JP2022151212A - 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).SOLUTION: 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(°C), (B) performing a heat treatment on the insulator layer at T2(°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).SELECTED DRAWING: None

Description

The present invention relates to a method for manufacturing a printed wiring board.

As a manufacturing technique for multilayer printed wiring boards, a manufacturing method using a build-up method in which insulating layers and conductor layers are alternately stacked on an inner layer substrate is known. An insulating layer is generally formed by curing a resin composition. For example, Patent Document 1 discloses forming an insulating layer in a printed wiring board using a resin composition containing a cyanate ester resin, a specific epoxy resin, and an active ester curing agent.

JP 2011-144361 A

2. Description of the Related Art In recent years, the size reduction of electronic devices and electronic components has become remarkable, and along with this, it is required to make the insulating layer of a printed wiring board thinner in order to make the printed wiring board thinner.

However, when the insulating layer is made thinner, cracks along the lower layer copper shape such as wiring and pads in the inner layer board after the desmear treatment (roughening treatment) process in the printed wiring board process, and holes made by laser etc. It is known that the occurrence of cracks, that is, the occurrence of cracks in the periphery of the

An object of the present invention is to provide a method for manufacturing a printed wiring board that can suppress the occurrence of cracks after desmearing (roughening treatment).

In order to achieve the object of the present invention, the present inventors conducted intensive studies and found that an active ester curing agent was used to form the insulating layer, and after the insulating layer was formed, the insulating layer was formed at a temperature near its glass transition temperature T ₁ (°C). The inventors have found that heat treatment at a temperature T ₂ (° C.) within ±20° C. can suppress the occurrence of cracks after desmearing (roughening treatment), leading to the completion of the present invention.

That is, the present invention includes the following contents.
[1] (A) An insulating layer having a glass transition temperature of T ₁ (° C.) is formed by thermally curing a resin composition layer of a laminate comprising an inner layer substrate and a resin composition layer bonded to the inner layer substrate. forming,
(B) heat-treating the insulating layer at T ₂ (°C); and (C) desmearing the insulating layer with an oxidant solution in this order,
A method for producing a printed wiring board, wherein the resin composition layer contains an epoxy resin and an active ester curing agent, and satisfies both the following formulas (1) and (2).
−20≦T ₁ −T ₂ ≦20 (1)
60≦T ₂ ≦150 (2)
[2] (A) step
(A-1) a step of preparing a resin sheet comprising a support and a resin composition layer provided on the support;
(A-2) a step of laminating resin sheets so that the resin composition layer is bonded to the inner layer substrate to obtain a laminate, and (A-3) thermosetting the resin composition layer so that the glass transition temperature is T ₁ (° C.) in this order, the printed wiring board manufacturing method according to [1] above.
[3] (A-3) step
(A-31) preheating the resin composition layer at a preheating temperature lower than the curing heating temperature; and (A-32) heating the resin composition layer at the curing heating temperature to form a resin composition layer. to form an insulating layer having a glass transition temperature of T ₁ (° C.) in this order.
[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 preheating temperature is 100°C to 150°C.
[5] (A) step is, after (A-3) step,
(A-4) The method for producing a printed wiring board according to any one of [2] to [4] above, further comprising the step of cooling the insulating layer to 30° C. or lower.
[6] (A) step
(A-5) The method for producing a printed wiring board according to any one of [1] to [5] above, further comprising the step of perforating the insulating layer or the resin composition layer.
[7] The method for producing a printed wiring board according to [6] above, wherein step (A-5) is performed using a laser.
[8] The method for producing a printed wiring board according to [6] or [7] above, wherein the holes formed in the step (A-5) include holes with 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 step (B) is 10 minutes or longer.
[10] The method for producing a printed wiring board according to any one of [1] to [9] above, wherein the heat treatment in 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 comprising (D) 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 component in the resin composition layer is taken as 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 radically 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 ester curing agent.

ADVANTAGE OF THE INVENTION 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.

