. In the hot-melt method, the resin composition is not temporarily dissolved in an organic solvent, but the resin composition is temporarily coated on a release paper with good releasability, and this is laminated on a sheet-like fiber substrate, or The prepreg is manufactured by directly coating on a sheet-like fibrous base material with a die coater. In addition, in the solvent, the flaky fiber base material is immersed in the resin varnish obtained by dissolving the resin composition in an organic solvent, thereby impregnating the flaky fiber base material with the resin composition After that, it was dried to form a prepreg. Furthermore, the prepreg may be formed by sandwiching two resin sheets made of a resin composition from both sides of the sheet-like fibrous base material and heating them under pressure. And continuous hot lamination, To form it.

The organic solvent used when preparing the resin varnish used to form the prepreg includes ketones such as acetone, methyl ethyl ketone, and cyclohexanone, ethyl acetate, butyl acetate, and celsulone. Acetate esters, propylene glycol monomethyl ether acetate, carbitol acetate, etc. acetates, carbitols such as cyclus and butyl carbitol, aromatic hydrocarbons such as toluene and xylene , Dimethylformamide, dimethylacetamide, N-methylpyrrolidone and other amide-based solvents. One type of organic solvent may be used alone, or two or more types may be used in combination.

The formation process of the prepreg can be carried out in a roll-to-roll manner using a long sheet-like fibrous base material, or it can also be carried out in a batch manner.

The hardened prepreg 22 can be formed by subjecting the prepreg to heat treatment under specific conditions. Specifically, as an example of a method of forming the hardened prepreg 22, a vacuum hot stamping process may be mentioned. The vacuum hot stamping process that can be used in the forming process of the hardened prepreg 22 will be described below.

The vacuum hot stamping process is performed, for example, by pressing a metal plate such as a heated stainless steel plate (SUS plate) from both sides of the prepreg.

Vacuum hot stamping works are ideal. It is carried out in a state in which buffer paper, release sheet, etc. are interposed on both sides of the metal plate used. As the buffer paper, for example, "AACP-9N" (thickness: 800 μm) manufactured by Awa Paper Co., Ltd. can be used. Also, as a thin mold For the sheet, for example, "AFLEX 50NNT" (thickness 50 μm) manufactured by Asahi Glass Co., Ltd. can be used.

The conditions of the vacuum hot stamping process are, for example, as long as the air pressure is usually 1 × 10 ⁻² MPa or less, preferably 1 × 10 ⁻³ MPa or less, and the heating temperature is set to, for example, 150 ° C. to 250 ° C. The pressure can be set to 10kgf / cm ² ~ 70kgf / cm ² .

The temperature increase from the normal temperature to the specific heating temperature and the temperature decrease from the specific heating temperature to the normal temperature are preferably performed by maintaining the specific temperature increase rate and temperature decrease rate. The temperature increase rate and the temperature decrease rate are preferably about 5 ° C / min.

Vacuum hot stamping engineering can be carried out using a general vacuum hot stamping device in this technical field. As a vacuum hot stamping apparatus, for example, "MNPC-V-750-5-200" manufactured by Meiji Co., Ltd. (Co., Ltd.), and "VH1-1603" by Kitagawa Seiki are mentioned.

(Molecular junction layer)

The molecular bonding layer 30 provided on both the first main surface 20a and the second main surface 20b of the hardened prepreg 22 can be a molecular bonding agent selected as a material for forming the molecular bonding layer 30, Form it in an appropriate way.

The molecular bonding agent which is the material of the molecular bonding layer 30 is not particularly limited, and for example, commercially available molecular bonding including compounds known in the prior art as described in the aforementioned Patent Document 1 can be used. Agent. As an example of such a molecular bonding agent, a letter can be cited Fluorinated alkyl type "X-24-9453" of triazine thiol functional silicone alkoxy oligomer made by Vietnam Chemical Industry Co., Ltd., aminotriazine novolak resin (for example, DIC Co., Ltd.) ("LA-1356") and epoxy silane coupling agent (eg Shin-Etsu Chemical Co., Ltd., 3-glycidoxypropyltrimethoxysilane, "KBM403"), etc., with a triazine structure Molecular bonding agent with alkoxysilane structure.

The molecular bonding layer 30 is, for example, a hardened prepreg 22 dissolved in a specific concentration in a specific solvent (for example, a mixed solvent in which water, isopropyl alcohol, and acetic acid are mixed) in a molecular bonding agent , Immersing under specific conditions (temperature, time, etc.), and then drying the extracted hardened prepreg 22 under specific conditions, etc., by which the first main surface 20a and The surface of the second main surface 20b. When forming the molecular bonding layer 30, in addition to drying treatment, any appropriate treatment corresponding to the selected material such as ultraviolet irradiation may be further performed.

<Protection film>

As shown in FIG. 2, generally, the process (A) is preferably a process for preparing a structure 60 further including a protective film 110 bonded to the molecular bonding layer 30.

If the molecular bonding layer 30 is covered by such a protective film 110, the molecular bonding layer 30 can be effectively protected. In addition, since the structure 60 provided with the protective film 110 can be stored, for example, it is possible to set the timing of the implementation after the project (B) to be arbitrary Timing.

Examples of the material of the protective film 110 include polyesters such as polyethylene terephthalate (PET) and polyethylene naphthalate (PEN), polycarbonate (PC), and polymethacrylate Acrylic acid such as ester (PMMA), cyclic polyolefin, cellulose triacetate (TAC), polyether sulfide (PES), polyether ketone, polyimide, etc.

In the protective film 110 including the aforementioned material, the surface on the side to which the hardened prepreg 22 is joined may be subjected to roughening treatment, corona treatment, or the like.

In addition, as the protective film 110, a "release film protective film" having a release layer on the side joined to the hardened prepreg 22 may also be used. Examples of the mold release agent used in the formation of the mold release layer with the mold release layer protective film include alkyd resins, polyolefin resins, urethane resins, and silicone resins. More than one release agent selected from the group. The release layer, for example, can be formed by applying a solution containing a release agent on the surface of the protective film 110 and drying it.

As a protective film attached to the release layer, commercially available products can also be used. As the protective film with a release layer, for example, "SK-1" manufactured by LINTEC (Co., Ltd.), which is a PET film having a release layer with an alkyd resin-based release agent as a main component, "AL-5", "AL-7", etc.

Although the thickness of the protective film 110 is not particularly limited, it is preferably in the range of 5 μm to 75 μm, and 10 μm to 60 μm. The range is more ideal, and the range of 12.5μm ~ 55μm is more ideal. In addition, when using a mold-releasing layer protective film, it is preferable to set the thickness of the entire mold-releasing layer protective film to the above range.

In the first embodiment, the protective film 110 may be formed by a layer by covering both the first main surface 20a side and the second main surface 20b side of the hardened prepreg 22 according to the usual method. Lamination can be done by pressing. The lamination of the protective film 110 of the hardened prepreg 22 can be performed using a lamination device well known in the prior art.

<Engineering (B)>

The project (B) will be described with reference to FIGS. 2 and 3. FIG. 3 is a schematic diagram for explaining the manufacturing process of the wiring board.

Process (B) is the process of forming a metal layer to be bonded to the molecular bonding layer.

As shown in FIGS. 2 and 3, generally, in the process (B) of the first embodiment, when the protective film 110 is provided, it is only necessary to peel off the protective film 110 from the structure 60 and form a bonded molecular bond The layer 30 may be a metal layer 42 for bonding.

The metal layer 42 can be formed by an electroplating process such as electroless plating process using the appropriate materials described above. The process (B) is preferably a process in which the metal layer 42 is formed by an electroless plating process (first electroless plating process) using copper as a material.

Hereinafter, regarding the metal layer 42 as a copper layer, To explain the example of forming the electroplating project.

(1) First, the surface of the molecular bonding layer 30 is washed and alkaline cleaning for charge adjustment is performed.

(2) Next, a prepreg process is performed to adjust the electric charge in order to apply palladium (Pd) to the surface of the molecular bonding layer 30.

(3) Next, palladium which is an activator is given to the molecular bonding layer 30.

(4) Next, palladium given to the surface of the molecular bonding layer 30 is reduced.

(5) Next, by depositing copper on the molecular bonding layer 30, the metal layer 42 is formed.

<Engineering (C)>

Referring to FIG. 3, the following description will be given for the project (C).

Process (C) is a process of performing laser irradiation to form a hole that penetrates the metal layer, the molecular bonding layer, and the insulating layer.

As shown in FIG. 3, generally, in the process (C), it is formed by laser irradiation from the first main surface 20a side of the structure 60 obtained in the aforementioned <process (B)>. A hole 26 (in the first embodiment, the body is a through hole) 26 penetrating through the metal layer 42, the molecular bonding layer 30, and the insulating layer 20.

