TW202308488A - Method for manufacturing printed wiring board - Google Patents

Abstract

To provide a method for manufacturing a printed wiring board, which can suppress the occurrence of a crack after a desmear treatment (roughening treatment). A method for manufacturing a printed wiring board comprises the steps of (A) hardening, by heat, a resin composition layer of a laminate having the inner layer substrate, and a resin composition layer joined to the inner layer substrate to form an insulator layer of which the glass transition temperature is T1(DEG C), (B) performing a heat treatment on the insulator layer at T2(DEG C), and (C) performing a desmear treatment on the insulator layer with an oxidant solution in this order. The resin composition layer contains an epoxy resin and an active ester-based hardening agent, and the following expressions (1) and (2) are satisfied: -20 ≤ T1-T2 ≤ 20 (1); and 60 ≤ T2 ≤ 150 (2).

Description

Manufacturing method of printed wiring board

This invention relates to the manufacturing method of a printed wiring board.

As a manufacturing technique of multilayer printed wiring boards, a manufacturing method of a build-up method in which insulating layers and conductive layers are alternately stacked on an inner substrate is known. The insulator layer is generally formed by curing a resin composition. For example, Patent Document 1 discloses that an insulating layer of a printed wiring board is formed using a resin composition including a cyanate resin, a specific epoxy resin, and an active ester hardener. [Prior Art Literature] [Patent Document]

[Patent Document 1] Japanese Patent Laid-Open No. 2011-144361

[Problem to be solved by the invention]

In recent years, the miniaturization of electronic equipment and electronic parts has become remarkable. Along with this, in order to make the printed wiring board thinner, the insulating layer of the printed wiring board must be thinner.

However, it is known that if the insulating layer is thinned, after the desmear treatment (roughening treatment) step in the printed wiring board process, it is known that the shape of the underlying copper along the wiring or pads in the inner substrate will be cracked. , and the periphery of the hole opened by laser etc. breaks, that is, the occurrence of cracks increases.

The object of this invention is to provide the manufacturing method of the printed wiring board which can suppress the generation|occurrence|production of the crack after a desmear process (roughening process). [Means to solve the problem]

In order to achieve the subject of the present invention, the present inventors found that by using an active ester-based hardener in the formation of the insulating layer, after the insulating layer is formed, the glass transition temperature T ₁ (°C) is near (± Heat treatment of the insulating layer at a temperature T ₂ (°C) within 20°C can suppress the occurrence of cracks after desmearing (roughening) treatment, thus completing the present invention.

That is, the present invention includes the following. [1] A method of manufacturing a printed wiring board, which sequentially includes the steps of: (A) thermosetting a resin composition layer of a laminate including an inner layer substrate and a resin composition layer bonded to the inner layer substrate , the step of forming an insulating layer with a glass transition temperature of T ₁ (°C), (B) the step of heat-treating the insulating layer at T ₂ (°C), and (C) the step of desmearing the insulating layer with an oxidant solution , the resin composition layer contains epoxy resin and active ester hardener, and satisfies the following formulas (1) and (2) at the same time, -20≦T ₁ -T ₂ ≦20 (1) 60≦T ₂ ≦150 ( 2). [2] The method for producing a printed wiring board according to the above [1], wherein step (A) includes the following steps in order: (A-1) preparing a substrate having a support and a resin composition layer provided on the support The step of the resin sheet, (A-2) the step of laminating the resin sheet so that the resin composition layer and the inner substrate are bonded to obtain a laminate, and (A-3) thermosetting the resin composition layer to form a glass transition The temperature is T ₁ (°C) the step of the insulating layer. [3] The method of manufacturing a printed wiring board according to the above [2], wherein the step (A-3) includes the following steps in order: (A-31) Preheating the resin composition layer at a preliminary heating temperature lower than the curing heating temperature The step of preheating, and (A-32) the step of heating the resin composition layer at the curing heating temperature to thermally harden the resin composition layer to form an insulating layer having a glass transition temperature of T ₁ (°C). [4] The method for producing a printed wiring board according to [3] above, wherein the curing heating temperature is 150°C to 210°C, and the preliminary heating temperature is 100°C to 150°C. [5] The method of manufacturing a printed wiring board according to any one of the above-mentioned [2] to [4], wherein the step (A) is after the step (A-3), and further includes the following steps: (A-4) The step of cooling the insulating layer to below 30°C. [6] The method for producing a printed wiring board according to any one of the above [1] to [5], wherein the step (A) further includes the following step: (A-5) Opening holes in the insulating layer or the resin composition layer the steps. [7] The method of manufacturing a printed wiring board according to the above [6], wherein the step (A-5) is performed using a laser. [8] The method of manufacturing a printed wiring board according to the above [6] or [7], wherein the holes formed in the step (A-5) include those having a top diameter of 100 μm or less. [9] The method for producing a printed wiring board according to any one of [1] to [8] above, wherein the heat treatment time in the step (B) is 10 minutes or more. [10] The method for producing a printed wiring board according to any one of [1] to [9] above, wherein the heat treatment in the step (B) is performed by heating the insulating layer in a gas atmosphere. [11] The method for producing a printed wiring board according to any one of [1] to [10] above, further including (D) a step of forming a conductor layer on the surface of the insulating layer after the step (C). [12] The method for producing a printed wiring board according to any one of [1] to [11] above, wherein T ₂ (°C) is 100 (°C) or more. [13] The method for producing a printed wiring board according to any one of [1] to [12] above, wherein T ₁ -T ₂ (°C) is -5 (°C) to 10 (°C). [14] The method for producing a printed wiring board according to any one of [1] to [13] above, wherein the resin composition layer further contains an inorganic filler. [15] The method for producing a printed wiring board according to [14] above, wherein the content of the inorganic filler is 50% by mass or more when the non-volatile content in the resin composition layer is 100% by mass. [16] The method for producing a printed wiring board according to any one of [1] to [15] above, wherein the resin composition layer further contains a phenoxy resin. [17] The method for producing a printed wiring board according to any one of [1] to [16] above, wherein the resin composition layer further contains a radical polymerizable compound. [18] The method for producing a printed wiring board according to any one of [1] to [17] above, wherein the resin composition layer further contains a cyanate-based hardener. [Invention effect]

According to this invention, the manufacturing method of the printed wiring board which can suppress generation|occurrence|production of the crack after a desmear process (roughening process) can be provided.

Hereinafter, the present invention will be described in detail about its preferred embodiments. However, the present invention is not limited to the following embodiments and illustrations, and any changes can be made within the scope of the present invention without departing from the scope of patent claims and its equivalent range.

<Manufacturing Method of Printed Wiring Board> The manufacturing method of the printed wiring board of the present invention includes the following steps in order: (A) making a laminated body including an inner layer substrate and a resin composition layer bonded to the inner layer substrate The step of thermally hardening the resin composition layer to form an insulating layer with a glass transition temperature of T ₁ (°C), (B) the step of heat-treating the insulating layer at T ₂ (°C), and (C) treating the insulating layer with an oxidant solution In the step of desmearing treatment, the resin composition layer contains epoxy resin and active ester hardener, and satisfies the following formulas (1) and (2) at the same time, -20≦T ₁ -T ₂ ≦20 (1) 60 ≦T ₂ ≦150 (2). Here, "≦" indicates that the value on the left is lower than the value on the right.

According to these production methods, the generation of cracks after the desmear treatment (roughening treatment) can be suppressed. This is presumed to be due to the fact that after the insulating layer is formed, by heating the insulating layer at a temperature T ₂ (°C) near its glass transition temperature T ₁ (°C) (within ±20°C), the heat of the resin composition layer Hardening slowly releases the stress accumulated inside the insulating layer.

Hereinafter, each step of the manufacturing method of the printed wiring board of this invention is demonstrated.

<(A) Step> (A) Step is to thermally harden the resin composition layer of the laminated body including the inner substrate and the resin composition layer bonded to the inner substrate to form a glass transition temperature T ₁ (°C) The steps of the insulating layer.

The step (A) preferably includes the following steps (A-1) to (A-3) in sequence. (A-1) Step (A-2) of preparing a resin sheet having a support and a resin composition layer provided on the support by laminating the resin sheet so that the resin composition layer and the inner substrate are bonded to obtain a laminate The step (A-3) of forming the resin composition layer by thermosetting to form an insulating layer having a glass transition temperature of T ₁ (°C).

The (A-1) step is to prepare a resin sheet including a support and a resin composition layer provided on the support.

The resin sheet can be produced by, for example, coating a varnish-like resin composition on a support using a coating device such as a die coater, and drying it as necessary to form a resin composition.

Drying can be carried out by conventional methods such as heating and blowing hot air. The drying conditions are not particularly limited, but they are dried until the content of the organic solvent in the resin composition layer is 10% by mass or less, preferably 5% by mass or less. Although it varies depending on the boiling point of the organic solvent in the varnish-like resin composition, for example, in the case of using a resin composition containing an organic solvent of 30% by mass to 60% by mass, by boiling at 50°C to 150°C (preferably (80-120°C) for 1-10 minutes to form a resin composition layer.

Examples of the support used for the resin sheet include films, metal foils, and release paper made of plastic materials, preferably films and metal foils made of plastic materials.

When a film made of plastic material is used as the support, examples of the plastic material include polyethylene terephthalate (hereinafter referred to as "PET"), polyethylene naphthalate (hereinafter referred to as "PEN"), and polyethylene terephthalate (hereinafter referred to as "PEN"). ) and other polyesters, polycarbonate (hereinafter referred to as "PC"), polymethyl methacrylate (PMMA) and other acrylics, cyclic polyolefins, triacetyl cellulose (TAC), polyether sulfide ( PES), polyether ketone, polyimide, etc. Among them, polyethylene terephthalate and polyethylene naphthalate are preferred, and inexpensive polyethylene terephthalate is particularly preferred.

When using a metal foil as a support body, as a metal foil, copper foil, an aluminum foil, etc. are mentioned, for example, Copper foil is preferable. As the copper foil, a foil made of a single metal of copper can be used, and a foil made of an alloy of copper and other metals (such as tin, chromium, silver, magnesium, nickel, zirconium, silicon, titanium, etc.) can be used.

The surface of the support that is bonded to the resin composition layer can be subjected to roughening treatment, corona treatment, and antistatic treatment.

Moreover, as a support body, the support body with a release layer which has a release layer on the surface bonded to a resin composition layer can be used. As the release agent used for the release layer of the support body with release layer, for example, one or more selected from the group consisting of alkyd resin, polyolefin resin, urethane resin and silicone resin Release agent. As the supporting body with a release layer, commercially available products can be used, for example, PET film having a release layer mainly composed of an alkyd resin release agent, "SK-1" manufactured by Lintec Corporation, "AL -5", "AL-7", "LUMIRROR T60" manufactured by TORAY Corporation, "PUREX" manufactured by Teijin Corporation, "UNIPEEL" manufactured by UNITIKA Corporation, etc.

The thickness of the support is not particularly limited, but is preferably in the range of 5 μm to 75 μm, more preferably in the range of 10 μm to 60 μm. Moreover, when using the support body with a release layer, it is preferable that the thickness of the whole support body with a release layer is in the said range.

In the resin sheet, a protective film based on the support can be further laminated on the surface of the resin composition layer that is not bonded to the support (that is, the surface opposite to the support). The thickness of the protective film is not particularly limited, but is, for example, 1 μm to 40 μm. By laminating the protective film, it is possible to prevent dust and scratches from adhering to the surface of the resin composition layer. These resin films can be wound into rolls and stored. When the resin sheet has a protective film, the protective film is peeled off and laminated on the inner substrate.

In the step (A-2), the resin sheets are laminated so as to join the resin composition layer inner layer substrate to obtain a laminate.

The so-called inner substrate is a component used as the substrate of the printed wiring board, such as glass epoxy substrate, metal substrate, polyester substrate, polyimide substrate, BT resin substrate, thermosetting polyphenylene ether substrate, etc. In addition, the substrate may have a conductive layer on one or both sides thereof, and the conductive layer may also be patterned. In addition, when manufacturing a printed wiring board, an intermediate product that should further form an insulating layer and/or a conductive layer is also included in the inner layer substrate. When the printed wiring board is a circuit board with built-in parts, the inner layer substrate of the built-in parts can be used.

The resin composition layer is bonded to the inner substrate, and the resin sheet is laminated on the inner substrate to obtain a laminate. In one embodiment, the lamination of the inner layer substrate and the resin sheet can be performed, for example, by heat-pressing the resin sheet to the inner layer substrate from the side of the support. As the member for heat-pressing the resin sheet to the inner layer substrate (hereinafter referred to as "heat-pressing member"), for example, a heated metal plate (SUS mirror plate, etc.) or a metal roll (SUS roll) can be exemplified. In addition, instead of directly applying pressure to the resin sheet by the heat-pressing member, it is preferable to press through the elasticity of heat-resistant adhesive or the like so that the resin sheet can fully follow the surface irregularities of the inner substrate.

The lamination of the inner substrate and the resin sheet can be carried out by vacuum lamination. In the vacuum lamination method, the heating and pressing temperature is preferably in the range of 60°C~160°C, more preferably in the range of 80°C~140°C, and the heating pressing pressure is preferably in the range of 0.098MPa~1.77MPa, more preferably 0.29MPa~1.47MPa The heating and pressing time is preferably in the range of 10 seconds to 400 seconds, more preferably in the range of 20 seconds to 300 seconds.

Lamination can be performed by a commercially available vacuum lamination machine. As a commercially available vacuum laminator, for example, a vacuum pressure laminator manufactured by Meiki Seisakusho Co., Ltd., a vacuum butcher manufactured by NIKKO‧Materials Co., Ltd., a batch type vacuum pressure laminator, etc. may be exemplified.