BEST MODE FOR CARRYING OUT THE INVENTION The present invention will now be described in detail with reference to its preferred embodiments. However, the present invention is not limited to the following embodiments and examples, and can be arbitrarily modified without departing from the scope of the claims of the present invention and their equivalents.

<Method for manufacturing printed wiring board>
The printed wiring board manufacturing method of the present invention comprises:
(A) A step of thermally curing a resin composition layer of a laminate comprising an inner layer substrate and a resin composition layer bonded to the inner layer substrate to form an insulating layer having a glass transition temperature of T ₁ (° C.). ,
(B) heat-treating the insulating layer at T ₂ (°C); and (C) desmearing the insulating layer with an oxidant solution in this order,
The resin composition layer contains an epoxy resin and an active ester curing agent, and satisfies both the following formulas (1) and (2).
−20≦T ₁ −T ₂ ≦20 (1)
60≦T ₂ ≦150 (2)
Here, "≦" indicates that the left numerical value is less than or equal to the right numerical value.

According to such a manufacturing method, it is possible to suppress the occurrence of cracks after the desmear treatment (roughening treatment). After forming the insulating layer, the insulating layer is heat-treated at _a temperature T2 (°C) in the vicinity of its glass transition temperature T1 ₍ °C) (within ±20°C), whereby the resin composition layer is thermally cured to provide insulation. It is presumed that this is due to the gradual relaxation of the stress accumulated inside the layer.

Each step in the method for manufacturing a printed wiring board of the present invention will be described below.

<(A) Process>
In the step (A), a resin composition layer of a laminate comprising an inner layer substrate and a resin composition layer bonded to the inner layer substrate is thermally cured to form an insulating layer having a glass transition temperature of T ₁ (° C.). Form.

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

In step (A-1), a resin sheet comprising a support and a resin composition layer provided on the support is prepared.

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

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

Examples of the support used for the resin sheet include a film made of a plastic material, a metal foil, and a release paper, and a film made of a plastic material and a metal foil are preferable.

When a film made of a plastic material is used as the support, examples of the plastic material include polyethylene terephthalate (hereinafter sometimes abbreviated as "PET") and polyethylene naphthalate (hereinafter sometimes abbreviated as "PEN"). ), polycarbonate (hereinafter sometimes abbreviated as "PC"), acrylic such as polymethyl methacrylate (PMMA), cyclic polyolefin, triacetyl cellulose (TAC), polyether sulfide (PES), polyether ketones, polyimides, and the like. Among them, polyethylene terephthalate and polyethylene naphthalate are preferable, and inexpensive polyethylene terephthalate is particularly preferable.

When a metal foil is used as the support, examples of the metal foil include copper foil and aluminum foil, with copper foil being preferred. As the copper foil, a foil made of a single metal of copper may be used, and a foil made of an alloy of copper and other metals (for example, tin, chromium, silver, magnesium, nickel, zirconium, silicon, titanium, etc.) may be used. may be used.

The support may be subjected to matte treatment, corona treatment, or antistatic treatment on the surface to be bonded to the resin composition layer.

Further, as the support, a support with a release layer having a release layer on the surface to be bonded to the resin composition layer may be used. The release agent used in the release layer of the release layer-attached support includes, for example, one or more release agents selected from the group consisting of alkyd resins, polyolefin resins, urethane resins, and silicone resins. . As the support with a release layer, a commercially available product may be used, for example, "SK-1" manufactured by Lintec Co., Ltd., "SK-1", " AL-5", "AL-7", Toray's "Lumirror T60", Teijin's "Purex", and Unitika's "Unipeel".

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. When a release layer-attached support is used, the thickness of the release layer-attached support as a whole is preferably within the above range.

In the resin sheet, a protective film conforming to the support may 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). Although the thickness of the protective film is not particularly limited, it is, for example, 1 μm to 40 μm. By laminating the protective film, it is possible to prevent dust from adhering to the surface of the resin composition layer and scratches on the surface of the resin composition layer. Such a resin sheet can be wound into a roll and stored. When the resin sheet has a protective film, the protective film is peeled off before lamination on the inner layer substrate.