This laser irradiation can be performed using any appropriate 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 can be used, for example, include lines HITACHI VIA MECHANICS (Co., Ltd.) manufactured by CO ₂ laser processing machine of the "LC-2k212 / 2C", "Mitsubishi Electric Corporation (Ltd.) made of ML605GTWII ", A laser processing machine made by Panasonic Fusion System (Co., Ltd.).

The conditions of the laser irradiation are not particularly limited, and the laser irradiation can be implemented by any suitable project according to the usual method corresponding to the selected means.

The shape of the hole 26, that is, the shape of the outline of the opening when viewed from the extending direction is not particularly limited, but generally it is circular (slightly circular). Hereinafter, when describing the "diameter" of the hole portion 26, it refers to the diameter (diameter) of the outline of the opening when viewed from the extending direction. In this specification, the top diameter refers to the diameter r1 of the contour of the hole 26 on the first main surface 20a side, and the bottom diameter refers to the diameter r2 of the contour of the hole 26 on the second main surface 20b side.

<Engineering (D)>

Referring to Fig. 3, the following description will be given for the project (D).

Process (D) is a process for removing slag from the hole.

The dross removal process is performed to remove the dross in the hole 26. This slag removal treatment can be either wet slag removal treatment or dry slag removal treatment.

The specific engineering of degumming slag treatment will not damage The function of the molecular bonding layer 30 is a condition and is not particularly limited. For example, well-known processes and conditions commonly used when forming an insulating layer of a multilayer printed wiring board can be adopted. Examples of dry slag removal treatment include plasma treatment, etc. As examples of wet slag removal treatment, swelling treatment caused by swelling liquid and removal of glue caused by oxidizing agent are listed. The slag treatment and the slag removal treatment caused by the neutralization solution are carried out in sequence. In the following, the wet slag removal treatment will be described.

The swelling liquid used in the wet slag removal treatment is not particularly limited. Examples of the swelling liquid include alkaline solutions and surfactant solutions, and the like is preferably an alkaline solution. As the alkaline solution, sodium hydroxide solution and potassium hydroxide solution are more preferable. Examples of the swelling liquid sold on the market include "Swelling Dip Securiganth P" and "Swelling Dip Securiganth SBU" manufactured by ATOTECH JAPAN (Co., Ltd.).

The swelling treatment caused by the swelling liquid is not particularly limited, but, for example, the structure 60 provided with the holes 26 can be immersed in the swelling liquid at 30 ° C to 90 ° C for 1 to 20 minutes , To do it. From the viewpoint of suppressing the degree of swelling of the resin constituting the insulating layer 20 to a moderate degree, the swelling treatment is performed by immersing the structure 60 in a swelling liquid of 40 ° C to 80 ° C for 5 seconds to 15 minutes Treatment is ideal.

The oxidant used in the wet slag removal treatment is not particularly limited. Examples of the oxidizing agent include alkaline permanganate in which potassium permanganate and sodium permanganate are dissolved in an aqueous solution of sodium hydroxide. Solution. Degumming slag treatment caused by an oxidizing agent such as an alkaline permanganic acid solution is preferably performed by immersing the structure 60 in an oxidizing agent solution heated to 60 ° C to 80 ° C for 10 to 30 minutes. In addition, the concentration of permanganate in the alkaline permanganic acid solution is preferably set to 5% by mass to 10% by mass.

Examples of the oxidizing agent sold in the market include alkaline permanganate solutions such as "Concentrate Compact P" and "Dosing Solution Securiganth P" manufactured by ATOTECH JAPAN (Co., Ltd.).

The neutralizing solution is preferably an acidic aqueous solution. Examples of commercially available products include "Reduction Solution Securiganth P" manufactured by ATOTECH JAPAN (Co., Ltd.).

The treatment by the neutralizing liquid can be performed by immersing the structure 60 treated with the oxidizing agent in the neutralizing liquid at 30 ° C to 80 ° C for 5 to 30 minutes. From the viewpoint of workability and the like, the method of immersing the object subjected to the degumming treatment by the oxidant solution at 40 ° C to 70 ° C and the liquid for 5 to 20 minutes is ideal.

As described above, in the manufacturing method of the wiring board 10 of the first embodiment, since the roughening treatment of the insulating layer 20 is not required, the flatness of the insulating layer 20 is maintained, and therefore, it is possible to achieve further The fine wiring. In addition, since the metal layer 42 covering the molecular bonding layer 30 is formed and the hole portion 26 is formed in a state where the molecular bonding layer 30 is protected by the metal layer, the metal layer can be prevented The bonding force between the 42 and the insulating layer 20 caused by the molecular bonding layer 30 is reduced. Therefore, the metal layer 42 and the insulating layer 20 can be firmly bonded. Furthermore, since the formed hole portion 26 is subjected to degumming treatment, even if the top diameter r1 and the bottom diameter r2 are small and the aspect ratio is large, the hole portion 26 can be formed In 26, the clean hole portion 26 is obtained by removing the residue of the material of the molecular bonding layer 30, the reactants generated in the formation process of the hole portion 26, and the like. Therefore, the conduction due to the hole portion 26 provided at the insulating layer 20 can be further improved.

<Engineering (E)>

Referring to Fig. 4, the description will be given for the project (E). FIG. 4 is a schematic diagram for explaining the manufacturing process of the wiring board.

Project (E) is a project to form a conductor layer.

As shown in FIG. 4, generally, in the process (E), the conductor layer 44 is formed on the surfaces of the metal layer 42 and the hole 26 of the structure 60 obtained in the aforementioned <process (C)>. That is, the first region 44a joined to the metal layer 42 on the first main surface 20a side, the second region 44b joined to the metal layer 42 on the second main surface 20b side, and the hole 26 are formed The inner wall layer is joined to the conductor layer 44 of the third region 44c.

The conductor layer 44 can be formed using the same process as that of the metal layer 42 described above. Therefore, the detailed description of the conductor layer 44 is omitted here.

The conductor layer 44 is ideally formed by electroless plating. When the metal layer 42 is formed by an electroless plating process, that is, by the first electroless plating process, there is a case where the metal layer 42 is called the first electroless plating layer, and there will be The conductor layer 44 formed by the same electroless plating process, that is, by the second electroless plating process is called a second electroless plating layer.

In addition, the metal layer 42 can be removed after the purpose of preventing damage to the molecular bonding layer 30 caused by the process performed after the process of forming the metal layer 42 is achieved. Therefore, the process (E) may be carried out after the metal layer 42 is removed. That is, if the metal layer 42 is first removed after the slag removal process, and then the conductor layer 44 is formed, it can be caused by the flashover process (removal process of the metal layer 42 and the conductor layer 44) described later The amount of removal is further reduced, and the treatment process can be performed under more gentle conditions. Therefore, it is possible to realize further fine wiring.

<Engineering (F)>

With reference to FIGS. 5 and 6, the project (F) will be described. 5 and 6 are schematic diagrams for explaining the manufacturing process of the wiring board.

Engineering (F) is an engineering to form a wiring layer.

Here, the first wiring layer 46 and the second wiring layer 48, which are wiring layers 40, can be formed by simultaneously performing a single project, or can be formed as separate projects. When the first wiring layer 46 And when the formation of the second wiring layer 48 is carried out as separate projects at different timings, it is only necessary to use a resist layer etc. in order to protect the surface on the side formed at a later timing The protective layer is covered, and after processing on the side formed at the earlier timing sequence, the protective layer may be removed and processed at the side formed at the later timing sequence.

Hereinafter, an example will be described in which the formation of the first wiring layer 46 and the second wiring layer 48 is performed as a single process by the semi-increase method.

As shown in FIG. 5, the mask pattern 100 is formed first. The mask pattern 100 is formed as a pattern that covers the conductor layer 44 that is the seed layer and is not covered by the area where the wiring is formed and exposes the area where the wiring is formed.

The mask pattern 100 can be formed using a dry film (photosensitive photoresist film) known in the prior art. As the dry film, for example, "ALPHO NIT3025" (trade name) manufactured by NICHIGO MORTON (CO., LTD.), Which is a dry film with a PET film, can be used.

The mask pattern 100 can be formed by, for example, bonding a dry film to the conductor layer 44 and performing exposure engineering, development engineering, and cleaning engineering under specific conditions.

As shown in FIG. 6, in general, the electrolytic plating process is performed under the condition that the material will be filled into the hole portion 26 as a through hole, and the structure 60 where the mask pattern 100 is formed is formed The electrolytic plating layer 45 bonded to the conductor layer 44. At this time, by combining the holes 26 is buried to form the wiring 50 in the through hole.

Next, the mask pattern 100 is stripped and removed by any suitable process corresponding to the selected material, and then the exposed conductive layer 44 and the metal layer directly below it are carried out 42 Under any suitable conditions for removal, a first wiring layer 46 is formed on the first main surface 20a side, and a second wiring layer 48 is formed on the second main surface 20b side (see FIG. 1).