After lamination, the smoothing treatment of the laminated resin sheet can also be performed under normal pressure (atmospheric pressure), for example, by pressing a heated pressing member from the support side. The pressure conditions of the smoothing treatment may be the same conditions as the above-mentioned heating and pressing conditions of the laminate. The smoothing treatment can be performed with a commercially available lamination machine. In addition, lamination and smoothing can also be performed continuously using the above-mentioned vacuum lamination machine.

(A-3) The step is to heat-cure the resin composition layer to form an insulating layer with a glass transition temperature of T ₁ (°C).

The curing heating temperature of the resin composition layer varies depending on the type of the resin composition, but is preferably at least 100°C, more preferably at least 150°C, and still more preferably at least 160°C. The upper limit is preferably at most 220°C, more preferably at most 210°C, and still more preferably at most 200°C.

The hardening and heating time of the resin composition layer varies according to the type of the resin composition, but is preferably at least 5 minutes, more preferably at least 10 minutes, and more preferably at least 15 minutes. The upper limit is not particularly limited, but is preferably 120 minutes or less, more preferably 100 minutes or less, and more preferably 90 minutes or less. The curing heating time of the resin composition layer means the time for maintaining the curing heating temperature of the resin composition layer. Thermal hardening is usually carried out in a gas (such as air, argon, nitrogen or the mixed gas) environment, for example, at a pressure of 0.05MPa~0.15MPa, preferably 0.08~0.12MPa.

The step of (A-3) preferably includes the following steps of (A-31) and (A-32) in this order. (A-31) A step of preheating the resin composition layer at a preliminary heating temperature lower than the curing heating temperature, and (A-32) heating the resin composition layer at a curing heating temperature to thermally harden the resin composition layer , a step of forming an insulating layer with a glass transition temperature of T ₁ (°C).

The preliminary heating temperature for the resin composition layer is preferably at least 50°C, more preferably at least 100°C, more preferably at least 120°C, preferably at most 160°C, more preferably at most 150°C, and more preferably at least 150°C. Below 140°C. The preheating time for the resin composition is preferably at least 5 minutes, more preferably at least 10 minutes, more preferably at least 15 minutes, more preferably at most 150 minutes, more preferably at most 130 minutes, and more preferably at least 120 minutes. minutes or less. Preliminary heating is usually carried out in a gas (such as air, argon, nitrogen or a mixture thereof) environment, for example, at a pressure of 0.05MPa~0.15MPa, preferably 0.08~0.12MPa.

The glass transition temperature (T ₁ ) of the insulating layer formed by thermosetting is preferably 60 (°C) or higher, more preferably 70 (°C) or higher, and still more preferably 80 (°C) from the viewpoint of heat resistance of the insulating layer. °C), more preferably above 90 (°C), more preferably above 100 (°C), especially preferably above 110 (°C), the upper limit is not particularly limited, but is preferably below 160 (°C), more preferably It is preferably below 150 (°C).

Between (A-31) step and (A-32) step, do not return to room temperature (preferably directly increase the temperature from the preliminary heating temperature to the hardening heating temperature), can continue to heat, or can also be in (A-31) After the step (A-32) before the step, it further includes the step of (A-33) cooling the insulating layer to 30° C. or lower. The cooling temperature in the step (A-33) is preferably 10°C to 30°C, more preferably 20°C to 30°C. The cooling method is not particularly limited, and the insulating layer may be left to cool, blowing cold air on the insulating layer, or pressing the insulating layer against a cooling roller to cool. (A-33) The cooling in step (A-33) is usually carried out in a gas (such as air, argon, nitrogen or the mixed gas) environment, for example, at a pressure of 0.05MPa~0.15MPa, preferably 0.08~0.12MPa.

The thickness of the insulating layer formed by thermosetting in step (A-3) depends on the thickness of the resin composition layer of the prepared resin sheet, but is, for example, 200 μm or less, preferably 100 μm or less, more preferably 80 μm or less , and more preferably 60 μm or less, particularly preferably 50 μm or less, the lower limit is not particularly limited, usually 1 μm or more, 5 μm or more, 10 μm or more, and the like.

The step (A) is preferably after the step (A-3), and further includes the step of (A-4) cooling the insulating layer to below 30°C.

By carrying out the step (A-4), it is possible to suppress excessive stress due to thermosetting of the resin composition. Therefore, the stress remaining in the insulating layer in the step (B) can be further suppressed, and the occurrence of cracks can be effectively suppressed. The cooling temperature in the step (A-4) is preferably from 10°C to 30°C, more preferably from 20°C to 30°C. The method of cooling is not particularly limited, and cooling may be performed by cooling the insulating layer, blowing cold air on the insulating layer, or pressing the insulating layer against a cooling roller. The cooling in step (A-4) is usually carried out in a gas (such as air, argon, nitrogen or a mixture thereof) environment, for example, at a pressure of 0.05MPa~0.15MPa, preferably 0.08~0.12MPa.

The (A) step preferably further includes (A-5) the step of opening holes in the insulating layer or the resin composition layer. (A-5) step, for example, can be included after (A-31) step (but preferably after (A-33) step when including (A-33) step) before (A-32) step, or (A- 3) after step (but preferably after (A-4) step when (A-4) step is included).

(A-5) The process can be implemented according to various methods well-known to those skilled in the art for the manufacture of a printed wiring board. Through the step (A-5), through holes and perforations can be formed in the insulating layer (resin composition). The step (A-5) can be performed using, for example, drilling, laser (CO ₂ (carbon dioxide gas) laser, YAG laser, etc.), plasma, or the like. The step (A-5) is preferably carried out using a laser.

The hole (through hole, through hole) formed in the step (A-5) may be in the form of penetrating the insulating layer (resin composition). The shape of the hole (through hole, perforation) formed by the step (A-5) is not particularly limited, but may be, for example, circular (slightly circular). The holes (via holes, through holes) formed in the step (A-5) may include those whose top diameter is, for example, 100 μm or less, preferably 70 μm or less, more preferably 50 μm or less, and more preferably 40 μm or less. Here, the top diameter of the through hole refers to the opening diameter of the through hole on the surface of the insulating layer (the side not connected to the inner substrate).

<(B) step> (B) step is to heat-treat the insulating layer at T ₂ (° C.). By carrying out the step (B), the occurrence of cracks occurring after the step (C) can be suppressed. It is speculated that this is because the stress dependent on the pattern shape of the inner substrate can be relaxed.

The heat treatment temperature (T ₂ ) in the (B) step is preferably a temperature lower than the curing heating temperature of the resin composition layer in the (A) step. The heat treatment temperature (T ₂ ) is not less than 60 (°C) and not more than 150 (°C). From the viewpoint of further suppressing the occurrence of cracks, it is preferably at least 70 (°C), more preferably at least 80 (°C), and still more Preferably it is 90 (°C) or higher, particularly preferably 100 (°C) or higher.

The difference (T ₁ -T ₂ ) between the glass transition temperature (T ₁ ) and the heat treatment temperature (T ₂ ) of the insulating layer is not more than 20 (°C), preferably not more than 15 (°C), more preferably not more than 10 (°C) or less, preferably less than 5 (°C), the lower limit of T ₁ -T ₂ is above -20 (°C), preferably above -15 (°C), more preferably above -10 (°C), More preferably, it is -5 (°C) or higher, and particularly preferably, it is 0 (°C) or higher.

The heat treatment time of the (B) step is preferably at least 1 minute, more preferably at least 10 minutes, and more preferably at least 20 minutes from the viewpoint of suppressing the occurrence of cracks. The upper limit is not particularly limited, but may be, for example, 120 minutes less than, less than 90 minutes, etc. The heat treatment time means the time for maintaining the heat treatment temperature.

The heat treatment in step (B) may be performed by heating the insulating layer in a gas environment, or by immersing the insulating layer in a liquid to heat the insulating layer, but is preferably performed by heating the insulator in a gas environment. The heat treatment is performed under a pressure of, for example, 0.05MPa~0.15MPa, preferably 0.08~0.12MPa.

Air, argon, nitrogen, or a mixed gas thereof can be used as the gas used for heating in a gas environment.

As the liquid used for heating in a liquid, a liquid having a boiling point equal to or higher than the heat treatment temperature (T ₂ ) can be used. As such liquids, for example, swelling liquids described below can be used. When using swelling liquid, it is preferable to set its heating temperature to the heat treatment temperature (T ₂ ), and its pH is preferably above 6, more preferably above 6.5, more preferably above 7, preferably below 14, and more preferably Preferably, it is 13.5 or less, 12 or less, 12.5 or less, 11 or less, 10 or less, 8 or less, and 7.5 or less.

The step (B) may also include the step of cooling the insulating layer to below 30° C. after heat-treating the insulating layer at T ₂ (° C.). The cooling temperature in this step is preferably from 10°C to 30°C, more preferably from 20°C to 30°C. The method of cooling is not particularly limited, but the insulation layer can be left to cool, the method of blowing cold air on the insulation layer, or the method of pressing the insulation layer to a cooling roller can be cooled. The cooling in this step is usually carried out under a gas (such as air, argon, nitrogen or a mixture thereof), for example, at a pressure of 0.05MPa~0.15MPa, preferably 0.08~0.12MPa.

The heat treatment may be performed only once or twice. When heat treatment is performed twice, as an embodiment, for example, after the first heat treatment of the insulating layer at T ₂ (°C), the insulating layer is cooled to below 30°C, and then the insulating layer is heated at T ₂ (°C). heat treatment. The cooling temperature and cooling method are the same as above. The heat treatment temperature and heat treatment time of the second time may also be different from the first time.

＜Step (C)＞ (C) The step is to use an oxidant solution to remove the scum on the insulating layer. The order and conditions of desmear processing are not specifically limited, The well-known order and conditions normally used when forming the insulating layer of a printed wiring board can be employ|adopted. The desmearing treatment can be performed, for example, by immersing the insulating layer in an oxidizing agent solution.

As the oxidizing agent solution, those commonly used in desmearing treatment can be used. As such an oxidizing agent solution, for example, an alkaline permanganic acid solution in which potassium permanganate or sodium permanganate is dissolved in an aqueous sodium hydroxide solution is exemplified. Also, the concentration of the oxidizing agent in the oxidizing agent solution is preferably at least 3% by mass, more preferably at least 5% by mass, more preferably at least 7% by mass, preferably at most 20% by mass, more preferably at most 15% by mass, Furthermore, it is more preferably at most 10% by mass.

As the oxidizing agent solution, a commercially available product can be used. Examples of commercially available oxidant solutions include alkaline permanganate solutions such as "Concentrate Compact CP" and "Doesing Solution Securiganth P" manufactured by Japan Atotech Co., Ltd.

The oxidizing agent solution is preferably heated and used during immersion of the insulating layer. The heating temperature of the oxidant solution is preferably at least 60°C, more preferably at least 65°C, more preferably at least 70°C, more preferably at most 100°C, more preferably at most 95°C, and more preferably at most 90°C .

The immersion time of the insulating layer in the oxidant solution is preferably at least 5 minutes, more preferably at least 10 minutes, more preferably at least 15 minutes, preferably at least 40 minutes, more preferably at least 30 minutes, and more preferably at least 30 minutes. Under 25 minutes.

In step (C), before the insulating layer is desmeared with an oxidant solution, the insulating layer may also be soaked in a swelling solution for swelling treatment.

Examples of swelling liquids include swelling liquids such as water, aqueous sodium hydroxide solution, and aqueous potassium hydroxide solution. Among them, water and swelling liquids are preferable, and water is more preferable. A commercially available product can be used as the swelling liquid. As a commercial item, "Swelling Dip Securiganth P" and "Swelling Dip Securiganth SBU" manufactured by Nippon Atotech Co., Ltd., etc. are mentioned, for example.

The swelling liquid is preferably used by heating when impregnating the insulating layer. The heating temperature of the swelling liquid is preferably above 30°C, more preferably above 35°C, more preferably above 40°C, preferably below 100°C, more preferably below 95°C, and more preferably below 90°C .

The immersion time of the insulating layer in the swelling solution is preferably at least 1 minute, more preferably at least 3 minutes, more preferably at least 5 minutes, more preferably at least 40 minutes, more preferably at least 30 minutes, and more preferably at least 25 minutes minutes or less.

The pH of the swelling liquid is preferably 6 or more, more preferably 6.5 or more, more preferably 7 or more, preferably 14 or less, more preferably 13.5 or less, 12 or less, 12.5 or less, 11 or less, 10 or less, 8 Below, below 7.5.

In step (C), after desmearing the insulating layer with an oxidizing agent solution, the insulating layer may also be dipped in a neutralizing solution for neutralization in view of removing the residue of the salt of the oxidizing agent.

As the neutralizing liquid, it is preferable to use an acidic aqueous solution. As the neutralizing solution, a commercially available product may be used, and examples of the commercially available neutralizing solution include "Reduction Solution Securiganth P" manufactured by ATOTECH Corporation in Japan.

The neutralizer is preferably used by heating when the insulating layer is impregnated. The heating temperature of the neutralizing solution is preferably 30°C or higher, more preferably 35°C or higher, preferably 80°C or lower, more preferably 70°C or lower, from the viewpoint of removing oxidant salt residues, etc. It is preferably below 60°C.

The immersion time of the insulating layer in the neutralizing solution is preferably 1 minute or more, more preferably 3 minutes or more, preferably 30 minutes or less, more preferably 20 minutes or less, from the viewpoint of removing oxidant salt residues and the like.

In the step (C), after desmearing the insulating layer with an oxidant solution (optionally dipping the insulating layer in a neutralizing solution for neutralization), drying can also be performed in the atmosphere.