In the step (A-2), resin sheets are laminated such that the resin composition layer is bonded to the inner layer substrate to obtain a laminate.

The inner layer substrate is a member that becomes the substrate of the printed wiring board, and examples thereof include glass epoxy substrates, metal substrates, polyester substrates, polyimide substrates, BT resin substrates, thermosetting polyphenylene ether substrates, and the like. The substrate may also have a conductor layer on one or both sides thereof, and the conductor layer may be patterned. The inner layer board also includes an intermediate product on which an insulating layer and/or a conductor layer are to be further formed when manufacturing the printed wiring board. When the printed wiring board is a circuit board with built-in components, an inner layer board with built-in components can be used.

A resin sheet is laminated on the inner layer substrate so that the resin composition layer is bonded to the inner layer 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 thermocompression bonding the resin sheet to the inner layer substrate from the support side. Examples of the member for thermocompression bonding the resin sheet to the inner layer substrate (hereinafter also referred to as "thermocompression bonding member") include heated metal plates (such as SUS end plates) and metal rolls (SUS rolls). Instead of pressing the thermocompression member directly onto the resin sheet, it is preferable to press through an elastic material such as heat-resistant rubber so that the resin sheet can sufficiently follow the uneven surface of the inner layer substrate.

Lamination of the inner layer substrate and the resin sheet may be performed by a vacuum lamination method. In the vacuum lamination method, the thermocompression temperature is preferably in the range of 60° C. to 160° C., more preferably 80° C. to 140° C., and the thermocompression pressure is preferably 0.098 MPa to 1.77 MPa, more preferably 0. 0.29 MPa to 1.47 MPa, and the heat pressing time is preferably 10 seconds to 400 seconds, more preferably 20 seconds to 300 seconds.

Lamination can be done with a commercially available vacuum laminator. Commercially available vacuum laminators include, for example, a vacuum pressurized laminator manufactured by Meiki Seisakusho, a vacuum applicator manufactured by Nikko Materials, a batch vacuum pressurized laminator, and the like.

After lamination, the laminated resin sheets may be smoothed under normal pressure (atmospheric pressure), for example, by pressing a thermocompression member from the support side. The pressing conditions for the smoothing treatment may be the same as the thermocompression bonding conditions for the lamination described above. Smoothing treatment can be performed with a commercially available laminator. Lamination and smoothing may be performed continuously using the above-mentioned commercially available vacuum laminator.

In step (A-3), the resin composition layer is thermally cured to form an insulating layer having a glass transition temperature of T ₁ (° C.).

The heating temperature for curing the resin composition layer varies depending on the type of the resin composition and the like, but is preferably 100° C. or higher, more preferably 150° C. or higher, and still more preferably 160° C. or higher. The upper limit is preferably 220° C. or lower, more preferably 210° C. or lower, and even more preferably 200° C. or lower.

The curing heating time of the resin composition layer varies depending on the type of resin composition, etc., but is preferably 5 minutes or longer, more preferably 10 minutes or longer, and still more preferably 15 minutes or longer, and the upper limit is particularly limited. However, it is preferably 120 minutes or less, more preferably 100 minutes or less, and still 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 curing is usually performed in a gas (eg, air, argon gas, nitrogen gas, or mixed gas thereof) atmosphere, for example, under a pressure of 0.05 MPa to 0.15 MPa, preferably 0.08 to 0.12 MPa. done.