Through the above process, a wiring board 10 having the structure described with reference to FIG. 1 can be manufactured.

In addition, according to the manufacturing method of the wiring board 10 of the present invention, when the wiring layer 40 is formed, it may also include the process of removing the metal layer 42 after the process (D) and before the process (E) ( G).

Hereinafter, this project (G) will be described.

<Engineering (G)>

The project (G) is a project to remove the metal layer after the project (D) and before the project (E).

When the process (G) is carried out, the process (E) is a process of forming the conductor layer 44 at the exposed molecular bonding layer 30 and the hole 26.

The process (G) may be any suitable process such as etching process performed under conditions corresponding to the material of the conductor layer 44.

In the case of project (G), since the wiring layer 40 is formed by using only the conductor layer 44 as the seed layer, the amount of conductors that should be removed when the wiring layer 40 is formed is reduced. Moreover, the wiring layer 40 can be patterned under more gentle conditions, and therefore, the wiring can be further miniaturized.

2. The second embodiment 〔Distribution board〕

First, a configuration example of a wiring board manufactured by the method of manufacturing a wiring board according to the second embodiment of the present invention will be described with reference to FIG. 7. FIG. 7 is a schematic diagram showing an end surface of a wiring board cut by a cutting line passing through a hole.

In addition, in the following description, the same components and materials as those in the first embodiment described above will be omitted in principle, and only the differences will be described.

As generally shown in FIG. 7, the wiring board 10 of the second embodiment is provided with a circuit board 24 having an electronic circuit 24a.

In the manufacturing method of the wiring board 10 of the present invention, the circuit board 24 corresponds to a glass epoxy substrate, a metal substrate, a polyester substrate, a polyimide substrate, a BT resin substrate, a thermosetting polyphenylene ether substrate A so-called core substrate having a patterned electronic circuit 24a on one or both sides of an insulating substrate, etc., and further formed with a build-up insulating layer and a build-up wiring layer.

The electronic circuit 24a of the circuit board 24, in the illustrated example, Although it is shown that the structure is provided only on one side, the system is not limited to this, but may be provided on both sides. The electronic circuit 24a includes wiring, electrode pads, electronic parts, etc., and is configured to perform a specific function.

As the circuit board 24, any suitable circuit board known in the prior art having wiring, electronic parts, etc. having a desired function as the electronic circuit 24a can be used.

The thickness of the electronic circuit 24a patterned on one or both sides of the insulating base material is not particularly limited. From the viewpoint of thinning, it is more preferably 70 μm or less, more preferably 60 μm or less, and even more preferably 50 μm or less, even more preferably 40 μm or less, and particularly preferably 30 μm or less. 20 μm or less, 15 μm or less, or 10 μm or less. Although the lower limit of the thickness of the electronic circuit 24a is not particularly limited, it is preferably 1 μm or more, more preferably, 3 μm or more, and more preferably, 5 μm or more.

The line / space ratio of the electronic circuit 24a patterned on one side or both sides of the insulating base material is not particularly limited, but it is excellent from reducing surface irregularities and obtaining smoothness From the standpoint of the build-up insulating layer, usually it is 900/900 μm or less, preferably, 700/700 μm or less, more preferably, 500/500 μm or less, and even more preferably, 300/300 μm or less Even more ideally, it is 200/200 μm or less. The lower limit of the line / space ratio of the electronic circuit 24a is not particularly limited, but from the viewpoint of making the embedding of the resin composition between the spaces good, it is preferably 1/1 μm or more.

As the circuit board 24, for example, "R1515A" made by PANASONIC (Co., Ltd.), which is a double-sided copper-clad laminate that is a glass cloth substrate epoxy resin, can be cited by patterning the copper layer A circuit board obtained by wiring or the like is formed.

At the circuit board 24, an insulating layer 20 is provided. In the illustrated example, the insulating layer 20 is provided so as to cover the electronic circuit 24a of the circuit board 24. The insulating layer 20 of the second embodiment is a build-up insulating layer. Therefore, it can be formed by using materials used in a build-up wiring board known in the prior art. In the insulating layer 20 of the second embodiment, a sheet-like fibrous base material such as a glass cross can also be included.

As an example of the sheet-like fibrous base material that can be used in the insulating layer 20 of the second embodiment, the sheet-like fibrous base material that can be included in the prepreg of the first embodiment described above can be cited.

The insulating layer 20 includes a first main surface 20a and a second main surface 20b facing the first main surface 20a.

In the wiring board 10 of the second embodiment, a molecular bonding layer 30 is provided on the first main surface 20a side.

The wiring board 10 is provided with a wiring layer 40 which is a build-up wiring layer provided at the molecular bonding layer 30 on the side of the first main surface 20a.

The wiring layer 40 is configured to include a conductive layer 44 bonded to the molecular bonding layer 30 and electrolysis bonded to the conductive layer 44 The laminated structure of the plating layer 45.

The wiring board 10 is provided with holes 26. The hole portion 26 of the second embodiment is a via hole that penetrates the insulating layer 20 and the molecular bonding layer 30 on the side of the first main surface 20a and exposes a part of the electronic circuit 24a.

The conductor layer 44 includes a first region 44a, which is a partial region on the side of the first main surface 20a, and a second region 44b, which is joined to a part of the electronic circuit 24a exposed from the hole 26, and defines a hole The inner wall of the portion 26 is constituted by a third region 44c which is covered, and these are constituted so as to be electrically connected to each other, that is, constituted integrally.

The electrolytic plating layer 45 is buried by the first region 45a, which is a partial region on the side of the first main surface 20a, and the hole 26 covered by the second region 44b and the third region 44c of the conductor layer 44 The buried region 45c is formed by electrically connecting to each other, that is, it is formed integrally.

In addition, the wiring layer 40 is not only linear wiring, but may also include, for example, electrode pads (pads) on which external terminals can be mounted.

The hole portion 26 as a via hole, the inner wall of which is covered by the second region 44b and the third region 44c in the conductor layer 44, and is electroplated to join the second region 44b and the third region 44c The third region 45c in the layer 45 is buried and is formed as a filled via 50 that electrically connects the wiring layer 40 and the electronic circuit 24a.

In the configuration example shown in FIG. 7, although the insulating layer 20 provided with the hole 26 and the wiring layer 40 as the build-up wiring layer are included The build-up layer is only shown as one layer, but the present invention is not limited to this structure. The wiring board 10 of the second embodiment may be a multilayer build-up wiring board in which build-up layers are laminated in two or more layers. In addition, in the configuration example shown in FIG. 7, although the build-up layer including the insulating layer 20 and the wiring layer 40 is shown as a configuration example provided only on one side, the configuration is not limited to Therefore, it may be provided on both sides of the circuit board 24.

[Manufacturing method of wiring board]

8 to 13, a method of manufacturing a wiring board according to the second embodiment having the aforementioned configuration will be described.

<Engineering (A)>

Referring to FIG. 8, first, the structure prepared in the process (A) of the second embodiment will be described. FIG. 8 is a schematic diagram of a structure used in the manufacture of a wiring board.

The process (A) of the second embodiment is to prepare the structure 60. The insulating layer 20 is provided on the circuit board 24, and the molecular bonding layer 30 is only provided on the circuit board 24 for bonding The first main surface 20a on the opposite side of the second main surface 20b.

As described above, the insulating layer 20 of the second embodiment is a build-up insulating layer. In the following, the insulating layer 20 which is a build-up insulating layer will be described.

First, for the structure 60 used to form the project (A) Next, the film and its manufacturing process will be described.

<Next Film>

Next, the film includes an organic support and a resin composition layer provided on the main surface of one of the organic supports.

(Organic support)

Examples of the material of the organic support include the same materials as the protective film 110 described in the first embodiment.

As the organic support, it is suitable to use an organic support with a high glass transition temperature (Tg). The glass transition temperature of the organic support is ideally above 100 ° C.

Examples of the material of the organic support having a glass transition temperature of 100 ° C. or higher include polyesters such as polyethylene naphthalate (PEN), polycarbonate (PC), and polymethyl methacrylate (PMMA). Acrylic acid, cyclic polyolefin, cellulose triacetate (TAC), polyether sulfide (PES), polyether ketone, polyether ether ketone, polyimide, etc. Among them, from the viewpoint of heat resistance, polyethylene naphthalate and polyimide are preferred.

In the organic support including the aforementioned material, a roughening treatment, a corona treatment, or the like may be applied to the surface joined to the resin composition layer described later.

Also, as an organic support, it may be used on the side where the resin composition layer is joined, that is, on the side coated with the resin composition There is an "organic support attached to the mold release layer" (hereinafter, the organic support attached to the mold release layer is simply referred to as an organic support). Examples of the mold release agent used in forming the mold release layer with the mold release layer organic support include alkyd resins, polyolefin resins, urethane resins, and silicone resins. More than one release agent selected from the group. The release layer, for example, can be formed by applying a solution containing a release agent on the surface of the organic support and drying it.