The drying temperature is preferably at least 40°C, more preferably at least 60°C, preferably at most 120°C, more preferably at most 100°C. The drying time is preferably at least 10 minutes, more preferably at least 20 minutes, preferably at most 60 minutes, more preferably at most 40 minutes.

＜Step (D)＞ The manufacturing method of the printed wiring board of the present invention may further include (D) the step of forming a conductor layer on the surface of the insulating layer after the (C) step.

The conductive material used in the conductive layer in the step (D) is not particularly limited. In a preferred embodiment, the conductor layer contains at least one selected from the group consisting of gold, platinum, palladium, silver, copper, aluminum, cobalt, chromium, zinc, nickel, titanium, tungsten, iron, tin, and indium Metal. The conductor layer can be a single metal layer or an alloy layer. As the alloy layer, for example, an alloy of two or more metals selected from the above-mentioned group (for example, nickel‧chromium alloy, copper‧nickel alloy and copper‧titanium alloy) alloy) formed layer. Among them, based on the viewpoints of ease of formation, cost, and pattern processing of the conductor layer, a single metal layer of chromium, nickel, titanium, aluminum, zinc, gold, palladium, silver, or copper, or nickel‧ The alloy layer of chromium alloy, copper‧nickel alloy, copper‧titanium alloy, more preferably a single metal layer of chromium, nickel, titanium, aluminum, zinc, gold, palladium, silver or copper, or an alloy layer of nickel‧chromium alloy, More preferably a single metal layer of copper.

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

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

In one embodiment, the conductive layer can be formed by plating. For example, the surface of the insulating layer can be plated on the surface of the insulating layer by semi-additive method, full-additive method, etc., and a conductor layer with a desired wiring pattern can be formed. Formed by the semi-additive method. Hereinafter, an example of forming a conductor layer by a semi-additive method will be shown.

First, a plating seed layer is formed on the surface of the insulating layer by electroless plating. Next, on the formed plating seed layer, form a mask pattern corresponding to a desired wiring pattern to expose a part of the plating seed layer. On the plating seed layer after exposure, a metal layer is formed by electrolytic plating, and the mask pattern is removed. Subsequently, by etching and removing the unnecessary plating seed layer, a conductor layer having a desired wiring pattern can be formed.

The support can be placed in the middle of the (A) step (for example, between (A-2) step and (A-3) step, between (A-2) step and (A-3) step, (A-3) step and (A-4) step, or (A-4) step and (A-5) step), between (A) step and (B) step, or (B) step and (C) step removed between. The support body is preferably removed between (B) step and (C) step. Moreover, after completion|finish of each process, you may perform a water washing process as needed.

＜Resin composition layer＞ Hereinafter, the components contained in the resin composition layer bonded to the inner substrate in the laminate (the resin composition layer provided on the support in the resin sheet) will be described.

The resin composition layer includes (a) epoxy resin and (b) active ester hardener.

＜(a) Epoxy resin＞ (a) Epoxy resin is a curable resin having an epoxy group. (a) Epoxy resins described here have an epoxy equivalent of 5,000 g/eq. or less.

Examples of (a) epoxy resins include bixylenol type epoxy resins, bisphenol A type epoxy resins, bisphenol F type epoxy resins, bisphenol S type epoxy resins, and bisphenol AF type epoxy resins. Resin, dicyclopentadiene type epoxy resin, triphenol type epoxy resin, naphthol novolac type epoxy resin, phenol novolak type epoxy resin, tert-butyl-catechol type epoxy resin, naphthalene Naphthol-type epoxy resin, naphthol-type epoxy resin, onion-type epoxy resin, glycidylamine-type epoxy resin, glycidyl ester-type epoxy resin, cresol novolac-type epoxy resin, phenol arane-type epoxy resin , biphenyl type epoxy resin, linear aliphatic epoxy resin, epoxy resin with butadiene structure, alicyclic epoxy resin, heterocyclic epoxy resin, spiro ring-containing epoxy resin, cyclohexane Type epoxy resin, cyclohexanedimethanol type epoxy resin, pernathyl ether type epoxy resin, trimethylol type epoxy resin, tetraphenylethane type epoxy resin, isocyanuric acid type epoxy resin, Phenol phthalimide type epoxy resin, etc. (a) Epoxy resins may be used alone or in combination of two or more.

It is preferable that the resin composition layer contains the epoxy resin which has 2 or more epoxy groups in 1 molecule as (a) epoxy resin. The proportion of the epoxy resin having two or more epoxy groups in one molecule is preferably at least 50 mass %, more preferably at least 60 mass %, relative to 100 mass % of the non-volatile components of the epoxy resin, Most preferably, it is 70% by mass or more.

There are epoxy resins that are liquid at a temperature of 20°C (hereinafter referred to as "liquid epoxy resin") and epoxy resins that are solid at a temperature of 20°C (hereinafter referred to as "solid epoxy resin"). In the resin composition layer, as the epoxy resin, only liquid epoxy resin may be contained, or only solid epoxy resin may be contained, or both liquid epoxy resin and solid epoxy resin may be contained, but preferably Both liquid epoxy resin and solid epoxy resin are included.

As a liquid epoxy resin, the epoxy resin which has 2 or more epoxy groups in 1 molecule is preferable.

As the liquid epoxy resin, preferable are glycyrrhizin type epoxy resin, bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol AF type epoxy resin, naphthalene type epoxy resin, glycidyl ester type epoxy resin, glycidylamine type epoxy resin, phenol novolac type epoxy resin, alicyclic epoxy resin with ester skeleton, cyclohexanedimethanol type epoxy resin, cycloaliphatic glycidyl ether, And epoxy resin with butadiene structure.

Examples of polymers of liquid epoxy resins include "EX-992L" manufactured by Nagase Chemtex Corporation, "YX7400" manufactured by Mitsubishi Chemical Corporation, "HP4032" manufactured by DIC Corporation, "HP4032D", and "HP4032SS" (naphthalene ring epoxy resin); Mitsubishi Chemical Corporation's "828US", "828EL", "825", "EPICOTE 828EL" (bisphenol A epoxy resin); Mitsubishi Chemical Corporation's "jER807", "1750" (bisphenol F type epoxy resin); Mitsubishi Chemical Corporation's "jER152" (phenol novolak type epoxy resin); Mitsubishi Chemical Corporation's "630", "630LSD", "604" (glycidylamine type epoxy resin) "ED-523T" (licyrrhizol-type epoxy resin) manufactured by ADEKA Corporation; "EP-3950L" and "EP-3980S" (glycidylamine-type epoxy resin) manufactured by ADEKA Corporation; "EP-3980S" manufactured by ADEKA Corporation -4088S" (dicyclopentadiene-type epoxy resin); "ZX1059" (mixture of bisphenol A type epoxy resin and bisphenol F type epoxy resin) manufactured by Nippon Steel Chemical and Materials Co., Ltd.; manufactured by Nagase Chemtex Corporation "EX-721" (glycidyl ester type epoxy resin); "EX-991L" (epoxy resin containing alkylene oxide skeleton and butadiene skeleton) manufactured by Nagase Chemtex Corporation; "CELLOXIDE 2021P" manufactured by DAICEL Corporation (alicyclic epoxy resin having an ester skeleton); "PB-3600" manufactured by DAICEL, "JP-100", "JP-200" and "JP-400" manufactured by Nippon Soda Corporation (with butadiene Epoxy resin for structure); "ZX1658" and "ZX1658GS" (liquid 1,4-glycidylcyclohexane type epoxy resin) manufactured by Nippon Steel Chemical & Materials Co., Ltd.; "EG- 280" (epoxy resin containing fennel structure); "EX-201" (cyclic aliphatic glycidyl ether) manufactured by Nagase Chemtex Co., Ltd., etc.

The solid epoxy resin is preferably a solid epoxy resin having three or more epoxy groups in one molecule, more preferably an aromatic solid epoxy resin having three or more epoxy groups in one molecule. resin.

As the solid epoxy resin, bidiphenol type epoxy resin, naphthalene type epoxy resin, naphthalene type 4 functional epoxy resin, naphthol novolak type epoxy resin, cresol novolac type epoxy resin, Dicyclopentadiene type epoxy resin, triphenol type epoxy resin, naphthol type epoxy resin, biphenyl type epoxy resin, pernaphthylether type epoxy resin, anthracene type epoxy resin, bisphenol A type ring Oxygen resin, bisphenol AF type epoxy resin, phenol arane type epoxy resin, tetraphenylethane type epoxy resin, phenol phthalimide type epoxy resin.

Specific examples of solid epoxy resins include "HP4032H" (naphthalene-type epoxy resin) manufactured by DIC Corporation; "HP-4700" and "HP-4710" (naphthalene-type tetrafunctional epoxy resin) manufactured by DIC Corporation; ); "N-690" (cresol novolak type epoxy resin) manufactured by DIC Corporation; "N-695" (cresol novolak type epoxy resin) manufactured by DIC Corporation; "HP-7200" manufactured by DIC Corporation ", "HP-7200HH", "HP-7200H", "HP-7200L" (dicyclopentadiene-type epoxy resin); "EXA-7311", "EXA-7311-G3", " EXA-7311-G4", "EXA-7311-G4S", "HP6000", "HP6000L" (perynalyl ether type epoxy resin); Nippon Kayaku "EPPN-502H" (triphenol type epoxy resin) ; "NC7000L" (naphthol novolak type epoxy resin) manufactured by Nippon Kayaku Corporation; "NC3000H", "NC3000", "NC3000L", "NC3000FH", "NC3100" (biphenyl type Epoxy resin); "ESN475V" and "ESN4100V" (naphthalene-type epoxy resin) manufactured by Nippon Steel Chemical and Materials Co., Ltd.; "ESN485" (naphthol-type epoxy resin) manufactured by Nippon Steel Chemical and Materials Co., Ltd.; Nippon Steel "ESN375" (dihydroxynaphthalene-type epoxy resin) manufactured by Chemical and Materials Corporation; "YX4000H", "YX4000", "YX4000HK", "YL7890" (bixylenol-type epoxy resin) manufactured by Mitsubishi Chemical Corporation; "YL6121" (biphenyl type epoxy resin) manufactured by Mitsubishi Chemical Corporation; "YX8800" (onion type epoxy resin) manufactured by Mitsubishi Chemical Corporation; "YX7700" (phenol aralkylene type epoxy resin) manufactured by Mitsubishi Chemical Corporation ; "PG-100" and "CG-500" manufactured by Osaka Gas Chemical Co., Ltd.; "YL7760" (bisphenol AF type epoxy resin) manufactured by Mitsubishi Chemical Corporation; resin); "jER1010" (bisphenol A type epoxy resin) manufactured by Mitsubishi Chemical Corporation; "jER1031S" (tetraphenylethane type epoxy resin) manufactured by Mitsubishi Chemical Corporation; "WHR991S" manufactured by Nippon Kayaku Corporation (phenol phthalimide type epoxy resin), etc. These may be used alone or in combination of two or more.

When (a) epoxy resin is used in combination of solid epoxy resin and liquid epoxy resin, the mass ratio (solid epoxy resin:liquid epoxy resin) is preferably 10:1~1:50 , more preferably 2:1~1:20, particularly preferably 1:1~1:10.

(a) The epoxy equivalent of epoxy resin is preferably 50g/eq.~5,000g/eq., more preferably 60g/eq.~2,000g/eq., and more preferably 70g/eq.~1,000g/ eq., and more preferably 80g/eq.~500g/eq. Epoxy equivalent is the mass of epoxy group per 1 equivalent of resin. This epoxy equivalent can be measured based on JISK7236.

(a) The weight average molecular weight (Mw) of the epoxy resin is preferably from 100 to 5,000, more preferably from 250 to 3,000, and still more preferably from 400 to 1,500. The weight average molecular weight of resin can be measured as the value of polystyrene conversion by the gel permeation chromatography (GPC) method.

The content of (a) epoxy resin in the resin composition layer is not particularly limited, but when the non-volatile content in the resin composition layer is 100% by mass, it is preferably 70% by mass or less, more preferably 50% by mass % or less, more preferably less than 30 mass %, particularly preferably less than 20 mass %. The lower limit of the (a) epoxy resin content in the resin composition layer is not particularly limited, but when the non-volatile components in the resin composition layer are 100% by mass, it is preferably 0.1% by mass or more, more preferably 1 mass % or more, more preferably 5 mass % or more, especially preferably 10 mass % or more.

＜(b) Active ester hardener＞ The (b) active ester-based hardener is an epoxy resin hardener capable of reacting with (a) epoxy resin to harden it. (b) The active ester-based curing agent may be used alone or in any combination of two or more.

As (b) active ester-based hardener, it is preferable to use general phenol esters, thiophenol esters, N-hydroxylamine esters, esters of heterocyclic hydroxyl compounds, etc., which have more than two reactivity in one molecule. Compounds with high ester groups. The active ester compound is preferably obtained by condensation reaction of carboxylic acid compound and/or thiocarboxylic acid compound with hydroxyl compound and/or thiol compound. In particular, from the viewpoint of improving heat resistance, an active ester compound obtained by combining a carboxylic acid compound with a hydroxyl compound is preferred, and an active ester compound obtained by combining a carboxylic acid compound with a phenol compound and/or a naphthol compound is more preferred. Examples of the carboxylic acid compound include benzoic acid, acetic acid, succinic acid, maleic acid, itaconic acid, phthalic acid, isophthalic acid, terephthalic acid, and pyromellitic acid. Examples of the phenol compound or naphthol compound include hydroquinone, resorcinol, bisphenol A, bisphenol F, bisphenol S, phenolphthalein, methylated bisphenol A, methylated bisphenol F, methylated Bisphenol S, phenol, o-cresol, m-cresol, p-cresol, catechol, α-naphthol, β-naphthol, 1,5-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 2, 6-dihydroxynaphthalene, dihydroxybenzophenone, trihydroxybenzophenone, tetrahydroxybenzophenone, pyrogallol, glucinol, dicyclopentadiene-type diphenol compounds, phenolic novolac, etc. . Here, the "dicyclopentadiene-type diphenol compound" means a diphenol compound obtained by condensing 2 molecules of phenol to 1 molecule of dicyclopentadiene.