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

The preheating temperature of the resin composition layer is preferably 50° C. or higher, more preferably 100° C. or higher, still more preferably 120° C. or higher, and preferably 160° C. or lower, more preferably 150° C. or lower, further preferably 140° C. ℃ or less. The preheating time of the resin composition layer is preferably 5 minutes or longer, more preferably 10 minutes or longer, still more preferably 15 minutes or longer, preferably 150 minutes or shorter, more preferably 130 minutes or shorter, and still more preferably 120 minutes. minutes or less. Preheating is usually performed in a gas (eg, air, argon gas, nitrogen gas, or mixed gas thereof) atmosphere, for example, under a pressure of 0.05 MPa to 0.15 MPa, preferably 0.08 to 0.12 MPa. done.

From the viewpoint of heat resistance of the insulating layer, 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, further preferably 80 (°C). ) or higher, still more preferably 90 (°C) or higher, even more preferably 100 (°C) or higher, and particularly preferably 110 (°C) or higher, and the upper limit is not particularly limited, but is preferably 160 (°C) or lower. , more preferably 150 (° C.) or less.

Between the step (A-31) and the step (A-32), the heating may be performed continuously without returning to room temperature (preferably, the temperature is raised as it is from the preheating temperature to the curing heating temperature). Alternatively, after the step of (A-31) and before the step of (A-32), a step of (A-33) cooling the insulating layer to 30° C. or less may be included. The cooling temperature in step (A-33) is preferably 10°C to 30°C, more preferably 20°C to 30°C. The method of cooling is not particularly limited, and the insulating layer may be allowed to cool, a method of blowing cold air against the insulating layer, a method of pressing the insulating layer against a cooled roll, or the like. (A-33) The cooling in the step is usually performed in a gas (eg, air, argon gas, nitrogen gas, or mixed gas thereof) atmosphere, for example, 0.05 MPa to 0.15 MPa, preferably 0.08 to 0.08 MPa. under a pressure of 0.12 MPa.

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, It is more preferably 60 µm or less, particularly preferably 50 µm or less, and although the lower limit is not particularly limited, it can usually be 1 µm or more, 5 µm or more, or 10 µm or more.

The step (A) preferably further includes the step of (A-4) cooling the insulating layer to 30° C. or lower after the step (A-3).

By performing the step (A-4), it is possible to suppress excessive stress caused by thermosetting of the resin composition. Therefore, in the step (B), the residual stress in the insulating layer can be further suppressed, and the occurrence of cracks can be effectively suppressed. The cooling temperature in step (A-4) is preferably 10°C to 30°C, more preferably 20°C to 30°C. The method of cooling is not particularly limited, and the insulating layer may be allowed to cool, a method of blowing cold air against the insulating layer, a method of pressing the insulating layer against a cooled roll, or the like. Cooling in step (A-4) is usually carried out in a gas (eg, air, argon gas, nitrogen gas, or mixed gas thereof) atmosphere, for example, 0.05 MPa to 0.15 MPa, preferably 0.08 to 0.08 MPa. under a pressure of 0.12 MPa.

The step (A) preferably further includes (A-5) a step of perforating the insulating layer or the resin composition layer. (A-5) step, for example, after (A-31) step (but preferably after (A-33) step if (A-33) step is included) (A-32) before step, or ( It may be included after step A-3) (however, if step (A-4) is included, preferably after step (A-4)).

The step (A-5) may be carried out according to various methods known to those skilled in the art that are used for manufacturing printed wiring boards. Through the step (A-5), via holes and through holes can be formed in the insulating layer (resin composition layer). The step (A-5) can be performed using, for example, a drill, laser (CO ₂ (carbon dioxide gas) laser, YAG laser, etc.), plasma, or the like. (A-5) step is preferably performed using a laser.

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

<(B) step>
In the step (B), the insulating layer is heat-treated at T ₂ (°C). By performing the step (B), it is possible to suppress the occurrence of cracks after the step (C). It is presumed that this is because the stress dependent on the pattern shape of the inner layer substrate can be relaxed.