As an organic support with a release layer, commercially available products can also be used. For example, LINTEC (Co., Ltd.), which is a PET film having a release layer with an alkyd resin release agent as a main component, can be cited. ) -Made "SK-1", "AL-5", "AL-7", etc.

Although the thickness of the organic support is not particularly limited, it is preferably in the range of 5 μm to 75 μm, more preferably in the range of 10 μm to 60 μm, and more preferably in the range of 12.5 μm to 55 μm. In addition, in the case of using an organic support with a mold-releasing layer, it is preferable to set the thickness of the entire organic support with a mold-releasing layer within the aforementioned range.

(Resin composition layer)

The thickness of the resin composition layer is not particularly limited as long as the wiring can be formed by the electroplating process. The resin composition layer is ideal, and its thickness is 0.5 μm to 10 μm, and more preferably, it is 1 μm to 5 μm.

(Resin composition)

The components and content of the resin composition that can be used in the formation of the resin composition layer are based on the condition that when the insulating layer 20 is hardened to have sufficient hardness and insulation, it is not specifically made limited.

The resin composition may also include inorganic fillers, epoxy resins, hardeners, organic fillers, hardening accelerators, thermoplastic resins, and flame retardants. The components that can be contained in the resin composition are the same as the components that can be used in the formation of the cured prepreg 22 described in the first embodiment, and therefore their description is omitted.

In addition, as the epoxy resin that is a component of the resin composition, when a liquid epoxy resin and a solid epoxy resin are used in combination, the ratio of these amounts (liquid epoxy resin: solid epoxy resin) Resin), ideally, it is in the range of 1: 0.1 to 1: 4 based on the mass ratio. By setting the ratio of the amount of the liquid epoxy resin and the solid epoxy resin to such a range, it is possible to obtain i) when used in the form of an adhesive film, moderate adhesion can be obtained, ii) When it is used in the form of an adhesive film, sufficient flexibility can be obtained, handling properties are improved, and iii) a hardened body having sufficient breaking strength can be obtained, and the like. From the viewpoint of the effects of i) to iii) above, the ratio of the amount of liquid epoxy resin to solid epoxy resin (liquid epoxy resin: solid epoxy resin) is more preferably based on the mass ratio It becomes the range of 1: 0.3 ~ 1: 3.5, which is more ideal. It becomes the range of 1: 0.6 ~ 1: 3, especially ideal, it becomes the range of 1: 0.8 ~ 1: 2.5.

(Then the film formation process)

The resin composition used in the resin composition layer can be suitably mixed by the above-mentioned components and, if necessary, by kneading means (3-roll method, ball mill, bead mill, sand mill, etc.) or It is prepared by mixing means (high-speed mixer, planetary mixer, etc.) for mixing or mixing.

The manufacturing method of the adhesive film provided with the resin composition layer is not particularly limited. For example, a resin varnish in which the resin composition is dissolved in an organic solvent can be prepared, and the resin varnish can be used by a die coater After being coated on the organic support, the coating film of the coated resin varnish is dried to make it.

The organic solvent used when preparing the resin varnish is the same as the organic solvent that can be used for the formation of the prepreg according to the first embodiment described above.

The drying process of the coating film made of resin varnish during the formation of the resin composition layer can be performed by any suitable drying method known by heating, hot air blowing, and the like. By this drying process, the coating film is made into a resin composition layer.

The drying conditions for this drying treatment may be any suitable conditions as long as the boiling point of the organic solvent contained in the resin composition and the resin varnish is considered. The drying conditions may be, for example, about 80 to 150 ° C. for 3 to 15 minutes.

Then the film formation process is based on the use of organic The elongated support body of the holder is ideally performed in a roll-to-roll manner, or it can also be performed in a batch manner.

The film forming process performed by the roll-to-roll method, specifically, can be performed by the following method: that is, one side will be stretched to include at least 2 rolls including the delivery roll and the take-up roll The long organic support between the rolls is continuously transported. The resin composition is coated on one of the main surfaces of the support exposed between the delivery roll and the take-up roll to form a coating film. The obtained coating film was continuously dried to form a resin composition layer.

In this way, it is possible to prepare an adhesive film provided with a resin composition layer on an organic support.

When the prepared adhesive film is temporarily stored, it is desirable to further provide an exposed surface on the side of the resin composition layer that is not bonded to the organic support (that is, A protective film bonded to the side opposite to the organic support). This protective film is useful for preventing dust and the like from adhering to the resin composition layer and preventing damage to the resin composition layer. As the protective film, for example, a polypropylene film, a polyethylene film, or the like can be used. In addition, a thin film made of the same material as the organic support can be used. The thickness of the protective film is not particularly limited, for example, it is 1 μm to 40 μm. The thickness of the protective film is ideal, which is thinner than the thickness of the organic support.

(Insulation)

Next, the formation process of the insulating layer 20 will be described.

First, a lamination process is carried out to laminate the prepared resin composition layer of the adhesive film in contact with the electronic circuit 24a of the circuit board 24.

The conditions of the lamination process are not particularly limited, and well-known conditions used when forming an insulating layer (build-up insulating layer) using an adhesive film can be adopted. For example, it can be carried out by pushing a metal plate such as a heated stainless steel mirror plate from the side of the organic support on which the film is adhered. In this case, it is preferable that the metal plate is not directly pressed, but that the subsequent film can sufficiently follow the irregularities of the surface of the circuit board 24 provided with the electronic circuit 24a, Press the elastic member made of heat-resistant rubber. The ideal stamping temperature is in the range of 70 ℃ ~ 140 ℃. The ideal stamping pressure is in the range of 1kgf / cm ² ~ 11kgf / cm ² (0.098MPa ~ 1.079MPa). The stamping time is ideal. The range is from 5 seconds to 3 minutes.

In addition, the lamination process is preferably performed under a reduced pressure environment of 20 mmHg (26.7 hPa) or less. The lamination process can be carried out using vacuum laminators sold on the market. Examples of vacuum laminators that are commercially available include vacuum press laminators manufactured by Meiji Machinery Co., Ltd. and vacuum film laminators manufactured by NICHIGO MORTON (Co., Ltd.).

After the lamination process is completed, a smoothing process may be performed to heat and pressurize the subsequent film laminated on the circuit board 24.

Smoothing works, generally speaking, are at atmospheric pressure (atmospheric Under pressure, a heated metal plate or a metal roll is used to heat and press the subsequent film laminated on the circuit board 24 to perform it. The conditions of the heat and pressure treatment can be the same as those of the above lamination process.

The lamination process and smoothing process can also be carried out continuously using the same vacuum laminator.

In addition, at any timing after the implementation of the lamination process or the smoothing process, a process of peeling the organic support derived from the adhesive film is performed. The process of peeling the organic support, for example, can be performed mechanically by an automatic peeling device that is commercially available.

Next, a thermosetting process of thermosetting the resin composition layer laminated on the circuit board 24 is performed to form an insulating layer (additional insulating layer).

The conditions of the thermal hardening process are not particularly limited, and the conditions generally adopted when forming the insulating layer of the multilayer printed wiring board can be applied.

The conditions of the thermosetting process can be set to any suitable conditions according to the composition of the resin composition used in the resin composition layer. The conditions of the thermal hardening process, for example, the curing temperature can be set in the range of 120 ° C ~ 240 ° C (more ideally, the range of 150 ° C ~ 210 ° C, more ideally, the range of 170 ° C ~ 190 ° C) The hardening time is set in the range of 5 minutes to 90 minutes (ideally, it is 10 minutes to 75 minutes, and more ideally, it is 15 minutes to 60 minutes).

Before the thermal hardening project, it can also be implemented The process of preheating the resin composition layer at a lower temperature. Before the implementation of the thermosetting process, for example, the temperature may be higher than 50 ° C but less than 120 ° C (preferably, 60 ° C or higher and 110 ° C or lower, and more preferably, 70 ° C or higher and 100 ° C or lower) The preliminary heating of the resin composition layer is performed for 5 minutes or more (preferably, it is 5 minutes to 150 minutes, more preferably, it is 15 minutes to 120 minutes). The preliminary heating is preferably performed under atmospheric pressure (normal pressure).

(Molecular junction layer)

The molecular bonding layer 30 provided on the first main surface 20a of the insulating layer 20 can be formed by an appropriate method using the selected molecular bonding agent.

The example of the molecular bonding agent which is the material of the molecular bonding layer 30 of the second embodiment and the method of forming the molecular bonding layer 30 are as described in the first embodiment.

As shown in FIG. 8, generally, the process (A) is preferably a process for preparing a structure 60 further including a protective film 110 bonded to the molecular bonding layer 30.