As (b) the active ester-based hardener, specifically, dicyclopentadiene-type active ester compounds, naphthalene-type active ester compounds containing a naphthalene structure, active ester compounds containing acetylated phenol novolaks, The active ester compound of a phenolic novolac-containing benzoyl compound is more preferably at least one selected from dicyclopentadiene-type active ester compounds and naphthalene-type active ester compounds. As the dicyclopentadiene-type active ester compound, an active ester compound containing a dicyclopentadiene-type diphenol structure is preferable.

(b) Commercially available active ester-based hardeners, examples of active ester compounds containing a dicyclopentadiene-type diphenol structure include "EXB9451", "EXB9460", "EXB9460S", and "HPC-8000L-65TM" , "HPC-8000-65T", "HPC-8000H", "HPC-8000H-65TM" (manufactured by DIC Corporation); examples of active ester compounds containing a naphthalene structure include "HP-B-8151-62T", "EXB -8100L-65T", "EXB-9416-70BK", "HPC-8150-62T", "EXB-8" (manufactured by DIC Corporation); examples of phosphorus-containing active ester compounds include "EXB9401" (manufactured by DIC Corporation), Examples of active ester compounds of acetylated phenol novolaks include "DC808" (manufactured by Mitsubishi Chemical Corporation), and examples of active ester compounds of benzoyl compounds of phenol novolaks include "YLH1026", "YLH1030", and "YLH1048" (manufactured by Mitsubishi Chemical Corporation), and "PC1300-02-65MA" (manufactured by Air Water Corporation) etc. are exemplified as active ester compounds having a styryl group and a naphthalene structure.

(b) The active ester group equivalent weight of the active ester hardener is preferably 50g/eq.~500g/eq., more preferably 50g/eq.~400g/eq., and more preferably 100g/eq.~300g /eq.. The active ester group equivalent is the mass of (b) active ester-based hardener per 1 equivalent of active ester group.

The content of (b) the active ester-based hardener in the resin composition layer is not particularly limited, but when the non-volatile content in the resin composition layer is 100% by mass, it is preferably 70% by mass or less, more preferably 50 mass % or less, more preferably 30 mass % or less, especially preferably 25 mass % or less. The lower limit of the content of (b) the active ester-based hardener in the resin composition layer is not particularly limited, but when the non-volatile content in the resin composition layer is 100% by mass, it is preferably at least 1% by mass, more preferably It is at least 3% by mass, more preferably at least 5% by mass, and most preferably at least 7% by mass.

＜(b') Other hardeners＞ The resin composition layer may contain (b') other curing agents as optional components in addition to the (b) active ester-based curing agent. The (b') other curing agents described here are components other than those corresponding to the (b) active ester-based curing agents described above. (b') Other curing agents may be used alone or in any combination of two or more. (b') Other hardeners are epoxy resin hardeners capable of reacting with (a) epoxy resin and hardening them like (b) active ester hardener.

(b') Other curing agents are not particularly limited, but examples include phenolic curing agents, carbodiimide curing agents, acid anhydride curing agents, amine curing agents, benzoxazine curing agents, cyanide curing agents, Ester-based hardeners and mercaptan-based hardeners, etc. In the resin composition layer, as (b') another curing agent, it is preferable to contain at least one curing agent selected from the group consisting of phenolic curing agents, carbodiimide curing agents, and cyanate ester curing agents, and further It preferably contains at least one curing agent selected from phenol-based curing agents and cyanate-based curing agents, and particularly preferably contains cyanate-based curing agents.

The phenolic curing agent is preferably a phenolic curing agent having a novolac structure from the viewpoint of heat resistance and water resistance. Also, from the viewpoint of adhesiveness to an adherend, a nitrogen-containing phenolic curing agent is preferred, and a triazine skeleton-containing phenolic curing agent is more preferred. Among them, a triazine skeleton-containing phenol novolak resin is preferable from the viewpoint of highly satisfying heat resistance, water resistance, and adhesiveness. Specific examples of phenolic curing agents include "MEH-7700", "MEH-7810", and "MEH-7851" manufactured by Meiwa Kasei Co., Ltd., "NHN", "CBN", " GPH", "SN-170", "SN-180", "SN-190", "SN-475", "SN-485", "SN-495", "SN- 375", "SN-395", "LA-7052", "LA-7054", "LA-3018", "LA-3018-50P", "LA-1356", "TD2090", " KA-1160", etc.

As the carbodiimide-based curing agent, there can be mentioned a curing agent having one or more, preferably two or more carbodiimide structures in one molecule, such as tetramethylene-bis(tert-butyl Carbodiimide), cyclohexanebis(methylene-tert-butylcarbodiimide) and other aliphatic biscarbodiimides; phenylene-bis(xylylcarbodiimide) Aromatic biscarbodiimides such as amines); polyhexamethylenecarbodiimide, polytrimethylhexamethylenecarbodiimide, polycyclohexylcarbodiimide, poly( Aliphatic polycarbodiimides such as methylenebiscyclohexylcarbodiimide), poly(isophoronecarbodiimide); poly(phenylenecarbodiimide), poly( Naphthylenecarbodiimide), poly(cresylcarbodiimide), poly(methyldiisopropylphenylenecarbodiimide), poly(triethylenylcarbodiimide amine), poly(diethylphenylenecarbodiimide), poly(triisopropylphenylenecarbodiimide), poly(diisopropylphenylenecarbodiimide), poly(di Tolylcarbodiimide), poly(tetramethylxylylenecarbodiimide), poly(methylenebisphenylenecarbodiimide), poly[methylenebis(methylxylylenecarbodiimide) Polycarbodiimides such as aromatic polycarbodiimides such as phenyl) carbodiimides.

Examples of commercially available carbodiimide hardeners include "CARBIDILITE V-02B", "CARBIDILITE V-03", "CARBIDILITE V-04K", "CARBIDILITE V-07" manufactured by Nisshinbo Chemical Co., Ltd. "CARBIDILITE V-09"; "STABAXOL P", "STABAXOL P400", "HICAZYL 510" manufactured by LANXESS Corporation.

Examples of the acid anhydride curing agent include those having one or more acid anhydride groups in one molecule, preferably those having two or more acid anhydride groups in one molecule. Specific examples of acid anhydride hardeners include phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methylhexahydrophthalic anhydride, Formic anhydride, methylnadic anhydride, hydrogenated methylnadic anhydride, trialkyltetramethylphthalic anhydride, dodecenylsuccinic anhydride, 5-(2,5-dioxotetrahydro-3 -furyl)-3-methyl-3-cyclohexene-1,2-dicarboxylic anhydride, trimellitic anhydride, pyromellitic anhydride, benzophenone tetracarboxylic dianhydride, biphenyl tetracarboxylic acid Dianhydride, Naphthalene tetracarboxylic dianhydride, Oxydiphthalic dianhydride, 3,3'-4,4'-Diphenylpyridine tetracarboxylic dianhydride, 1,3,3a,4,5,9b -Hexahydro-5-(tetrahydro-2,5-dioxo-3-furyl)-naphtho[1,2-c]furan-1,3-dione, ethylene glycol bis(triphenylene anhydride), polymeric anhydrides such as styrene-maleic acid resin copolymerized with styrene and maleic acid, etc. Examples of commercially available acid anhydride hardeners include "HNA-100", "MH-700", "MTA-15", "DDSA", "OSA" manufactured by Nippon Chemical Corporation, and " YH-306", "YH-307", "HN-2200", "HN-5500" manufactured by Hitachi Chemical Co., Ltd., "EF-30", "EF-40", "EF-60" manufactured by Cray Valley Corporation , "EF-80" and so on.

Examples of amine-based hardeners include those having one or more, preferably two or more, amine groups in one molecule, such as aliphatic amines, polyether amines, alicyclic amines, aromatic Among the amines, aromatic amines are preferred from the viewpoint of exerting the desired effect of the present invention. The amine hardener is preferably a primary amine or a secondary amine, more preferably a primary amine. Specific examples of amine hardeners include 4,4'-methylene bis(2,6-dimethylaniline), 4,4'-diamine diphenylmethane, 4,4'-diamine Diphenylene, 3,3'-diaminodiphenylene, m-phenylenediamine, m-xylylenediamine, diethyltoluenediamine, 4,4'-diaminodiphenyl ether, 3 ,3'-Dimethyl-4,4'-diaminobiphenyl, 2,2'-dimethyl-4,4'-diaminobiphenyl, 3,3'-dihydroxybenzidine, 2 ,2-bis(3-amino-4-hydroxyphenyl)propane, 3,3-dimethyl-5,5-diethyl-4,4-diphenylmethanediamine, 2,2-bis (4-aminophenyl)propane, 2,2-bis(4-(4-aminophenoxy)phenyl)propane, 1,3-bis(3-aminophenoxy)benzene, 1, 3-bis(4-aminophenoxy)benzene, 1,4-bis(4-aminophenoxy)benzene, 4,4'-bis(4-aminophenoxy)biphenyl, bis( 4-(4-aminophenoxy)phenyl)pyridine, bis(4-(3-aminophenoxy)phenyl)pyridine, etc. Commercially available amine hardeners can also be used, such as "SEIKACURE-S" manufactured by SEIKA Corporation, "KAYABOND C-200S" manufactured by Nippon Kayaku Co., Ltd., "KAYABOND C-100", "KAYAHARD A-A", " KAYAHARD A-B", "KAYAHARD A-S", "EPICURE W" manufactured by Mitsubishi Chemical Corporation, etc.

Specific examples of benzoxazine-based curing agents include "JBZ-OP100D" and "ODA-BOZ" manufactured by JFE Chemical Co., Ltd.; "HFB2006M" manufactured by Showa High Polymer Co., Ltd.; "P-d" manufactured by Shikoku Chemical Industry Co., Ltd. ", "F-a" and so on.

As the cyanate-based hardener, for example, bisphenol A dicyanate, polyphenol cyanate (oligo(3-methylene-1,5-phenylene cyanate)), 4, 4'-methylene bis(2,6-dimethylphenyl cyanate), 4,4'-ethylene diphenyl dicyanate, hexafluorobisphenol A dicyanate, 2, 2-bis(4-cyanato)phenylpropane, 1,1-bis(4-cyanatophenylmethane), bis(4-cyanato-3,5-dimethylphenyl ) methane, 1,3-bis(4-cyanatophenyl-1-(methylethylene))benzene, bis(4-cyanatophenyl)sulfide and bis(4-cyanate Bifunctional cyanate ester resins such as phenyl) ether, polyfunctional cyanate ester resins derived from phenol novolac and cresol novolac, etc., partially triazinated prepolymers of these cyanate resins, etc. Specific examples of cyanate-based hardeners include "PT30" and "PT60" (both phenolic novolac type multifunctional cyanate resins), "BA230" and "BA230S75" (bisphenol A prepolymer of a part or all of a triazinated trimer of a dicyanate), etc.

Examples of thiol-based hardeners include trimethylolpropane tris(3-mercaptopropionate), pentaerythritol tetrakis(3-mercaptobutyrate), tris(3-mercaptopropyl)isocyanurate, etc. .

(b') The reactive group equivalent weight of other curing agents is preferably 50g/eq.~3000g/eq., more preferably 100g/eq.~1000g/eq., and more preferably 100g/eq.~500g/eq. , especially 100g/eq.~300g/eq. Reactive group equivalent refers to the mass of (b') other hardeners per 1 equivalent of reactive group.

The content of (b') other hardeners in the resin composition layer is not particularly limited, but when the non-volatile content in the resin composition layer is 100% by mass, it is preferably 50% by mass or less, more preferably 30% by mass % or less, more preferably less than 20 mass %, particularly preferably less than 10 mass %. The lower limit of the content of (b') other curing agents in the resin composition layer is not particularly limited, but when the non-volatile content in the resin composition layer is 100 mass %, it may be, for example, 0 mass % or more, or 0.01 mass % % or more, preferably at least 0.1% by mass, more preferably at least 0.5% by mass, particularly preferably at least 1% by mass.

＜(c) Inorganic filler＞ The resin composition layer may also contain (c) an inorganic filler as an optional component. (c) The inorganic filler is contained in the resin composition layer in the state of particles.

As a material of (c) the inorganic filler, an inorganic compound is used. Examples of materials for the (c) inorganic filler include silicon oxide, aluminum oxide, glass, cordierite, silicon oxide, barium sulfate, barium carbonate, talc, clay, mica powder, zinc oxide, hydrotalcite, diaspore, Aluminum hydroxide, magnesium hydroxide, calcium carbonate, magnesium carbonate, magnesium oxide, boron nitride, aluminum nitride, manganese dinitride, aluminum borate, strontium carbonate, strontium titanate, calcium titanate, magnesium titanate, titanium Bismuth oxide, titanium oxide, zirconium oxide, barium titanate, barium titanate zirconate, barium zirconate, calcium zirconate, zirconium phosphate and zirconium phosphotungstate, etc. Among them, silicon oxide is particularly preferable. Examples of silicon oxide include amorphous silicon oxide, fused silicon oxide, crystalline silicon oxide, synthetic silicon oxide, and hollow silicon oxide. Moreover, as silicon oxide, spherical silicon oxide is preferable. (c) The inorganic filler may be used individually by 1 type, and may use it combining 2 or more types by arbitrary ratios.