The heat treatment temperature (T ₂ ) in the step (B) is preferably lower than the heating temperature for curing the resin composition layer in the step (A). The heat treatment temperature (T ₂ ) is 60 (° C.) or higher and 150 (° C.) or lower, preferably 70 (° C.) or higher, more preferably 80 (° C.) or higher, from the viewpoint of further suppressing the occurrence of cracks. , more preferably 90 (°C) or higher, and 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 20 (° C.) or less, preferably 15 (° C.) or less, more preferably 15 (° C.) or less. 10 (° C.) or less, particularly preferably 5 (° C.) or less, and the lower limit of T ₁ −T ₂ is −20 (° C.) or more, preferably −15 (° C.) or more, more preferably −10 ( ° C.) or higher, more preferably −5 (° C.) or higher, and particularly preferably 0 (° C.) or higher.

The heat treatment time in the step (B) is preferably 1 minute or longer, more preferably 10 minutes or longer, and still more preferably 20 minutes or longer, from the viewpoint of suppressing the generation of cracks, and the upper limit is not particularly limited. However, for example, it may be set to 120 minutes or less, 90 minutes or less, or the like. The heat treatment time means the time during which the heat treatment temperature is maintained.

The heat treatment in step (B) may be performed by heating the insulating layer in a gas atmosphere, or may be performed by immersing the insulating layer in a liquid and heating the insulating layer. It is preferably carried out by heating the insulating layer in an atmosphere. Heat treatment is performed under a pressure of, for example, 0.05 MPa to 0.15 MPa, preferably 0.08 to 0.12 MPa.

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

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

The step (B) may include a step of cooling the insulating layer to 30° C. or lower after heat-treating the insulating layer at T ₂ (° C.). The cooling temperature in the process can be preferably 10°C to 30°C, more preferably 20°C to 30°C. The method of cooling is not particularly limited, and the insulating layer may be allowed to cool, a method of blowing cold air against the insulating layer, a method of pressing the insulating layer against a cooled roll, or the like. Cooling in the process is usually performed in a gas (eg, air, argon gas, nitrogen gas, or mixed gas thereof) atmosphere, for example, a pressure of 0.05 MPa to 0.15 MPa, preferably 0.08 to 0.12 MPa. done below.

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

<(C) step>
The step (C) desmears the insulating layer with an oxidant solution. The procedure and conditions for the desmear treatment are not particularly limited, and known procedures and conditions that are commonly used for forming insulating layers of printed wiring boards can be employed. Desmear treatment can be performed, for example, by immersing the insulating layer in an oxidant solution.

As the oxidizing agent solution, an oxidizing agent solution used in normal desmear treatment can be used. Examples of such an oxidant solution include an alkaline permanganate solution prepared by dissolving potassium permanganate or sodium permanganate as an oxidant in an aqueous solution of sodium hydroxide. The oxidant concentration of the oxidant solution is preferably 3% by mass or more, more preferably 5% by mass or more, still more preferably 7% by mass or more, and preferably 20% by mass or less, more preferably 15% by mass. 10% by mass or less, and more preferably 10% by mass or less.

A commercially available product may be used as the oxidant solution. Examples of commercially available oxidant solutions include alkaline permanganate solutions such as "Concentrate Compact CP" and "Dosing Solution Security P" manufactured by Atotech Japan.

The oxidizing agent solution is preferably used after being heated when the insulating layer is immersed. The heating temperature of the oxidant solution is preferably 60° C. or higher, more preferably 65° C. or higher, still more preferably 70° C. or higher, and preferably 100° C. or lower, more preferably 95° C. or lower, further preferably 90° C. or lower. is.

The immersion time of the insulating layer in the oxidant solution is preferably 5 minutes or longer, more preferably 10 minutes or longer, still more preferably 15 minutes or longer, preferably 40 minutes or shorter, more preferably 30 minutes or shorter, and even more preferably. is 25 minutes or less.

In the step (C), the insulating layer may be immersed in a swelling liquid for swelling treatment before desmearing the insulating layer with the oxidant solution.