In the second embodiment, the protective film 110 may be laminated so as to cover the first main surface 20a side of the insulating layer 20.

The details of the protective film 110 are as described in the first embodiment, so the explanation is omitted.

So and so, and prepare the general structure as shown in Figure 8 The structure 60 and the structure 60 are provided with the insulating layer 20 on the circuit board 24, and the molecular bonding layer 30 is provided only on the first main surface 20a of the insulating layer 20.

<Engineering (B)>

With reference to Fig. 9, an explanation will be given for the project (B). FIG. 9 is a schematic diagram for explaining the manufacturing process of the wiring board.

As shown in FIG. 9, in general, in the process (B) of the second embodiment, when the protective film 110 is provided, the molecular bonding layer 30 exposed by peeling the protective film 110 from the structure 60 is formed. The work of joining the metal layer 42.

The metal layer 42 can be formed by an electroplating process such as electroless plating process using the appropriate materials described above. The process (B) is preferably a process of forming the metal layer 42 by an electroless plating process (first electroless plating process) using copper as a material. The details of the metal layer 42 are the same as those already explained in the first embodiment, so their explanations are omitted.

<Engineering (C)>

Referring to Fig. 10, the following description will be given for the project (C). FIG. 10 is a schematic diagram for explaining the manufacturing process of the wiring board.

As shown in FIG. 10, generally, in the process (C), it is formed by laser irradiation from the first main surface 20a side of the structure 60 obtained in the aforementioned <process (B)>. Through metal layer 42, A hole portion (in the second embodiment, the body is a via hole) 26 in which the molecular bonding layer 30 and the insulating layer 20 expose a part of the electronic circuit 24a.

The details of the laser irradiation and the details of the hole 26 are the same as those already explained in the first embodiment, so their explanation is omitted.

<Engineering (D)>

With reference to FIG. 10, the following describes the project (D).

Process (D) is a process for removing slag from the hole. This slag removal treatment can be either wet slag removal treatment or dry slag removal treatment.

The specific procedures, conditions, and the like of this kind of degumming slag treatment are generally as described in the first embodiment, so their description is omitted.

As described above, in the manufacturing method of the wiring board 10 of the second embodiment, since the roughening treatment of the insulating layer 20 is not required, the flatness of the insulating layer 20 is maintained, and therefore, it is possible to achieve further The fine wiring. In addition, since the metal layer 42 covering the molecular bonding layer 30 is formed and the hole portion 26 is formed in a state where the molecular bonding layer 30 is protected by the metal layer, it is possible to prevent the gap between the conductor layer 44 and the insulating layer 20 Of the bonding force caused by the molecular bonding layer 30 is reduced. Therefore, the conductor layer 44 and the insulating layer 20 can be firmly bonded. Furthermore, since the formed hole portion 26 is subjected to slag removal treatment, even if the top diameter r1 and the bottom diameter r2 are smaller The hole portion 26 having a larger aspect ratio can also form a clean hole from which the residue of the material of the molecular bonding layer 30, the reactants generated in the formation process of the hole portion 26, etc. is removed from the hole portion 26部 26. Therefore, the conduction due to the hole portion 26 provided at the insulating layer 20 can be further improved.

<Engineering (E)>

Referring to FIG. 11, the description will be given for the project (E). FIG. 11 is a schematic diagram for explaining the manufacturing process of the wiring board.

Project (E) is a project to form a conductor layer.

As shown in FIG. 11, in general, the process (E) of the second embodiment depends on the exposed molecular bonding layer 30, the inner wall of the hole 26, and a part of the electronic circuit 24a exposed from the hole 26. The bonding layer forms the conductor layer 44. That is, a first region 44a that is joined to the molecular bonding layer 30 on the side of the first main surface 20a, a second region 44b that is joined to a part of the electronic circuit 24a exposed from the hole 26, and a The inner wall of the hole 26 is joined to the conductor layer 44 of the third region 44c.

The conductor layer 44 can be formed by the same process as the formation process of the metal layer 42 described in the first embodiment. Therefore, the detailed description of the conductor layer 44 is omitted here.

In the second embodiment, as described above, the conductor layer 44 is formed so as to be bonded to the molecular bonding layer 30. Therefore, before performing the aforementioned process (E), the process of removing the metal layer 42 is performed Cheng (G). Since this process (G) is as described in the first embodiment, its description will be omitted.

In the case of project (G), since the wiring layer 40 is formed by using only the conductor layer 44 as the seed layer, the amount of conductors that should be removed when the wiring layer 40 is formed is reduced. Moreover, the wiring layer can be patterned under more gentle conditions. Therefore, the wiring can be further miniaturized. Therefore, the form in which the engineering (E) is carried out after the implementation of the engineering (G) can be suitably applied to the formation of a build-up wiring layer that requires wiring miniaturization.

In addition, in the manufacturing method of the wiring board 10 of the second embodiment, when the specifications of the wiring pitch and the like are allowed, it can be the same as the first embodiment described above, and Without removing the metal layer 42, that is, the project (G) is not implemented, and the project (E) is directly implemented.

<Engineering (F)>

The project (F) will be described with reference to FIGS. 12 and 13. 12 and 13 are schematic diagrams for explaining the manufacturing process of the wiring board.

Engineering (F) is an engineering to form a wiring layer.

The wiring layer 40 is preferably formed by a semi-additive method using the conductor layer 44 as a seed layer. Hereinafter, an example of forming the wiring layer 40 by the semi-additive method will be described.

As shown in FIG. 12, the mask pattern 100 is first formed. The mask pattern 100 is formed as a pattern that covers the conductor layer 44 that is the seed layer and is not covered by the area where the wiring is formed and exposes the area where the wiring is formed. Since the mask pattern 100 is as described in the first embodiment, its description is omitted.

As shown in FIG. 13, in general, the electrolytic plating process is carried out under the condition that the material will be filled into the hole portion 26 as the via hole, and the structure 60 where the mask pattern 100 is formed is formed The electrolytic plating layer 45 includes a first region 45a provided on the first main surface 20a side so as to be joined to the first region 44a of the conductor layer 44 and a buried region 45c in which the hole 26 is buried. At this time, the filling via 50 is formed by burying the hole 26 together.

Next, the mask pattern 100 is peeled off and removed, and then the exposed conductive layer 44 is subjected to flash etching under any suitable conditions to be used as a build-up wiring on the first main surface 20a side. Layer to form the wiring layer 40.

Through the above process, the wiring board 10 having the structure described with reference to FIG. 7 can be manufactured.

When two or more layers of the build-up layer including the insulating layer 20 as the build-up insulating layer and the wiring layer 40 as the build-up wiring layer are required, as long as the project (F) has been implemented For the wiring board 10, the series of the above-mentioned project (A) to the above-mentioned project (F) may be repeated one or more times.

[Use of wiring board]

The wiring board manufactured by the manufacturing method of the present invention can be used as a wiring board for mounting electronic components such as semiconductor wafers. Furthermore, the wiring board can be used to manufacture various types of semiconductor devices. The semiconductor device equipped with the wiring board can be suitably used in electrical products (for example, computers, mobile phones, digital cameras, televisions, etc.) and vehicles (for example, locomotives, automobiles, trams, ships, and airplanes) in.

[Example]

Hereinafter, the present invention will be described more specifically based on examples, but the present invention is not limited to the following examples. In addition, "part" in the following description means "part by mass".

<Formation of prepreg>

5 parts of naphthalene type epoxy resin ("HP4032SS" made by DIC (share), epoxy equivalent of about 144), and 5 parts of naphthalene type epoxy resin ("HP-4710" made by DIC (share), about 171 of epoxy equivalent) 5 parts of naphthalene type epoxy resin ("HP-6000" made by DIC (share), epoxy equivalent of about 248), biphenyl type epoxy resin ("YX4000HK" made by Mitsubishi Chemical (share), epoxy equivalent of about 185) 5 parts, biphenyl type epoxy resin ("NC3000H" manufactured by Nippon Kayaku Co., Ltd., epoxy equivalent of about 288) 10 parts, phenoxy resin ("YL7553BH30" manufactured by Mitsubishi Chemical Corporation), 30 masses of non-volatile components % Of MEK: cyclohexanone = 1: 1 solution) 5 parts, dissolved in 50 parts of solvent naphtha with heating while stirring. After cooling to room temperature, a phenolic novolac-based hardener containing a triazine skeleton ("LA-7054" made by DIC Corporation), a hydroxyl equivalent of 125, and a 60% non-volatile component MEK solution was used6 Parts, active ester hardener ("HPC8000-65T" made by DIC Corporation), active group equivalent of about 223, nonvolatile component 65% by mass in toluene solution 20 parts, hardening accelerator (4-dimethylamine group) Pyridine, 5% by mass of MEK solution with non-volatile components) 4 parts, spherical silica (average particle size 0.5μm) surface-treated with phenylaminosilane-based coupling agent ("KBM573" manufactured by Shin-Etsu Chemical Co., Ltd.) , (stocks) manufactured by ADMATECHS "SOC2", the carbon amount per unit area of 0.39mg / m ²⁾ 160 parts of flame-retardant (Sanko (shares) manufactured by "HCA-HQ-HST", 10- (2,5- Hydroxyphenyl) -10-hydro-9-oxa-10-phosphaphenanthrene-10-oxide, average particle size 2 μm) 4 parts are mixed and dispersed uniformly with a high-speed rotary mixer to prepare a resin Varnish 1. The composition is shown in Table 1 below.