Commercially available products of (c) inorganic fillers include, for example, "SP60-05" and "SP507-05" manufactured by Nippon Steel Chemical & Materials Co., Ltd.; "YC100C", "YA050C" and "YA050C- MJE", "YA010C"; "UFP-30" manufactured by DENKA Corporation; "SILFIL NSS-3N", "SILFIL NSS-4N" and "SILFIL NSS-5N" manufactured by TOKUYAMA Corporation; "SC2500SQ" manufactured by ADMATECHS Corporation, "SO-C4", "SO-C2", "SO-C1"; "DAW-03", "FB-105FD" manufactured by DENKA Corporation, etc.

(c) The average particle size of the inorganic filler is not particularly limited, but is preferably not more than 10 μm, more preferably not more than 5 μm, more preferably not more than 3 μm, still more preferably not more than 2 μm, and most preferably not more than 1.5 μm. (c) The lower limit of the average particle diameter of the inorganic filler is not particularly limited, but is preferably at least 0.01 μm, more preferably at least 0.05 μm, still more preferably at least 0.1 μm, and most preferably at least 0.2 μm. (c) The average particle size of the inorganic filler can be measured by the laser diffraction‧scattering method based on the Mie scattering theory. Specifically, the particle size distribution of the inorganic filler can be prepared on a volume basis with a laser diffraction scattering type particle size distribution measuring device, and can be measured with the median diameter as the average particle size. The measurement sample can be used to weigh 100mg of inorganic filler and 10g of methyl ethyl ketone in a small glass bottle, and disperse it by ultrasonic wave for 10 minutes. The measurement sample uses a laser diffraction particle size distribution measuring device, sets the wavelength of the light source to blue and red, and measures the volume-based particle size distribution of the inorganic filler by means of a flow cell. The obtained particle size The average particle diameter was calculated as the median diameter from the distribution. As a laser diffraction-scattering type particle size distribution measuring device, "LA-960" etc. by Horiba Manufacturing Co., Ltd. can be mentioned, for example.

(c) The specific surface area of the inorganic filler is not particularly limited, but is preferably at least 0.1m ² /g, more preferably at least 0.5m ² /g, still more preferably at least 1m ² /g, most preferably at least 3m ^{2 /} g more than g. (c) The upper limit of the specific surface area of the inorganic filler is not particularly limited, but is preferably at most 100m ² /g, more preferably at most 70m ² /g, still more preferably at most 50m ² /g, still more preferably at most 30m ² /g or less, particularly preferably 10 m ² /g or less. The specific surface area of the inorganic filler is based on the BET method, using a specific surface area measuring device (Macsorb HM-1210 manufactured by MOUNTECH Co., Ltd.) to adsorb nitrogen on the surface of the sample, and calculate the specific surface area using the BET multi-point method.

(c) The inorganic filler is preferably treated with a surface treatment agent from the viewpoint of improving moisture resistance and dispersibility. Examples of surface treatment agents include fluorine-containing silane coupling agents, aminosilane coupling agents, epoxysilane coupling agents, mercaptosilane coupling agents, silane coupling agents, alkoxysilanes, and organosilazane compounds. , Titanate coupling agent, etc. Moreover, a surface treatment agent may be used individually by 1 type, and may use it in combination of 2 or more types arbitrarily.

Examples of commercially available surface treatment agents include Shin-Etsu Chemical Co., Ltd. "KBM403" (3-glycidyloxypropyltrimethoxysilane), Shin-Etsu Chemical Co., Ltd. "KBM803" (3-mercaptopropyltrimethoxysilane) oxysilane), Shin-Etsu Chemical Co., Ltd. "KBE903" (3-aminopropyltriethoxysilane), Shin-Etsu Chemical Co., Ltd. "KBM573" (N-phenyl-3-aminopropyltrimethoxysilane ), Shin-Etsu Chemical Co., Ltd. "SZ-31" (hexamethyldisilazane), Shin-Etsu Chemical Co., Ltd. "KBM103" (phenyltrimethoxysilane), Shin-Etsu Chemical Co., Ltd. "KBM-4803" ( long-chain epoxy silane coupling agent), "KBM-7103" (3,3,3-trifluoropropyltrimethoxysilane) manufactured by Shin-Etsu Chemical Co., Ltd., etc.

The degree of surface treatment by the surface treatment agent is preferably limited to a specific range from the viewpoint of improving the dispersibility of the inorganic filler. Specifically, 100% by mass of the inorganic filler is preferably treated with a surface treatment agent at 0.2% to 5% by mass, more preferably at 0.2% to 3% by mass, and more preferably at 0.3% to 3% by mass. 2% by mass for surface treatment.

The degree of surface treatment by the surface treatment agent can be evaluated by the amount of carbon per unit surface area of the inorganic filler. The amount of carbon per unit surface area of the inorganic filler is preferably 0.02 mg/m ² or more, more preferably 0.1 mg/m ² or more, and more preferably 0.2 mg/m 2 from the viewpoint of improving the dispersibility of the inorganic filler ² or more. On the other hand, from the viewpoint of the melt viscosity of the resin composition and the prevention of an increase in the melt viscosity of the flake form, it is preferably 1.0 mg/m ² or less, more preferably 0.8 mg/m ² or less, and still more preferably 0.5 mg/m 2 ² or less.

(c) The amount of carbon per unit surface area of the inorganic filler can be measured by washing the surface-treated inorganic filler with a solvent (such as methyl ethyl ketone (MEK)). Specifically, a sufficient amount of MEK as a solvent was added to the inorganic filler surface-treated with a surface treatment agent, and cleaned with ultrasonic waves at 25° C. for 5 minutes. After removing the supernatant and drying the solid content, the amount of carbon per unit surface area of the inorganic filler was measured using a carbon analyzer. As the carbon analyzer, "EMIA-320V" manufactured by HORIBA CO., LTD., etc. can be used.

The content of (c) the inorganic filler in the resin composition layer is not particularly limited, but when the non-volatile content in the resin composition layer is 100 mass%, it is preferably 95 mass% or less, more preferably 90 mass% It is not more than 85% by mass, more preferably not more than 85% by mass, and most preferably not more than 80% by mass. The lower limit of the content of (c) the inorganic filler in the resin composition layer is not particularly limited, but from the viewpoint of suppressing the dielectric loss factor to be lower, when the non-volatile components in the resin composition layer are 100% by mass, For example, it may be at least 0% by mass, at least 1% by mass, or at least 5% by mass, preferably at least 10% by mass, more preferably at least 30% by mass, more preferably at least 40% by mass, and even more preferably at least 50% by mass. % or more, especially preferably more than 60% by mass.

＜(d) Radical polymerizable compound＞ The resin composition layer may contain (d) a radically polymerizable compound as an optional component. (d) The freely polymerizable compound may be used alone or in any combination of two or more.

(d) The radically polymerizable compound is a radically polymerizable compound having an ethylenically unsaturated bond in one embodiment. (d) The radically polymerizable compound is not particularly limited, but may have, for example, allyl, 3-cyclohexenyl, 3-cyclopentenyl, 2-vinylphenyl, 3-vinylphenyl, 4- Unsaturated hydrocarbon groups such as vinylphenyl; acryl, methacryl, maleimide (2,5-dihydro-2,5-dioxo-1H-pyrrol-1-yl) Free radical polymerizable groups such as α, β-unsaturated carbonyl, etc. (d) The radically polymerizable compound preferably has two or more radically polymerizable groups.

(d) The radically polymerizable compound in the first embodiment preferably includes a thermoplastic resin having a vinylphenyl group and/or a (meth)acryl group. (Meth)acryl means acryl or methacryl. Vinylphenyl includes 2-vinylphenyl, 3-vinylphenyl, 4-vinylphenyl or those whose aromatic carbon atoms are further substituted with one or more alkyl groups. It is preferable to have 2 or more vinylphenyl groups and/or (meth)acryloyl groups in 1 molecule. Examples of thermoplastic resins include phenoxy resins, polyvinyl acetal resins, polystyrene resins, polyethylene resins, polypropylene resins, polybutadiene resins, polyimide resins, and polyamideimide resins. , polyetherimide resin, polyether imide resin, polyether imide resin, polyether imide resin, polyphenylene ether resin, polyether ether ketone resin, polyester resin, etc., (d) radically polymerizable compounds in this embodiment include these Modified resins with vinylphenyl and/or (meth)acryl groups.

(d) The radically polymerizable compound in the first embodiment preferably includes modified polyphenylene ether resins having vinylphenyl groups and/or (meth)acryl groups and modified polyphenylene ether resins having vinylphenyl groups and/or (meth)acryl groups. Or the resin of the modified polystyrene resin of (meth)acryl group, more preferably comprises the modified polyphenylene ether resin that has vinylphenyl and/or (meth)acryl group, particularly preferably comprises the formula Resin represented by (B-1):

[In the formula, R ¹¹ and R ¹² each independently represent an alkyl group; R ¹³ , R ¹⁴ , R ²¹ , R ²³ and R ²⁴ each independently represent a hydrogen atom or an alkyl group; R ³¹ and R ³² each independently represent a vinyl phenyl group or (meth)acryloyl; Y ¹ represents a single bond, -C(R ^y ) ₂ -, -O-, -CO-, -S-, -SO- or -SO ₂ -; R ^y independently represents a hydrogen atom or an alkyl group; Y ² represents a single bond or an alkylene group; p represents 0 or 1; q and r each independently represent an integer of 1 or more]. The q unit and the r unit may be the same or different for each unit.

R ¹¹ and R ¹² each independently represent an alkyl group, preferably a methyl group. R ¹³ and R ¹⁴ each independently represent a hydrogen atom or an alkyl group, preferably a hydrogen atom or an alkyl group, more preferably a hydrogen atom. R ²¹ and R ²² each independently represent a hydrogen atom or an alkyl group, preferably a hydrogen atom or a methyl group, more preferably a methyl group. R ²³ and R ²⁴ each independently represent a hydrogen atom or an alkyl group, preferably a hydrogen atom or a methyl group.

The term "alkyl group" means a linear, branched and/or cyclic monovalent aliphatic saturated hydrocarbon group. Unless otherwise specified, the alkyl group is preferably an alkyl group having 1 to 14 carbon atoms, more preferably an alkyl group having 1 to 10 carbon atoms, and still more preferably an alkyl group having 1 to 6 carbon atoms. Examples of the alkyl group include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, second butyl, third butyl, pentyl, hexyl, heptyl, octyl, nonyl, Decyl, cyclopentyl, cyclohexyl, methylcyclohexyl, dimethylcyclohexyl, trimethylcyclohexyl, cyclopentylmethyl, cyclohexylmethyl, etc.

R ³¹ and R ³² each independently represent a vinylphenyl group or a (meth)acryl group, and Y ² represents a single bond or an alkylene group. The term "alkylene group" means a linear, branched and/or cyclic divalent aliphatic saturated hydrocarbon group. The alkylene group is preferably an alkylene group having 1 to 14 carbon atoms, more preferably an alkylene group having 1 to 10 carbon atoms, more preferably an alkylene group having 1 to 6 carbon atoms. Examples of the alkylene group include -CH ₂ -, -CH ₂ -CH ₂ -, -CH(CH ₃ )-, -CH ₂ -CH ₂ -CH ₂ -, -CH ₂ -CH(CH ₃ )-, -CH(CH ₃ )-CH ₂ -, -C(CH ₃ ) ₂ -, etc. Preferably R ³¹ and R ³² are vinylphenyl, and Y ² is alkylene (especially preferably -CH ₂ -), or R ³¹ and R ³² are (meth)acryloyl, and Y ² is mono key.

Y ¹ represents a single bond, -C(R ^y ) ₂ -, -O-, -CO-, -S-, -SO- or -SO ₂ -, preferably a single bond, -C(R ^y ) ₂ - or -O-. R ^y each independently represent a hydrogen atom or an alkyl group, preferably a hydrogen atom or a methyl group. p represents 0 or 1, preferably 1. q and r each independently represent an integer of 1 or more, preferably an integer of 1 to 200, more preferably an integer of 1 to 100.

Commercially available products of (d) the radically polymerizable compound of the first embodiment include "OPE-2St 1200" and "OPE-2St 2200" (vinylbenzyl-modified polyphenylene ether) manufactured by Mitsubishi Gas Chemical Co., Ltd. resin); "SA9000" and "SA9000-111" (methacrylic acid-modified polyphenylene ether resin) manufactured by SABIC Innovative Plastics Co., Ltd.;

The content of (d) the radically polymerizable compound in the resin composition layer is not particularly limited, but when the non-volatile content in the resin composition layer is 100% by mass, it is preferably 50% by mass or less, more preferably 30% by mass. % by mass or less, more preferably less than 20 mass %, particularly preferably less than 10 mass %. The lower limit of the content of (d) the radically polymerizable compound in the resin composition layer is not particularly limited, but from the viewpoint of suppressing the dielectric dissipation factor to be lower, the non-volatile components in the resin composition layer are set to 100% by mass , for example, 0% by mass or more, 0.01% by mass or more, preferably 0.1% by mass or more, more preferably 1% by mass or more, more preferably 1% by mass or more, particularly preferably 3% by mass or more.

＜(e) Thermoplastic resin＞ The resin composition layer may further contain (e) a thermoplastic resin as an optional component. The (e) thermoplastic resin described here is not a component corresponding to (a) epoxy resin, (b) other curing agent, and (d) radically polymerizable compound.

Examples of (e) thermoplastic resins include polyimide resins, phenoxy resins, polyvinyl acetal resins, polyolefin resins, polybutadiene resins, polyamideimide resins, and polyetherimide resins. , Polyester resin, polyether resin, polyphenylene ether resin, polycarbonate resin, polyether ether ketone resin, polyester resin, etc. In one embodiment, the resin composition layer preferably includes a thermoplastic resin selected from the group consisting of polyimide resin and phenoxy resin, more preferably includes phenoxy resin. Moreover, a thermoplastic resin may be used individually by 1 type, or may use it in combination of 2 or more types.