Examples of the swelling liquid include swelling liquids such as water, an aqueous sodium hydroxide solution, an aqueous potassium hydroxide solution, etc. Among them, water and the swelling liquid are preferable, and water is more preferable. A commercially available product can be used as the swelling liquid. Examples of commercially available products include "Swelling Dip Securigans P" and "Swelling Dip Securigans SBU" manufactured by Atotech Japan.

The swelling liquid is preferably used after being heated when the insulating layer is immersed. The heating temperature of the swelling liquid is preferably 30° C. or higher, more preferably 35° C. or higher, still more preferably 40° C. or higher, and preferably 100° C. or lower, more preferably 95° C. or lower, further preferably 90° C. or lower. is.

The immersion time of the insulating layer in the swelling liquid is preferably 1 minute or longer, more preferably 3 minutes or longer, still more preferably 5 minutes or longer, preferably 40 minutes or shorter, more preferably 30 minutes or shorter, and even more preferably. 25 minutes or less.

The pH of the swelling liquid is preferably 6 or higher, more preferably 6.5 or higher, still more preferably 7 or higher, and preferably 14 or lower, further preferably 13.5 or lower, 12 or lower, 12.5 or lower, 11. 10 or less, 8 or less, 7.5 or less.

In the step (C), after desmearing the insulating layer with an oxidant solution, neutralization may be performed by immersing the insulating layer in a neutralizing solution from the viewpoint of removing residues of salts of the oxidant. .

As the neutralization liquid, it is preferable to use an acidic aqueous solution. A commercial product may be used as the neutralizing solution, and examples of the commercial product of the neutralizing solution include "Reduction Solution Securigant P" manufactured by Atotech Japan.

It is preferable to use the neutralizing solution after heating when the insulating layer is immersed. The heating temperature of the neutralization solution is preferably 30° C. or higher, more preferably 35° C. or higher, and preferably 80° C. or lower, more preferably 70° C. or lower, from the viewpoint of removing the residue of the salt of the oxidizing agent. , and more preferably 60° C. or less.

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

In the step (C), the insulating layer may be desmeared with an oxidant solution (optionally neutralized by immersing the insulating layer in a neutralizing solution), and then dried in the air.

The drying temperature is preferably 40° C. or higher, more preferably 60° C. or higher, and preferably 120° C. or lower, more preferably 100° C. or lower. The drying time is preferably 10 minutes or longer, more preferably 20 minutes or longer, and preferably 60 minutes or shorter, more preferably 40 minutes or shorter.

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

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

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

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

In one embodiment, the conductor layer may be formed by plating. For example, a conductive layer having a desired wiring pattern can be formed by plating the surface of an insulating layer by a conventionally known technique such as a semi-additive method or a full-additive method. It is preferably formed by a method. An example of forming a conductor layer by a semi-additive method is shown below.

First, a plating seed layer is formed on the surface of the insulating layer by electroless plating. Next, a mask pattern is formed on the formed plating seed layer to expose a portion of the plating seed layer corresponding to a desired wiring pattern. After forming a metal layer on the exposed plating seed layer by electroplating, the mask pattern is removed. After that, the unnecessary plating seed layer is removed by etching or the like, and a conductor layer having a desired wiring pattern can be formed.

The support is used during the (A) step (for example, between the (A-2) step and the (A-3) step, between the (A-2) step and the (A-3) step, (A-3 ) between step and (A-4) step, or between (A-4) step and (A-5) step), between (A) step and (B) step, or (B) step and (C) step. The support is preferably removed between steps (B) and (C). Moreover, you may wash with water after completion|finish of each process as needed.

<Resin composition layer>
Components contained in the resin composition layer bonded to the inner layer substrate in the laminate (the resin composition layer provided on the support in the resin sheet) are described below.

The resin composition layer contains (a) an epoxy resin and (b) an active ester curing agent.