Next, a 30 μm thick glass interwoven body (“1067NS” manufactured by Yusawa Manufacturing Co., Ltd.) is immersed and impregnated in the resin varnish 1 by a solvent method, and the solvent is volatilized by heating to form Prepreg. The residual solvent in the prepreg was 0.5% and the thickness of the prepreg was 50 μm, so that it was dried and wound into a roll. In addition, the thickness of the prepreg was measured using a contact layer thickness meter ("MCD-25MJ" manufactured by MITUTOYO (Co., Ltd.)).

<Continuous film manufacturing>

Mixed bisphenol epoxy resin ("ZX1059" manufactured by Nippon Steel Chemical Co., Ltd.), 1: 1 mixture of bisphenol A epoxy resin and bisphenol F epoxy resin, epoxy equivalent 169) 8 parts, naphthalene type epoxy resin ("HP4032SS" made by DIC (Co., Ltd.), epoxy equivalent of about 144) 3 parts, "YX4000HK" made by biphenyl type epoxy resin (made by Mitsubishi Chemical Co., Ltd.), Epoxy equivalent of about 185) 6 parts, biphenyl type epoxy resin ("NC3000H" manufactured by Nippon Kayaku Co., Ltd., epoxy equivalent of about 288) 15 parts, phenoxy resin (Mitsubishi Chemical (Co., Ltd.) ) Made of "YX6954BH30", 30% by mass of non-volatile component MEK: cyclohexanone = 1: 1 solution) 25 parts, dissolved in 10 parts of solvent oil (Solvent naphtha) while stirring and heating. After cooling to room temperature (normal temperature), a MEK containing phenol novolac hardener ("LA-7054" manufactured by DIC (Co., Ltd.), a hydroxyl equivalent of 125, and 60% of non-volatile components) containing triazine skeleton Solution) 12 parts, naphthol-based hardener ("SN-485" manufactured by Nippon Steel Chemical Co., Ltd., hydroxyl equivalent 215, MEK solution with 60% non-volatile components) 12 parts, polyvinyl alcohol acetal 25 parts of a mixed solution of resin solution ("KS-1" manufactured by Sekisui Chemical Industry Co., Ltd.), 1: 1 solution of non-volatile components 15% ethanol and toluene, hardening accelerator (4-dimethyl Aminopyridine, MEK solution of 5% by mass of non-volatile components) 1 part, spherical dioxide surface-treated with phenylaminosilane-based coupling agent ("KBM573" manufactured by Shin-Etsu Chemical Industry Co., Ltd.) 60 parts of silicon (average particle size 0.24 μm, "SOC1" manufactured by ADMATECHS Co., Ltd., carbon amount per unit area 0.36 mg / m ² ), organic rubber particles (GANZ Chemical Co., Ltd.) "STAFYROID AC3816N") 4 parts are mixed and dispersed uniformly with a high-speed rotating mixer, 2 to prepare a resin varnish. The composition converted from nonvolatile components is shown in Table 1 below.

Next, on the release layer side of the PET film ("AL5" manufactured by LINTEC (Co., Ltd.), with a thickness of 38 μm) that is an organic support with an alkyd-type release layer, to dry the resin composition The resin varnish 2 is uniformly applied so that the thickness of the layer becomes 30 μm, and is dried at 80 ° C. to 120 ° C. (average 100 ° C.) for 4 minutes to produce an adhesive film. In addition, the thickness of the resin composition layer was measured using a contact-type layer thickness meter ("MCD-25MJ" manufactured by MITUTOYO Co., Ltd.).

[Example 1] (1) Vacuum hot stamping project

Cut the prepreg formed in the above "Prepreg Formation" into 250mm squares, and sequentially stack buffer paper ("AACP-9N" made by Awa Paper (Co., Ltd.), Thickness 800μm) / Stainless steel (SUS) plate (thickness 1mm) / Release sheet ("AFLEX 50N NT" manufactured by Asahi Glass Co., Ltd., thickness 50μm) / Prepreg / Release sheet / SUS plate / Buffer paper, A vacuum hot stamping device ("VH1-1603" manufactured by Kitagawa Seiki Co., Ltd.) was used to perform the vacuum hot stamping process and form a hardened prepreg.

The implementation conditions of the vacuum hot stamping project are as follows.

Temperature: from room temperature (normal temperature) at a heating rate of 5 ° C / min until it reaches 200 ° C, and holding at 200 ° C for 90 minutes, then cooling to room temperature at a cooling rate of 5 ° C / min temperature

Pushing pressure: hold for 20 minutes without pushing (0kg / cm ² ), and maintain the pushing pressure at 50kg / cm ² at the time when the temperature becomes about 125 ° C until the end of cooling

Air pressure: 70mm / hg ~ 74mm / hg (9.3 × 10 ^-3 MPa ~ 9.9 × 10 ^-3 MPa)

(2) Formation of molecular bonding layer

The formed hardened prepreg was added to a molecular bonding agent (Shin-Etsu Chemical Industry Co., Ltd.) triazinethiol functional silicon at 23 ° C. A ketone alkoxy oligomer, fluorinated alkyl type "X-24-9453") was immersed in a 0.5% by weight solution (mixed solvent; water: isopropyl alcohol: acetic acid = 70: 30: 0.5) for 3 minutes Then, it was dried at 100 ° C. for 30 minutes, and a molecular bonding layer was formed on the surface of the hardened prepreg including the first main surface and the second main surface.

(3) Formation of metal layer

In order to form a metal layer on the surface of the hardened prepreg on which the molecular bonding layer is formed, the first electroless plating process (using a chemical solution manufactured by ATOTECH JAPAN (Co., Ltd.), the following electroless copper plating process ). The thickness of the metal layer (first electroless plating layer) formed by the first electroless plating process is 0.5 μm.

<First Electroless Copper Plating Project> 1. Alkaline cleaning (cleaning of the surface of the molecular binding layer and charge adjustment)

Using Cleaning Cleaner Securiganth 902 (trade name), it was washed at 60 ° C for 2 minutes.

2. Pre-impregnation (adjustment of the charge on the surface of the molecular bonding layer for Pd)

Pre.Dip Neoganth B (trade name) was used to perform treatment at room temperature for 1 minute.

3. Activated (to give Pd on the surface of the molecular binding layer)

Using Activator Neoganth 834 (trade name), treatment was carried out at 35 ° C for 5 minutes.

4. Reduction (reduction of Pd given to the surface of the molecular bonding layer)

A mixture of Reducer Neoganth WA (trade name) and Reducer Acceralator 810 mod. Was used for treatment at 30 ° C for 5 minutes.

5. Electroless copper plating (make Cu precipitate on the surface of molecular bonding layer (Pd surface))

Using a mixture of Basic Solution Printganth MSK-DK (brand name), Copper solution Printganth MSK (brand name), Stabilizer Printganth MSK-DK (brand name) and Reducer Cu (brand name), the mixture was made at 35 ℃ for 10 minutes. Treatment.

(4) Formation of through holes

Using the CO ₂ laser processing machine "LC-2k212 / 2C" manufactured by HITACHI VIA MECHANICS (CO., LTD.) To perform hole drilling, a through hole penetrating the metal layer and the hardened prepreg was formed. The top diameter (diameter) of the through hole on the surface of the hardened prepreg was 65 μm. In addition, for hole drilling, the mask diameter is set to 3.5 mm, the power is set to 1 W, the frequency is set to 2000 Hz, the pulse width is set to 4 μs, and the number of shots is set to 3. The circular mode was implemented.

(5) Slag removal treatment

The through-hole structure was made in "Swelling Dip Securiganth P" containing diethylene glycol monomethyl ether made by ATOTECH JAPAN (Co., Ltd.) as a swelling fluid at 60 ° C for 5 minutes. Immersion, and then, as a roughening liquid, immersed in "Concentrate Compact P" (KMnO ₄ : 60g / L, NaOH: 40g / L aqueous solution) of ATOTECH JAPAN (Co., Ltd.) at 80 ° C for 15 minutes , And washed with water, then, as a neutralizing solution, in "ReductionSolution Securiganth P" of ATOTECH JAPAN (Co., Ltd.) at 40 ℃ for 5 minutes of immersion. Thereafter, it was dried at 130 ° C for 15 minutes.