Specific examples of the polyimide resin include "SLK-6100" manufactured by Shin-Etsu Chemical Co., Ltd., "RIKACOAT SN20" and "RIKACOAT PN20" manufactured by Shin Nippon Chemical Co., Ltd., and the like.

Examples of phenoxy resins include bisphenol A skeleton, bisphenol F skeleton, bisphenol S skeleton, bisphenol acetophenone skeleton, novolac skeleton, biphenyl skeleton, fennel skeleton, dicyclopentadiene skeleton, A phenoxy resin having one or more skeletons of the group consisting of a norbornene skeleton, a naphthalene skeleton, an onion skeleton, an adamantane skeleton, a terpene skeleton, and a trimethylcyclohexane skeleton. The terminal of the phenoxy resin can be any functional group such as phenolic hydroxyl group or epoxy group.

Specific examples of phenoxy resins include "1256" and "4250" manufactured by Mitsubishi Chemical Corporation (both phenoxy resins containing a bisphenol A skeleton); "YX8100" manufactured by Mitsubishi Chemical Corporation (a bisphenol S skeleton containing phenoxy resin); "YX6954" manufactured by Mitsubishi Chemical Corporation (phenoxy resin containing bisphenol acetophenone skeleton); "FX280" and "FX293" manufactured by Nippon Steel & Sumikin Chemical Corporation; "YL7500BH30" manufactured by Mitsubishi Chemical Corporation ", "YX6954BH30", "YX7553", "YX7553BH30", "YL7769BH30", "YL6794", "YL7213", "YL7290", "YL7482" and "YL7891BH30".

Examples of the polyvinyl acetal resin include polyvinyl formal resin, polyvinyl butyral resin, and the like, and polyvinyl butyral resin is preferred. Specific examples of polyvinyl butyral resins include "DENKA BUTYRAL 4000-2", "DENKA BUTYRAL 5000-A", "DENKA BUTYRAL 6000-C", "DENKA BUTYRAL 6000-EP" manufactured by Denki Kagaku Kogyo Co., Ltd. "; S-LEC BH series, BX series (such as BX-5Z), KS series (such as KS-1), BL series, BM series, etc. manufactured by Sekisui Chemical Industry Co., Ltd.

Examples of polyolefin resins include ethylene-based resins such as low-density polyethylene, ultra-low-density polyethylene, high-density polyethylene, ethylene-vinyl acetate copolymer, ethylene-ethyl acrylate copolymer, and ethylene-methyl acrylate copolymer. Copolymer resins; polyolefin polymers such as polypropylene and ethylene-propylene block copolymers, etc.

Examples of polybutadiene resins include hydrogenated polybutadiene skeleton-containing resins, hydroxyl-containing polybutadiene resins, phenolic hydroxyl-containing polybutadiene resins, carboxyl-containing polybutadiene resins, and acid anhydride group-containing polybutadiene resins. Vinyl resin, epoxy-containing polybutadiene, isocyanate-containing polybutadiene resin, urethane-containing polybutadiene resin, polyphenylene ether-polybutadiene resin, etc.

Specific examples of the polyamideimide resin include "VYLOMAX HR11NN" and "VYLOMAX HR16NN" manufactured by Toyobo Co., Ltd. Specific examples of the polyamide-imide include modified polyamide-imides such as "KS9100" and "KS9300" (polysiloxane skeleton-containing polyamide-imide) manufactured by Hitachi Chemical Co., Ltd.

Specific examples of the polyethersulfone resin include "PES5003P" manufactured by Sumitomo Chemical Co., Ltd. and the like.

Specific examples of the polyester resin include "P1700" and "P3500" manufactured by Solvay Specialty Polymers Japan Co., Ltd., and the like.

Specific examples of the polyphenylene ether resin include "NORYL SA90" manufactured by SABIC. Specific examples of the polyetherimide resin include "Ultem" manufactured by GE, and the like.

Examples of the polycarbonate resin include hydroxyl-containing carbonate resins, phenolic hydroxyl-containing carbonate resins, carboxyl-containing carbonate resins, acid anhydride group-containing carbonate resins, isocyanate-group-containing carbonate resins, and urethane-containing carbonate resins. resin etc. Specific examples of polycarbonate resins include "FPC0220" manufactured by Mitsubishi Gas Chemicals, "T6002" and "T6001" (polycarbonate diol) manufactured by Asahi Kasei Chemicals, and "C-1090" manufactured by Kuraray Corporation. ", "C-2090", "C-3090" (polycarbonate diol), etc. Specific examples of the polyether ether ketone resin include "Sumiploy K" manufactured by Sumitomo Chemical Co., Ltd., and the like.

Examples of the polyester resin include polyethylene terephthalate resin, polyethylene naphthalate resin, polybutylene terephthalate resin, polybutylene naphthalate resin, polyethylene terephthalate Propylene glycol resin, polytrimethylene naphthalate resin, polycyclohexanedimethyl terephthalate resin, etc.

(e) The weight-average molecular weight (Mw) of the thermoplastic resin is preferably at least 5,000, more preferably at least 8,000, still more preferably at least 10,000, particularly preferably at least 20,000, and most preferably at least 20,000, from the viewpoint of remarkably obtaining the effect of the present invention. It is less than 100,000, more preferably less than 70,000, more preferably less than 60,000, and most preferably less than 50,000.

The content of (e) thermoplastic resin in the resin composition layer is not particularly limited, but when the non-volatile content in the resin composition layer is 100% by mass, it is preferably at most 20% by mass, more preferably at most 10% by mass , more preferably at most 5% by mass, particularly preferably at most 2% by mass. The lower limit of the (e) thermoplastic resin content in the resin composition layer is not particularly limited, but when the non-volatile content in the resin composition layer is 100 mass %, for example, it is 0 mass % or more, preferably 0.001 mass % or more , more preferably at least 0.01% by mass, more preferably at least 0.1% by mass, particularly preferably at least 0.5% by mass.

＜(f) Hardening Accelerator＞ The resin composition layer may further contain (f) a curing accelerator as an optional component. (f) The hardening accelerator has a function as a hardening catalyst which accelerates hardening of (a) epoxy resin.

Examples of the (f) curing accelerator include phosphorus-based curing accelerators, urea-based curing accelerators, guanidine-based curing accelerators, imidazole-based curing accelerators, metal-based curing accelerators, and amine-based curing accelerators. (f) The hardening accelerator preferably includes a hardening accelerator selected from imidazole-based hardening accelerators and amine-based hardening accelerators. (f) The hardening accelerator may be used alone or in combination of two or more.

Examples of phosphorus-based hardening accelerators include tetrabutylphosphonium bromide, tetrabutylphosphonium chloride, tetrabutylphosphonium acetate, tetrabutylphosphonium caprate, tetrabutylphosphonium laurate, bis(tetrabutylphosphonium Phosphonium) pyromellitate, tetrabutylphosphonium hydrogen hexahydrophthalate, tetrabutylphosphonium 2,6-bis(2-hydroxy-5-methylphenyl)methyl]-4-methanol Aliphatic phosphonium salts such as di-tert-butylmethylphosphonium tetraphenylborate; methyltriphenylphosphonium bromide, ethyltriphenylphosphonium bromide, propyltriphenylphosphonium bromide, Butyltriphenylphosphonium bromide, benzyltriphenylphosphonium chloride, tetraphenylphosphonium bromide, p-tolyltriphenylphosphonium-p-tolyl borate, tetraphenylphosphonium tetraphenylborate , tetraphenylphosphonium tetra-p-tolyl borate, triphenylethylphosphonium tetraphenylborate, tris(3-methylphenyl)ethylphosphonium tetraphenylborate, tris(2-methoxy Phenyl)ethylphosphonium tetraphenylborate, (4-methylphenyl)triphenylphosphonium thiocyanate, tetraphenylphosphonium thiocyanate, butyltriphenylphosphonium thiocyanate Aromatic phosphonium salts such as salts; aromatic phosphine‧borane complexes such as triphenylphosphine‧triphenylborane; aromatic phenylphosphine‧quinone additions such as triphenylphosphine‧p-benzoquinone addition reactants Reactants; tributylphosphine, tri-tertiary butylphosphine, trioctylphosphine, di-tertiary butyl (2-butenyl) phosphine, di-tertiary butyl (3-methyl-2- Aliphatic phosphines such as butenyl)phosphine and tricyclohexylphosphine; dibutylphenylphosphine, di-tert-butylphenylphosphine, methyldiphenylphosphine, ethyldiphenylphosphine, butyldiphenylphosphine Phenylphosphine, diphenylcyclohexylphosphine, triphenylphosphine, tri-o-tolylphosphine, tri-m-tolylphosphine, tri-p-tolylphosphine, tri(4-ethylphenyl)phosphine , Tri(4-propylphenyl)phosphine, tri(4-isopropylphenyl)phosphine, tri(4-butylphenyl)phosphine, tri(4-tert-butylphenyl)phosphine, tri( 2,4-Dimethylphenyl)phosphine, Tris(2,5-Dimethylphenyl)phosphine, Tris(2,6-Dimethylphenyl)phosphine, Tris(3,5-Dimethylphenyl)phosphine base)phosphine, tris(2,4,6-trimethylphenyl)phosphine, tris(2,6-dimethyl-4-ethoxyphenyl)phosphine, tris(2-methoxyphenyl) Phosphine, tris(4-methoxyphenyl)phosphine, tris(4-ethoxyphenyl)phosphine, tris(4-tert-butoxyphenyl)phosphine, diphenyl-2-pyridylphosphine, 1,2-bis(diphenylphosphinoyl)ethane, 1,3-bis(diphenylphosphinoyl)propane, 1,4-bis(diphenylphosphinoyl)butane, 1,2 -Aromatic phosphines such as bis(diphenylphosphinoyl)acetylene and 2,2'-bis(diphenylphosphinoyl)diphenyl ether, etc.

Examples of urea-based hardening accelerators include 1,1-dimethylurea; 1,1,3-trimethylurea, 3-ethyl-1,1-dimethylurea, 3-cyclohexyl-1 , 1-dimethyl urea, 3-cyclooctyl-1,1-dimethyl urea and other aliphatic dimethyl urea; 3-phenyl-1,1 dimethyl urea, 3-(4-chloro Phenyl)-1,1-dimethylurea, 3-(3,4-dichlorophenyl)-1,1-dimethylurea, 3-(3-chloro-4-methylphenyl)- 1,1-Dimethylurea, 3-(2-methylphenyl)-1,1-dimethylurea, 3-(4-methylphenyl)-1,1-dimethylurea, 3 -(3,4-Dimethylphenyl)1,1-dimethylurea, 3-(4-isopropylphenyl)-1,1-dimethylurea, 3-(4-methoxy Phenyl)-1,1-dimethylurea, 3-(4-nitrophenyl)-1,1-dimethylurea, 3-[4-(4-methoxyphenoxy)phenyl] -1,1-Dimethylurea, 3-[4-(4-chlorophenoxy)phenyl]-1,1-dimethylurea, 3-[3-(trifluoromethyl)phenyl] -1,1-dimethylurea, N,N-(1,4-phenylene)bis(N',N'-dimethylurea), N,N-(4-methyl-1,3 -Aromatic dimethyl urea, such as phenylene)bis(N',N'-dimethylurea)[toluene bisdimethylurea], etc.

Examples of guanidine hardening accelerators include dicyandiamide, 1-methylguanidine, 1-ethylguanidine, 1-cyclohexylguanidine, 1-phenylguanidine, 1-(o-tolyl)guanidine, Dimethylguanidine, diphenylguanidine, trimethylguanidine, tetramethylguanidine, pentamethylguanidine, 1,5,7-triazabicyclo[4.4.0]dec-5-ene, 7-methyl -1,5,7-Triazabicyclo[4.4.0]dec-5-ene, 1-methylbiguanide, 1-ethylbiguanide, 1-n-butylbiguanide, 1-n-octadecylbiguanide, 1,1-Dimethylbiguanide, 1,1-diethylbiguanide, 1-cyclohexylbiguanide, 1-allylbiguanide, 1-phenylbiguanide, 1-(o-tolyl)biguanide, etc.

Examples of imidazole-based hardening accelerators include 2-methylimidazole, 2-undecylimidazole, 2-heptadecylimidazole, 1,2-dimethylimidazole, 2-ethyl-4-methyl Imidazole, 1,2-dimethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 1-benzyl-2-methylimidazole, 1-Benzyl-2-phenylimidazole, 1-cyanoethyl-2-methylimidazole, 1-cyanoethyl-2-undecylimidazole, 1-cyanoethyl-2-ethyl-4- Methylimidazole, 1-cyanoethyl-2-phenylimidazole, 1-cyanoethyl-2-undecylimidazolium trimellitate, 1-cyanoethyl-2-phenylimidazolium trimellitate Triformate, 2,4-diamino-6-[2'-methylimidazoline-(1')]-ethyl-s-triazine, 2,4-diamino-6-[2' -Undecylimidazoline-(1')]-ethyl-s-triazine, 2,4-diamino-6-[2'-ethyl-4'-methylimidazoline-(1' )]ethyl-s-triazine, 2,4-diamino-6-[2'-methylimidazoline-(1')]ethyl-s-triazine isocyanuric acid adduct, 2- Phenylimidazole isocyanuric acid adduct, 2-phenyl 4,5-dihydroxymethylimidazole, 2-phenyl-4-methyl-5-hydroxymethylimidazole, 2,3-dihydro-1H- Imidazole compounds such as pyrrolo[1.2-a]benzimidazole, 1-dodecyl-2-methyl-3-benzylimidazolium chloride, 2-methylimidazolium, 2-phenylimidazolium, and Adduct of imidazole compound and epoxy resin.