<(a) epoxy resin>
(a) Epoxy resin is a curable resin having an epoxy group. The (a) epoxy resin described here has an epoxy equivalent of 5,000 g/eq. They are:

(a) Epoxy resins include, for example, bixylenol type epoxy resin, bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, bisphenol AF type epoxy resin, dicyclopentadiene type epoxy resin, and trisphenol type epoxy resin. Epoxy resin, naphthol novolac type epoxy resin, phenol novolac type epoxy resin, tert-butyl-catechol type epoxy resin, naphthalene type epoxy resin, naphthol type epoxy resin, anthracene type epoxy resin, glycidylamine type epoxy resin, glycidyl ester type epoxy resin , cresol novolac type epoxy resin, phenol aralkyl type epoxy resin, biphenyl type epoxy resin, linear aliphatic epoxy resin, epoxy resin having a butadiene structure, alicyclic epoxy resin, heterocyclic epoxy resin, spiro ring-containing epoxy resin, cyclohexane-type epoxy resin, cyclohexanedimethanol-type epoxy resin, naphthylene ether-type epoxy resin, trimethylol-type epoxy resin, tetraphenylethane-type epoxy resin, isocyanurate-type epoxy resin, phenolphthalimidine-type epoxy resin, and the like. . (a) Epoxy resins may be used singly or in combination of two or more.

The resin composition layer preferably contains (a) an epoxy resin having two or more epoxy groups in one molecule as the epoxy resin. (a) The proportion of the epoxy resin having two or more epoxy groups in one molecule is preferably 50% by mass or more, more preferably 60% by mass or more, and particularly preferably 100% by mass of the non-volatile component of the epoxy resin. is 70% by mass or more.

Epoxy resins include liquid epoxy resins at a temperature of 20° C. (hereinafter sometimes referred to as “liquid epoxy resins”) and solid epoxy resins at a temperature of 20° C. (hereinafter sometimes referred to as “solid epoxy resins”). ). As the epoxy resin, the resin composition layer may contain only a liquid epoxy resin, may contain only a solid epoxy resin, or may contain both a liquid epoxy resin and a solid epoxy resin. However, it is preferable to contain both a liquid epoxy resin and a solid epoxy resin.

A liquid epoxy resin having two or more epoxy groups in one molecule is preferable as the liquid epoxy resin.

Liquid epoxy resins include glycyrrol type epoxy resins, bisphenol A type epoxy resins, bisphenol F type epoxy resins, bisphenol AF type epoxy resins, naphthalene type epoxy resins, glycidyl ester type epoxy resins, glycidyl amine type epoxy resins, phenol novolac type epoxy resins. Resins, alicyclic epoxy resins having an ester skeleton, cyclohexanedimethanol-type epoxy resins, cycloaliphatic glycidyl ethers, and epoxy resins having a butadiene structure are preferred.

Specific examples of liquid epoxy resins include "EX-992L" manufactured by Nagase ChemteX Corporation, "YX7400" manufactured by Mitsubishi Chemical Corporation, "HP4032", "HP4032D", and "HP4032SS" manufactured by DIC Corporation (naphthalene type epoxy resin ); "828US", "828EL", "825", "Epikote 828EL" (bisphenol A type epoxy resin) manufactured by Mitsubishi Chemical Corporation; "jER807" and "1750" (bisphenol F type epoxy resin) manufactured by Mitsubishi Chemical Corporation ; "jER152" (phenol novolac type epoxy resin) manufactured by Mitsubishi Chemical Corporation; "630", "630LSD", "604" (glycidylamine type epoxy resin) manufactured by Mitsubishi Chemical Corporation; "ED-523T" manufactured by ADEKA Corporation (Glycyrrol type epoxy resin); ADEKA "EP-3950L", "EP-3980S" (glycidylamine type epoxy resin); ADEKA "EP-4088S" (dicyclopentadiene type epoxy resin); Nippon Steel "ZX1059" (mixture of bisphenol A type epoxy resin and bisphenol F type epoxy resin) manufactured by Chemical &Materials; "EX-721" (glycidyl ester type epoxy resin) manufactured by Nagase ChemteX; manufactured by Nagase ChemteX "EX-991L" (alkyleneoxy skeleton and butadiene skeleton-containing epoxy resin); Daicel "Celoxide 2021P" (alicyclic epoxy resin having an ester skeleton); Daicel "PB-3600", Nippon Soda "JP-100", "JP-200", "JP-400" (epoxy resins having a butadiene structure) manufactured by Nippon Steel Chemical & Materials Co., Ltd.; glycidylcyclohexane-type epoxy resin); “EG-280” (fluorene structure-containing epoxy resin) manufactured by Osaka Gas Chemicals; and “EX-201” (cycloaliphatic glycidyl ether) manufactured by Nagase ChemteX.