(6) Formation of conductor layer

In order to form a conductor layer on the surface of the metal layer and in the through hole, the electroless plating process (the second part of the following electroless copper plating process using the chemical solution manufactured by ATOTECH JAPAN (Co., Ltd.) as follows) Electrolytic plating process) to form a conductor layer (second electroless plating layer). The thickness of the formed conductor layer was 0.8 μm. The total thickness of the metal layer and the conductor layer on the surface of the hardened prepreg is about 1.3 μm.

<The second electroless copper plating project> 1. Alkaline cleaning (cleaning of the surface of the metal layer and the surface in the through hole and charge adjustment)

Using "Cleaning Cleaner Securiganth 902" (brand name), it was washed at 60 ° C for 2 minutes.

2. Pre-dip (the surface of the metal layer and the through-holes in order to give Pd Adjustment of the charge on the surface)

Using "Pre.Dip Neoganth B" (brand name), the treatment was performed at room temperature for 1 minute.

3. Activation (for Pd on the surface of the metal layer and the surface of the through hole)

Using "Activator Neoganth 834" (trade name), treatment was carried out at 35 ° C for 5 minutes.

4. Reduction (reduction of Pd applied to the surface of the metal layer and the surface of the through hole)

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

5. Electroless copper plating (precipitating Cu on the surface of the metal layer and the surface of the through hole (Pd surface))

Use a mixture of "Basic Solution Printganth MSK-DK" (brand name), "Copper solution Printganth MSK" (brand name), "Stabilizer Printganth MSK-DK" (brand name), and "Reducer Cu" (brand name) to It was treated at 35 ° C for 18 minutes.

(7) Formation of wiring layer <Formation Engineering of Mask Pattern>

Next, the surface of the structure was treated with a 5% sulfuric acid aqueous solution for 30 seconds, and a mask pattern-forming body with a thickness of 25 μm was formed. "ALPHO NIT3025" (trade name) manufactured by NICHIGO MORTON (CO., LTD), a dry film with PET film, is laminated on both sides of the structure by a vacuum laminator. For the lamination, a batch-type vacuum press laminator "MVLP-500" (trade name) manufactured by (J Corporation) was used, and the pressure was set to 0.1 MPa and the temperature was set to 70 ° C Then, the pressure is reduced for 30 seconds and the air pressure is set to 13 hPa or less, and then the pressure is increased for 20 seconds.

After that, a glass mask was placed on the side of the PET film that was the respective protective layer of the dry film provided on both sides of the structure, and UV-lamps were used to irradiate 150mJ / cm ² of ultraviolet light to The dry film is placed on both sides of the structure to perform the exposure process, and a mask pattern is formed. The glass mask is L (line: line width of dry film) / S (space: linear The distance between the dry films) = 8μm / 8μm, that is, a comb pattern with a pitch of 16μm (wiring length 15mm, 16 lines), L / S = 10μm / 10μm, that is, a comb tooth with a pitch of 20μm Patterns (wiring length 15mm, 16 lines), L / S = 15μm / 15μm, that is, a comb pattern (wiring length 15mm, 16 lines) with a pitch of 30μm, each formed with 10 pieces.

Next, spraying was performed by spraying the structure with a 1% sodium carbonate aqueous solution at a temperature of 30 ° C. at a pressure of 0.15 MPa for 30 seconds.

<Electrolytic plating layer and formation of wiring in through holes>

Next, the structure was washed with water and developed. Use ATOTECH JAPAN (share Chemical Co., Ltd., under the condition that copper is filled in the through hole, electrolytic plating process (electrolytic copper plating process) is performed, and electrolysis is formed at the conductor layer exposed from the mask pattern The electroplated layer (electrolytic copper electroplated layer), and a pair of through holes are buried together to form wiring in the through holes.

<Formation of wiring layer>

Next, the structure was sprayed with a 3% NaOH solution at a temperature of 50 ° C. at a pressure of 0.2 MPa, and the mask pattern was peeled off from both sides of the structure. Next, using the etchant for SAC process (Flash Etch Engineering) manufactured by Ebara Electric Co., Ltd., the exposed conductive layer and the exposed conductive layer directly underneath the mask pattern removal The metal layer in the region is removed, and a wiring layer including fine plural wirings is formed on both surfaces of the structure.

Through the above process, the wiring board of Example 1 was manufactured.

[Example 2] (1) Base treatment of circuit board

On a glass cloth substrate with an electronic circuit (wiring layer) formed on the epoxy resin double-sided copper-clad laminate (copper layer (wiring layer) thickness 18 μm, substrate thickness 0.3 mm, PANASONIC (Co., Ltd. ) Made of "R1515A") on both sides, copper was etched by removing 1 μm of the thickness of the copper layer with a micro-etching agent ("CZ8100" made by MEC (Co., Ltd.)) and copper was removed. Degumming treatment on the surface of the layer.

(2) Lamination of the next film

Prepare the adhesive film produced by the same process as the <Production of Adhesive Film> already described, and use the two-stage platform of a batch type vacuum press laminator (NICHIGO MORTON (Co., Ltd.)) to apply the adhesive film Lamination machine "CVP700" is used to laminate the resin composition layer and the circuit board on both sides of the circuit board. Lamination is performed after depressurizing for 30 seconds and setting the air pressure to 13hPa , Set the temperature to 100 ° C., and set the pressure to 0.74 MPa, and press for 30 seconds, and then implement it. Then, the laminated adhesive film was laminated under atmospheric pressure, The temperature was set to 100 ° C., and the pressing pressure was set to 0.5 MPa, and hot pressing for 60 seconds was performed, thereby smoothing.

(3) Hardening of the resin composition layer

Next, the structure laminated with the adhesive film was subjected to a heat treatment at 100 ° C for 30 minutes, and then a heat treatment at 160 ° C for 30 minutes, by which the resin composition layer was hardened, and An insulating layer is formed.

(4) Formation of molecular bonding layer

From the circuit board on which the insulating layer has been formed, the release PET film derived from the adhesive film is peeled off and used as a molecular bonding agent in the amino triazine novolak resin (DIC (Co., Ltd.), "LA- 1356 ", 60% by weight of non-volatile MEK solution, N content 19% by weight, solid content hydroxyl value 146) 0.5% by weight, epoxy silane coupling agent (made by Shin-Etsu Chemical Industry Co., Ltd.), 3-ring Oxypropyloxypropyltrimethoxysilane, "KBM403", molecular weight 236.3) 0.5% by weight of a mixed solution (mixed solution dissolved in a mixed solvent of ethanol: MEK: water = 50: 50: 1), with 23 The immersion was carried out at 3 ° C for 3 minutes, and then dried at 100 ° C for 30 minutes.

(5) Formation of metal layer

In order to form a metal layer on the surface of the circuit board (structure) on which the molecular bonding layer is formed, the first electroless plating process (using ATOTECH JAPAN (manufactured by ATOTECH JAPAN) The chemical solution, electroless copper plating project). The thickness of the metal layer (first electroless plating layer) formed by the first electroless plating process is 0.5 μm.

(6) Formation of guide holes

Using a CO ₂ laser processing machine ("LC-2E21B / 1C" manufactured by HITACHI VIA MECHANICS (Co., Ltd.)), the mask diameter is 1.60 mm, the focus offset value is 0.050, the pulse width is 25 μs, and the power is 0.66 W. The aperture 13, the number of shots 2, and the burst mode are subjected to hole processing, thereby forming a via hole that penetrates the metal layer, the molecular bonding layer, and the insulating layer and exposes a part of the wiring layer. The top diameter (diameter) of the via hole on the surface of the insulating layer is 50 μm.

(7) Slag removal treatment

For the structure in which the guide hole has been formed, use "Swelling Dip Securiganth P" containing diethylene glycol monomethyl ether made by ATOTECH JAPAN (Co., Ltd.) as the swelling fluid at 60 ° C for 5 minutes. Immersion, and then, as a roughening liquid, immersed in "Concentrate Compact P" (KMnO ₄ : 60g / L, NaOH: 40g / L aqueous solution) of ATOTECH JAPAN (Co., Ltd.) at 80 ° C for 15 minutes , And washed with water. After that, as a neutralizing solution, "ReductionSolution Securiganth P" of ATOTECH JAPAN (Co., Ltd.) was immersed at 40 ° C for 5 minutes, and then dried at 130 ° C for 15 minutes. And the slag removal of the guide hole was carried out.

(8) Removal of the metal layer

After the slag removal process, in order to reduce the thickness of the layer removed by the flash etching process in the formation process of the wiring layer described later and form finer wiring, the metal layer is made of ferric chloride (III) The aqueous solution was immersed at 25 ° C for 1 minute and removed.