Commercially available products can also be used as the imidazole-based hardening accelerator, for example, "1B2PZ", "2MZA-PW", "2PHZ-PW" manufactured by Shikoku Chemical Industry Co., Ltd., "P200-H50" manufactured by Mitsubishi Chemical Corporation, etc. .

Examples of metal-based hardening accelerators include organometallic complexes or organometallic salts of metals such as cobalt, copper, zinc, iron, nickel, manganese, and tin. Specific examples of organometallic complexes include organocobalt complexes such as cobalt(II) acetylacetonate and cobalt(III) acetylacetonate, and organocopper complexes such as copper(II) acetylacetonate. Organic zinc complexes such as zinc (II) acetylpyruvate, organic iron complexes such as iron (III) acetylpyruvate, organic nickel complexes such as nickel (II) acetylpyruvate , Organomanganese complexes such as manganese (II) acetylpyruvate, etc. Examples of organic metal salts include zinc octylate, tin octylate, zinc naphthenate, cobalt naphthenate, tin stearate, zinc stearate, and the like.

As the amine-based hardening accelerator, for example, trialkylamines such as triethylamine and tributylamine, 4-dimethylaminopyridine, benzyldimethylamine, 2,4,6-heavy (dimethylamine methyl)phenol, 1,8-azabicyclo(5,4,0)-undecene, etc.

A commercial item can also be used as an amine hardening accelerator, For example, "MY-25" by Ajinomoto Fin-Techno Co., Ltd. etc. are mentioned.

The content of the (f) hardening accelerator in the resin composition layer is not particularly limited, but when the non-volatile content in the resin composition layer is 100% by mass, it is preferably 5% by mass or less, more preferably 1% by mass At most, more preferably at most 0.5% by mass, particularly preferably at most 0.2% by mass. The lower limit of the content of the (f) hardening accelerator in the resin composition layer is not particularly limited, but when the non-volatile content in the resin composition layer is 100% by mass, it may be, for example, 0% by mass or more, 0.01% by mass or more, 0.1% by mass or more.

＜(g)Other additives＞ The resin composition of the present invention may further contain arbitrary additives as non-volatile components. Examples of such additives include radical polymerization initiators such as peroxide-based radical polymerization initiators and azo-based radical polymerization initiators; epoxy acrylate resins, urethane acrylate resins, etc. Thermosetting resins other than epoxy resins such as resins, urethane resins, cyanate resins, benzoxazine resins, unsaturated polyester resins, phenol resins, melamine resins, and silicone resins; rubber particles Organic fillers such as organic fillers; organometallic compounds such as organic copper compounds, organic zinc compounds, organic cobalt compounds, etc.; colorants such as phthalocyanine blue, phthalocyanine green, iodine green, diazo yellow, crystal violet, titanium oxide, carbon black, etc.; Polymerization inhibitors of hydroquinone, catechol, pyrogallol, phenothiazine, etc.; leveling agents of silicone-based leveling agents, acrylic polymer-based leveling agents, etc.; of BENTONE, montmorillonite, etc. Thickening agent; defoamer of silicone-based defoamer, acrylic defoamer, fluorine-based defoamer, vinyl resin-based defoamer, etc.; benzotriazole-based UV absorber, etc. UV absorber; Adhesive enhancer for urea silane, etc.; Adhesive imparting agent for triazole-based adhesive, tetrazole-based adhesive, triazine-based adhesive, etc.; hindered phenolic antioxidant Antioxidants such as stilbene derivatives; Fluorescent whitening agents such as stilbene derivatives; Surfactants such as fluorine-based surfactants, silicone-based surfactants, etc.; Phosphonic acid compounds, red phosphorus), nitrogen-based flame retardants (such as melamine sulfate), halogen-based flame retardants, inorganic-based flame retardants (such as antimony trioxide) and other flame retardants; phosphate-based dispersants, poly Dispersants such as oxyalkylene-based dispersants, acetylene-based dispersants, silicone-based dispersants, anionic dispersants, and cationic dispersants; borate-based stabilizers, titanate-based stabilizers, aluminate-based stabilizers stabilizers, zirconate-based stabilizers, isocyanate-based stabilizers, carbonic acid-based stabilizers, carbonic anhydride-based stabilizers, etc. (g) Other additives may be used alone or in combination of two or more in arbitrary ratios. (g) The content of other additives can be appropriately set by those skilled in the art.

＜(h) Organic solvents＞ The resin composition of the present invention may further contain an optional organic solvent as a volatile component in addition to the above-mentioned non-volatile components. As (h) organic solvent, a known one can be used suitably, and the kind is not specifically limited. Examples of (h) organic solvents include ketone-based solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone; methyl acetate, ethyl acetate, butyl acetate, and isobutyl acetate. , isoamyl acetate, methyl propionate, ethyl propionate, γ-butyrolactone and other ester solvents; tetrahydropyran, tetrahydrofuran, 1,4-dioxane, dimethyl ether, diisopropyl ether , dibutyl ether, diphenyl ether, anisole and other ether-based solvents; methanol, ethanol, propanol, butanol, ethylene glycol and other alcohol-based solvents; 2-ethoxyethyl acetate, propylene glycol monomethyl ether Ether ester solvents such as acetate, diethylene glycol monoethyl ether acetate, ethyl diglycol acetate, γ-butyrolactone, methyl methoxypropionate, etc.; methyl lactate, ethyl lactate , 2-hydroxyisobutyrate methyl ester and other ester alcohol solvents; 2-methoxypropanol, 2-methoxyethanol, 2-ethoxyethanol, propylene glycol monomethyl ether, diethylene glycol monobutyl ether Ester alcohol solvents such as (butyl carbitol); Amides such as N,N-dimethylformamide, N,N-dimethylacetamide, N-methyl-2-pyrrolidone, etc. Solvents; Arthrine-based solvents such as dimethylsulfide; Nitrile-based solvents such as acetonitrile and propionitrile; Aliphatic hydrocarbon-based solvents such as hexane, cyclopentane, cyclohexane, and methylcyclohexane; Benzene , Toluene, xylene, ethylbenzene, trimethylbenzene and other aromatic hydrocarbon solvents. (h) The organic solvent may be used individually by 1 type, and may use it combining 2 or more types by arbitrary ratios.

The content of (h) organic solvent in the resin composition layer after drying is not particularly limited, but when all components in the resin composition layer are taken as 100% by mass, it is preferably 5% by mass or less, more preferably 3% by mass % or less, more preferably less than 2 mass %, particularly preferably less than 1 mass %.

＜Semiconductor Devices＞ A semiconductor device including a printed wiring board can be manufactured using the printed wiring board obtained by the manufacturing method of the present invention.

Examples of semiconductor devices include various semiconductor devices used in electrical products (such as computers, mobile phones, digital cameras, and televisions, etc.) and vehicles (such as locomotives, automobiles, trains, ships, and airplanes, etc.).

A semiconductor device can be manufactured by mounting components (semiconductor chips) on the conduction portion of a printed wiring board. The so-called conductive part refers to the part that transmits electrical signals in the printed wiring board, and its position can be either the surface or the embedded part. Also, the semiconductor wafer is not particularly limited as long as it is an electronic circuit element made of a semiconductor.

The mounting method of the semiconductor chip in the manufacture of a semiconductor device is not particularly limited as long as the semiconductor chip can effectively function. Specifically, examples include a wire bonding mounting method, a flip chip mounting method, and a bumpless build-up method. (BBUL) mounting method, mounting method using anisotropic conductive film (ACF), mounting method of non-conductive film (NCF), etc. [Example]

Hereinafter, the present invention will be specifically described by way of examples. The present invention is not limited to these examples. In addition, in the following, "parts" and "%" indicating amounts mean "parts by mass" and "% by mass", respectively, unless otherwise specified. The temperature conditions in the following descriptions are at normal temperature (25°C) unless otherwise specified, and the pressure conditions are at normal pressure (0.1MPa) unless otherwise specified

＜Production example A: Production of resin sheet A＞ 5 parts of biphenyl arane type epoxy resin ("NC-3000H" manufactured by Nippon Kayaku Co., Ltd., epoxy equivalent is about 271g/eq.), naphthalene type epoxy resin ("HP403SS" manufactured by DIC Corporation, epoxy equivalent About 145g/eq.) 10 parts, bisphenol A type epoxy resin and bisphenol F epoxy mixture ("ZX1059" manufactured by Nippon Steel Chemical and Material Co., Ltd., epoxy equivalent 165g/eq.) 5 parts, active ester Curing agent ("HPC-8150-62T" manufactured by DIC Corporation, toluene solution with an active group equivalent of about 229 g/eq. and a solid content of 61.5% by mass) 30 parts, phenolic curing agent ("LA-3018-50P" manufactured by DIC Corporation) , active group equivalent of about 151, 50% solid content of 2-methoxypropanol solution) 5 parts, phenoxy resin ("YX7553BH30" manufactured by Mitsubishi Chemical Corporation, solid content of 30% by mass MEK and 1 of cyclohexanone: 1 solution) 5 parts, 4-dimethylaminopyridine (MEK solution with a solid content of 5% by mass) 4 parts, MEK 30 parts, and surface treatment with an amine-based alkoxysilane compound ("KBM573" manufactured by Shin-Etsu Chemical Co., Ltd.) 80 parts of treated spherical silicon oxide ("SO-C2" manufactured by ADMATECHS Co., Ltd., average particle size: 0.5 μm) were uniformly dispersed using a mixer to obtain a varnish-like resin composition.

The obtained varnish-like resin composition was uniformly coated on a PET film ("AL5" manufactured by Lintec Co., Ltd., thickness 38 μm) with a die coater so that the thickness after drying was 25 μm. average 100° C.) for 4 minutes to obtain a resin sheet A.

＜Production example B: Production of resin sheet B＞ Except that the amount of spherical silicon oxide ("SO-C2" manufactured by ADMATECHS, average particle size 0.5 μm) surface-treated with an amine-based alkoxysilane compound ("KBM573" manufactured by Shin-Etsu Chemical Co., Ltd.) was changed from 80 parts Changed to 120 parts, instead of 30 parts of active ester hardener ("HPC-8150-62T" manufactured by DIC Corporation), active ester hardener ("HPC-8000-65T" manufactured by DIC Corporation, active group equivalent of about 223g /eq., except for 30 parts of toluene solution with a solid content of 65% by mass, resin sheet B was produced in the same manner as Production Example A.

＜Production example C: Production of resin sheet C＞ Except that the amount of spherical silicon oxide ("SO-C2" manufactured by ADMATECHS, average particle size 0.5 μm) surface-treated with an amine-based alkoxysilane compound ("KBM573" manufactured by Shin-Etsu Chemical Co., Ltd.) was changed from 80 parts Resin sheet C was produced in the same manner as Production Example A except that the amount of active ester-based hardener ("HPC-8150-62T" manufactured by DIC Corporation) was changed from 30 parts to 45 parts, except that it was changed to 60 parts.

＜Production example D: Production of resin sheet D＞ Except that the amount of spherical silicon oxide ("SO-C2" manufactured by ADMATECHS, average particle size 0.5 μm) surface-treated with an amine-based alkoxysilane compound ("KBM573" manufactured by Shin-Etsu Chemical Co., Ltd.) was changed from 80 parts Change to 100 parts, change the usage amount of active ester hardener ("HPC-8150-62T" manufactured by DIC Corporation) from 30 parts to 45 parts, and further use carbodiimide hardener (manufactured by Nisshinbo Chemical Co., Ltd. "V-03", active group equivalent of about 216g/eq., non-volatile matter 50 mass% toluene solution) except 5 parts, the resin sheet D was produced in the same manner as in production example A.

＜Production Example E: Production of Resin Sheet E＞ Except that the amount of spherical silicon oxide ("SO-C2" manufactured by ADMATECHS, average particle size 0.5 μm) surface-treated with an amine-based alkoxysilane compound ("KBM573" manufactured by Shin-Etsu Chemical Co., Ltd.) was changed from 80 parts Change to 140 parts, change the amount of phenolic hardener ("LA-3018-50P" manufactured by DIC Corporation) from 5 parts to 10 parts, and further use oligophenylene ether‧styrene resin (manufactured by Mitsubishi Gas Chemical Co., Ltd. Resin sheet E was prepared in the same manner as in Production Example A except for "OPE-2St 1200", 15 parts of toluene solution with a solid content of 65% by mass.

＜Production example F: Production of resin sheet F＞ Except that the amount of spherical silicon oxide ("SO-C2" manufactured by ADMATECHS, average particle size 0.5 μm) surface-treated with an amine-based alkoxysilane compound ("KBM573" manufactured by Shin-Etsu Chemical Co., Ltd.) was changed from 80 parts Changed to 140 parts, changed the amount of active ester hardener ("HPC-8150-62T" manufactured by DIC Corporation) from 30 parts to 25 parts, and did not use phenolic hardener ("LA-3018-50P" manufactured by DIC Corporation) ”), and then use 15 parts of bisphenol A dicyanate (manufactured by Japan LONZA Company) BA230S75”, the cyanate equivalent is about 232g/eq., and the MEK solution with a solid content of 75% by mass) to mix 4-dimethylamino The amount of pyridine (MEK solution with a solid content of 5% by mass) was changed from 4 parts to 2 parts, and 1-benzyl-2-phenylimidazole (MEK solution with a solid content of 5% by mass) was used in addition to 2 parts, and Resin sheet F was produced in the same manner as production example A.

＜Production example G: Production of resin sheet G＞ Except that the amount of spherical silicon oxide ("SO-C2" manufactured by ADMATECHS, average particle size 0.5 μm) surface-treated with an amine-based alkoxysilane compound ("KBM573" manufactured by Shin-Etsu Chemical Co., Ltd.) was changed from 80 parts Changed to 120 parts, no active ester hardener ("HPC-8150-62T" manufactured by DIC Corporation), no phenolic hardener ("LA-3018-50P" manufactured by DIC Corporation), and bisphenol A bisphenol A 30 parts of cyanate ("BA230S75" produced by Japan LONZA Co., Ltd., cyanate equivalent of about 232g/eq., solid content of 75 mass% MEK solution) to replace 4-dimethylaminopyridine (solid content of 5 mass% Resin sheet G was produced in the same manner as Production Example A except that 4 parts of MEK solution) and 4 parts of 1-benzyl-2-phenylimidazole (MEK solution with a solid content of 5% by mass) were used.

＜Production example H: Production of resin sheet H＞ In addition to not using an active ester hardener ("HPC-8150-62T" manufactured by DIC Corporation), a phenolic hardener ("LA-3018-50P" manufactured by DIC Corporation) is not used, and a phenolic novolak type polyfunctional cyanic acid is used 25 parts of ester resin ("PT30" produced by LONZA Co., Ltd. in Japan, hydroester equivalent about 124 g/eq., MEK solution with 80 mass % solid content) to replace 4-dimethylaminopyridine (MEK solution with 5 mass % solid content) ) and 4 parts of 1-benzyl-2-phenylimidazole (MEK solution with a solid content of 5% by mass) was used, and the resin sheet H was produced in the same manner as in Production Example A.

The amount of raw materials used and the amount of non-volatile components used to obtain the varnish-like resin composition in the production examples are summarized in Table 1 below.

<Example 1> (Steps of preparing the inner layer substrate laminated with resin sheets) A glass cloth substrate with copper layers on both surfaces was prepared as an inner layer substrate with epoxy resin double-sided copper-clad laminate (copper layer thickness 18 μm, substrate thickness 0.8 mm, Panasonic Electric Works Co., Ltd. "R1515A"). Roughen the surface of the copper layer by immersing both sides of the inner layer substrate in "CZ8100" manufactured by MEC Corporation.

The resin sheet A produced in Production Example A was laminated on both sides of the roughened inner-layer substrate in such a manner that the resin composition layer and the inner-layer substrate were bonded. The lamination system uses a vacuum pressurized laminator MVLP-500 manufactured by Meiji Co., Ltd., after vacuum suction at a temperature of 100°C for 30 seconds, by using a temperature of 100°C and a pressure of 7.0Kg/cm ² , from the PET film , Pressurized for 30 seconds through heat-resistant rubber. Next, under atmospheric pressure, using a SUS mirror plate, pressurize for 60 seconds at a temperature of 100°C and a pressure of 5.5kg/cm ² to fabricate an inner substrate laminated with a resin sheet.

(Step of forming insulating layer) The inner substrate laminated with the resin sheet is heated at 130°C for 30 minutes (preheating condition) in the state of the support body, and then heated at 180°C for 30 minutes (thermal curing condition) without returning to room temperature. The resin composition layer was thermally cured and returned to room temperature (25° C.) to form an insulating layer to obtain a laminate. The maximum thickness of the obtained insulator (the distance from the interface between the copper layer and the insulating layer of the inner substrate to the interface between the insulating layer and the support) was 25 μm. Return to room temperature (25°C) after thermal hardening.

(Step of opening holes in the insulating layer) After the insulating layer is formed, use a CO ₂ laser processing machine ("LC-K212" manufactured by HITACHI Co., Ltd. ), under the conditions of power: 1.35W, number of shots: 2, target hole top diameter: 30μm, and process more than 3 parts. Thereby, a plurality of through holes opening on the circuit conductors of the inner substrate are formed, which are substantially circular in plan view and rectangular in cross-section, and the conductor layer of the inner substrate is exposed on the bottom surface of each through hole.

(Step of heat-treating the insulating layer at T ₂ (°C)) After the step of opening holes by laser, heat at a temperature of 130°C (T ₂ ) in air at normal pressure (0.1 MPa) for 30 minutes Heat treatment (annealing treatment) under the same conditions. Then, return to room temperature (25° C.), and remove the support.

(Step of desmearing treatment with oxidant solution) Immerse the surface of the insulating layer in Swelling Dip Securiganth P manufactured by ATOTECH Corporation of Japan at 80°C for 10 minutes, then dip in Concentrate Compact CP manufactured by ATOTECH Corporation of Japan at 80°C for 20 minutes, and finally, at 40°C Soak for 5 minutes in Reduction solution Securiganth P manufactured by Japan ATOTECH Co., Ltd. in a neutralizing solution. Then, it dried at 80 degreeC for 30 minutes, and produced the evaluation board|substrate.

<Example 2> The resin sheet-laminated inner substrate produced in the same manner as in Example 1 was heated at 130°C for 30 minutes (preparatory heating conditions) in the state of attaching a support, and then returned to room temperature (25 ℃). Then, with the support attached, a CO ₂ laser processing machine ("LC-K212" manufactured by HITACHI Co., Ltd.) was used for the resin composition layer located on one of the main surfaces of the laminate. Power: 1.35W, number of shots : 2 and the target hole top diameter: 30μm, the hole processing is carried out over more than 10 parts. In this way, a plurality of through holes opening on the circuit conductors of the inner substrate are formed, which are approximately circular in plan view and rectangular in cross-section, and the conductor layer of the inner substrate is exposed on the bottom surface of each through hole. Subsequently, the resin sheet-laminated inner substrate having through holes was heated at 170° C. for 30 minutes (thermosetting conditions) to thermoset the resin composition layer to form an insulating layer to obtain a laminate. Subsequently, heat treatment (annealing treatment) was carried out under the conditions of heat treatment temperature of 130°C (T ₂ ) and heat treatment time of 30 minutes in air at normal pressure, and then returned to room temperature (25°C), and the support body was removed to be compatible with Under the same conditions as in Example 1, desmearing treatment was performed on the surface of the insulating layer to produce an evaluation substrate.

<Example 3> The resin sheet B produced in Production Example B was used instead of the resin sheet A, and the heat treatment temperature (T ₂ ) in the heat treatment (annealing treatment) was changed from 130°C to 115°C, in order to be the same as in Example 1 In the same way, the evaluation substrate was produced.

<Example 4> Using the resin sheet C produced in Production Example C instead of the resin sheet A, the heat treatment temperature (T ₂ ) in the heat treatment (annealing treatment) was changed from 130°C to 115°C, and the heat treatment time was changed from Instead of changing 30 minutes to 60 minutes, an evaluation substrate was produced in the same manner as in Example 1.

<Example 5> The resin sheet D produced in Production Example D was used instead of resin sheet A, and the heat treatment temperature (T ₂ ) in the heat treatment (annealing treatment) was changed from 130°C to 140°C, so as to be the same as in Example 1 In the same way, the evaluation substrate was produced.

<Example 6> The resin sheet E prepared in Production Example E was used instead of the resin sheet A, and the heat treatment temperature (T ₂ ) in the heat treatment (annealing treatment) was changed from 130°C to 120°C, so as to be the same as in Example 1 In the same way, the evaluation substrate was produced.

<Example 7> The resin sheet F produced in Production Example F was used instead of the resin sheet A, and the heat treatment temperature (T ₂ ) in the heat treatment (annealing treatment) was changed from 130°C to 145°C, so as to be the same as in Example 1 In the same way, the evaluation substrate was produced.

＜Comparative example 1＞ An evaluation substrate was produced in the same manner as in Example 1, except that desmearing was performed without heat treatment (annealing treatment) after the step of opening holes in the insulating layer.

<Comparative Example 2> An evaluation substrate was produced in the same manner as in Example 1 except that the heat treatment temperature (T ₂ ) in the heat treatment (annealing treatment) was changed from 130°C to 80°C.

<Comparative example 3> Except having changed the heat processing temperature ( _T2 ) in heat processing (annealing process) from 130 degreeC to 150 degreeC, it carried out similarly to Example 1, and produced the evaluation board|substrate.

<Comparative Example 4> The resin sheet G produced in Production Example G was used instead of the resin sheet A, and the heat treatment temperature (T ₂ ) in the heat treatment (annealing treatment) was changed from 130°C to 150°C, so as to be the same as in Example 1 In the same way, the evaluation substrate was produced.

<Comparative Example 5> The resin sheet H produced in Production Example H was used instead of the resin sheet A, and the heat treatment temperature (T ₂ ) in the heat treatment (annealing treatment) was changed from 130°C to 170°C, so as to be the same as in Example 1 In the same way, the evaluation substrate was produced.

<Test Example 1: Measurement of the glass transition temperature (T ₁ ) of the insulating layer> The resin sheets A~H produced in each production example were thermally cured under the preheating conditions and thermosetting conditions corresponding to the examples and comparative examples to obtain sample. A model DMS-6100 manufactured by Seiko Instruments was used as a thermomechanical analyzer (DMA), and the sample was measured in the "tensile mode". The measurement is carried out at a temperature increase of 2°C/min in the range of 25°C~240°C. The maximum value of the loss tangent factor (tanδ) calculated from the ratio of the measured storage elastic modulus (E') to the loss elastic modulus (E'') is the value rounded to the first decimal place as the insulating layer of glass Transition temperature (T ₁ ).

<Test Example 2: Evaluation of Cracks> Cracks (via hole cracks) were evaluated using a scanning electron microscope (manufactured by Hitachi-Hightech Co., Ltd., S-4800) for the surface layer around the via hole in the evaluation substrate produced in each Example and Comparative Example. Whether or not cracks occurred in the surface layer around the 100 through-holes was confirmed, the ratio of no cracks (cracks) was calculated, and the following evaluation criteria were used for evaluation.

Evaluation benchmark "○": When the number of cracks (number of cracks) is less than 20 "×": When the number of cracks (number of cracks) is 20 or more

Table 2 below summarizes the production methods of the resin sheets and evaluation substrates used in each of the examples and comparative examples, the measurement results and evaluation results of each test example.

time of opening "I": (A-32) after step (A-4) before step "II": (A-31) after step (A-32) before step

As shown in Table ₂ , it is known that active ester hardener is used in the formation of the insulating layer. Heat treatment at temperature T ₂ (°C) can suppress the occurrence of cracks after desmearing treatment (roughening treatment).

Claims (18)

A method of manufacturing a printed wiring board, which sequentially includes the following steps: (A) thermosetting a resin composition layer of a laminate including an inner substrate and a resin composition layer bonded to the inner substrate to form a glass The step of transferring the insulating layer at T ₁ (°C), (B) the step of heat-treating the insulating layer at T ₂ (°C), and (C) the step of desmearing the insulating layer with an oxidant solution, resin composition The material layer includes epoxy resin and active ester hardener, and satisfies the following formulas (1) and (2) at the same time, -20≦T ₁ -T ₂ ≦20 (1) 60≦T ₂ ≦150 (2). The method for manufacturing a printed wiring board according to claim 1, wherein the step (A) includes the following steps in sequence: (A-1) The step of preparing a resin sheet having a support and a resin composition layer provided on the support , (A-2) a step of laminating resin sheets in such a way that the resin composition layer and the inner substrate are bonded to obtain a laminate, and (A-3) thermosetting the resin composition layer to form a glass transition temperature T ₁ (°C) step of insulating layer. The method of manufacturing a printed wiring board according to claim 2, wherein the step (A-3) includes the following steps in sequence: (A-31) preheating the resin composition layer at a preliminary heating temperature lower than the curing heating temperature step, and (A-32) heating the resin composition layer at a curing heating temperature to thermally harden the resin composition layer to form an insulating layer having a glass transition temperature of T ₁ (°C). The method of manufacturing a printed wiring board as claimed in item 3, wherein the hardening heating temperature is 150°C to 210°C, and the preliminary heating temperature is 100°C to 150°C. The method for manufacturing a printed wiring board as in claim 2, wherein step (A) is after step (A-3), and further includes the following steps: (A-4) A step of cooling the insulating layer to 30°C or lower. The method for manufacturing a printed wiring board as in claim 1, wherein step (A) further includes the following steps: (A-5) A step of opening holes in the insulating layer or the resin composition layer. The method of manufacturing a printed wiring board according to Claim 6, wherein the step (A-5) is implemented using a laser. The method of manufacturing a printed wiring board according to Claim 6, wherein the holes formed in the step (A-5) include holes with a top diameter of 100 μm or less. The method of manufacturing a printed wiring board according to claim 1, wherein the heat treatment time in step (B) is 10 minutes or more. The method of manufacturing a printed wiring board according to claim 1, wherein the heat treatment in step (B) is performed by heating the insulating layer in a gas environment. The method of manufacturing a printed wiring board according to claim 1, further comprising (D) the step of forming a conductor layer on the surface of the insulating layer after the step (C). The method of manufacturing a printed wiring board according to Claim 1, wherein T ₂ (°C) is 100 (°C) or higher. The method of manufacturing a printed wiring board according to claim 1, wherein T ₁ -T ₂ (°C) is -5(°C)~10(°C). The method of manufacturing a printed wiring board according to Claim 1, wherein the resin composition layer further contains an inorganic filler. The method of manufacturing a printed wiring board according to claim 14, wherein the content of the inorganic filler is 50% by mass or more when the non-volatile content in the resin composition layer is 100% by mass. The method of manufacturing a printed wiring board according to claim 1, wherein the resin composition layer further includes a phenoxy resin. The method of manufacturing a printed wiring board according to claim 1, wherein the resin composition layer further contains a radically polymerizable compound. The method of manufacturing a printed wiring board according to claim 1, wherein the resin composition layer further contains a cyanate-based hardener.