(9) Formation of conductor layer

In order to form a conductor layer on the molecular bonding layer exposed by removing the metal layer, the second electroless plating process (using ATOTECH JAPAN (Limited) electroless copper Plating project). The thickness of the formed conductor layer was 0.8 μm.

(10) Formation of wiring layer <Formation Engineering of Mask Pattern>

Next, the surface of the structure was treated with a 5% sulfuric acid aqueous solution for 30 seconds, and a mask film with a thickness of 25 μm was formed by NICHIGO MORTON (CO., LTD.) As a dry film with a PET film. The "ALPHO NIT3025" (brand name) is laminated on both sides of the structure by a vacuum laminator. For the lamination, a batch-type vacuum press laminator ("MVLP-500" (trade name) manufactured by Meiji Co., Ltd. (brand name)) was used, the pressure was set to 0.1 MPa, and the temperature was set to 70 ° C , And first depressurize for 30 seconds and set the air pressure to 13hPa or less, and then pressurize for 20 seconds to proceed.

After that, a glass mask was placed on the side of the PET film that was the protective layer of the dry film provided on the top diameter side of the guide hole, and a UV-lamp was used to perform the exposure process of irradiating 150mJ / cm ² of ultraviolet light , And a mask pattern is formed, the glass mask is L (line: line width of dry film) / S (space: space between line-shaped dry films) = 8μm / 8μm, which is the node Comb pattern at 16 μm (wiring length 15 mm, 16 lines), L / S = 10 μm / 10 μm, that is, comb pattern at 20 μm pitch (wiring length 15 mm, 16 lines), L / S = 15 μm / Ten combs of 15 μm, that is, a comb pattern with a pitch of 30 μm (wiring length 15 mm, 16 lines) were each formed. In addition, the dry film layered on the bottom diameter side of the via hole was fully exposed, and a mask pattern covering the entire surface of the conductor layer was formed.

Next, spraying was performed by spraying the structure with a 1% sodium carbonate aqueous solution at a temperature of 30 ° C. at a pressure of 0.15 MPa for 30 seconds.

<Formation of electrolytic plating layer and filled via hole>

Next, the structure was washed with water and developed. For the structure that has undergone the development process, use the chemical solution manufactured by ATOTECH JAPAN (Co., Ltd.), and perform electrolytic plating process (electrolytic copper plating process) under the condition that copper is filled in the guide hole, and At the conductor layer exposed from the mask pattern, an electrolytic plating layer (electrolytic copper plating layer) is formed, and a pair of via holes are buried together to form a filled via hole.

<Formation of wiring layer>

Next, the structure was sprayed with a 3% NaOH solution at a temperature of 50 ° C. at a pressure of 0.2 MPa, and the mask pattern was peeled off from both sides of the structure. Next, using an etchant for SAC process (Flash Etch Engineering) manufactured by Ebara Electric Co., Ltd., only the conductive layer exposed due to the removal of the mask pattern was removed, and a fine layer containing fine particles was formed. Wiring layer for multiple wiring.

Through the above process, the wiring board of Example 2 was manufactured.

[Comparative Example 1]

After the through-holes were formed, a roughening process that doubled as a slag removal process was carried out, and then, a molecular bonding layer formation process was carried out, except for this In addition, the wiring board of Comparative Example 1 was manufactured in the same manner as in Example 1 until the process of forming the wiring layer.

[Comparative Example 2]

After the molecular bonding layer is formed, a via hole is formed, and then a roughening process which also serves as a degumming process is performed. After that, a process of forming a conductor layer is carried out without forming a metal layer. The wiring board of Comparative Example 2 was manufactured in the same manner as in Example 2 until the process of forming the wiring layer.

[Measurement of arithmetic average roughness Ra and root mean square roughness Rq]

For each of the wiring boards manufactured in Example 1, Example 2, Comparative Example 1, and Comparative Example 2, a non-contact surface roughness meter ("WYKO NT3300" manufactured by Veeco Instruments) was used based on In the VSI contact mode, a 50x lens, and the measurement value obtained by setting the measurement range to 121 μm × 92 μm, the arithmetic mean roughness Ra and the root mean square roughness Rq (surface roughness) were obtained. By averaging the measured values of 10 randomly selected points, this is used as the value of the arithmetic mean roughness Ra or the root mean square roughness Rq. The results are shown in Table 2 below.

[Measurement of peel strength (peer strength) of wiring layer]

For each of the wiring layers formed in Example 1, Example 2, Comparative Example 1, and Comparative Example 2, a width of 10 mm and a length of 100 mm were drawn The rectangular cut, and one end is grasped by a peeling gripper (TSE Co., Ltd., AUTO COM type testing machine "AC-50C-SL"), and at room temperature, for The load (kgf / cm) at the time of peeling 35 mm in the vertical direction at a speed of 50 mm / min was measured and evaluated. The evaluation criteria are as follows. The results are shown in Table 2 below.

Evaluation criteria:

○: Peel strength is more than 0.4kgf / cm

×: Peel strength is less than 0.4kgf / cm

[Evaluation of minimum pitch]

For each of the wirings formed in Example 1, Example 2, Comparative Example 1, and Comparative Example 2, the minimum pitch of the comb-tooth pattern that can be formed was evaluated visually. The results are shown in Table 2 below.

[Evaluation of wiring]

For each of the wirings formed in Example 1, Example 2, Comparative Example 1, and Comparative Example 2, the presence or absence of peeling was confirmed by an optical microscope, and further the conductor layer to be removed (and The presence or absence of the residue of the metal layer) was confirmed and evaluated. The evaluation criteria are as follows. The results are shown in Table 2 below.

Evaluation criteria:

○: The linear part in the comb pattern is not problematic if 9 or more out of 10

×: The linear part of the comb-tooth pattern has a problem with two or more of ten

As is apparent from Table 2, in the wiring boards manufactured in Examples 1 and 2, the minimum pitch of the wiring can be set to 20 μm or less, and fine wiring can be realized. In addition, in Example 1 and Example 2, it is obvious that compared with Comparative Example 1 and Comparative Example 2 in which the roughening process is performed as in the prior art, the peel strength is not inferior. On the other hand, in Comparative Example 1 and Comparative Example 2, since the roughening process was implemented, the surface roughness (Ra and Rq) was slightly large, and the surface roughness was caused by this. In Comparative Example 1 and Comparative Example 2 In both cases, the minimum pitch of wiring cannot be set to 20 μm or less.

As is obvious from the above, according to the manufacturing method of the wiring board of the present invention, even if the roughening process is not carried out, fine wiring can be realized while maintaining the peel strength.

Claims (7)

A method of manufacturing a wiring board, characterized in that it includes: process (A), which is a process for preparing a structure having a hardened prepreg and a molecular bonding layer, the hardened prepreg has a first main The surface and the second main surface opposite to the first main surface, the molecular bonding layer is provided only on the first main surface or on the first main surface and the second main surface On both sides; and project (B), which is a process for forming a metal layer bonded to the molecular bonding layer; and project (C), which is to perform laser irradiation to form a through metal layer, the molecular bonding layer, and the foregoing The process of hardening the prepreg through holes; and the process (D), which is the process of removing the slag treatment for the aforementioned through holes; and the process (E), the process of forming the conductor layer; and the process (F) , Is a project to form a wiring layer. The method of manufacturing a wiring board as described in item 1 of the patent application scope, wherein the step (A) is to prepare the molecular bonding layer to be provided on the first main surface of the hardened prepreg and the second The construction of structures on both sides of the main surface. The method of manufacturing a wiring board as described in item 1 of the scope of the patent application, wherein the process (A) is to prepare the hardened prepreg to be provided on the circuit board and the molecular bonding layer to be provided only with the The construction of the structure on the first main surface opposite to the second main surface to which the circuit board is joined. The method of manufacturing a wiring board as described in item 1 of the scope of the patent application, wherein the above-mentioned process (A) is a process for preparing a structure further comprising a protective film bonded to the molecular bonding layer, and the above-mentioned process ( B) is a process of peeling the protective film and forming a metal layer bonded to the molecular bonding layer. The method of manufacturing a wiring board as described in item 1 of the scope of the patent application, wherein the aforementioned process (A) further includes a process of providing a protective film bonded to the molecular bonding layer, the aforementioned process (B) In order to peel off the protective film from the structure and form a metal layer bonded to the molecular bonding layer. The method for manufacturing a wiring board as described in item 1 of the patent application scope, wherein, after the aforementioned process (D) and before the aforementioned process (E), it further includes: Project (G), which is the The removal process, the process (E), is a process of forming a conductor layer on the exposed molecular bonding layer and the through hole. The method for manufacturing a wiring board as described in item 1 of the scope of the patent application, wherein the aforementioned process (B) is a process of forming a metal layer by an electroless plating process.