The solid epoxy resin is preferably a solid epoxy resin having 3 or more epoxy groups per molecule, more preferably an aromatic solid epoxy resin having 3 or more epoxy groups per molecule.

Solid epoxy resins include bixylenol type epoxy resin, naphthalene type epoxy resin, naphthalene type tetrafunctional epoxy resin, naphthol novolak type epoxy resin, cresol novolak type epoxy resin, dicyclopentadiene type epoxy resin, trisphenol type epoxy resin, Naphthol type epoxy resin, biphenyl type epoxy resin, naphthylene ether type epoxy resin, anthracene type epoxy resin, bisphenol A type epoxy resin, bisphenol AF type epoxy resin, phenol aralkyl type epoxy resin, tetraphenylethane type epoxy resin, phenol phthalate A mijin-type epoxy resin is preferred.

Specific examples of solid epoxy resins include "HP4032H" (naphthalene-type epoxy resin) manufactured by DIC; "HP-4700" and "HP-4710" (naphthalene-type tetrafunctional epoxy resin) manufactured by DIC; "N-690" (cresol novolac type epoxy resin) manufactured by DIC Corporation; "N-695" (cresol novolak type epoxy resin) manufactured by DIC Corporation; "HP-7200", "HP-7200HH", "HP -7200H", "HP-7200L" (dicyclopentadiene type epoxy resin); DIC's "EXA-7311", "EXA-7311-G3", "EXA-7311-G4", "EXA-7311-G4S" ”, “HP6000”, “HP6000L” (naphthylene ether type epoxy resin); Nippon Kayaku Co., Ltd. “EPPN-502H” (trisphenol type epoxy resin); Nippon Kayaku Co., Ltd. “NC7000L” (naphthol novolac type epoxy resin); "NC3000H", "NC3000", "NC3000L", "NC3000FH", "NC3100" (biphenyl type epoxy resin) manufactured by Nippon Kayaku; "ESN475V" and "ESN4100V" manufactured by Nippon Steel Chemical & Materials Co., Ltd. " (naphthalene type epoxy resin); "ESN485" (naphthol type epoxy resin) manufactured by Nippon Steel Chemical &Materials; "ESN375" (dihydroxynaphthalene type epoxy resin) manufactured by Nippon Steel Chemical &Materials; "YX4000H", "YX4000", "YX4000HK", "YL7890" (bixylenol type epoxy resin); "YL6121" manufactured by Mitsubishi Chemical Corporation (biphenyl type epoxy resin); "YX8800" manufactured by Mitsubishi Chemical Corporation (anthracene type epoxy resin); "YX7700" (phenol aralkyl type epoxy resin) manufactured by Mitsubishi Chemical; "PG-100" and "CG-500" manufactured by Osaka Gas Chemicals; "YL7760" manufactured by Mitsubishi Chemical (bisphenol AF type epoxy Resin); "YL7800" manufactured by Mitsubishi Chemical Corporation (fluorene type epoxy resin); "jER1010" manufactured by Mitsubishi Chemical Corporation (bisphenol A type epoxy resin); "jER1031S" manufactured by Mitsubishi Chemical Corporation (tetraphenylethane type epoxy resin) "WHR991S" (phenolphthalimidine type epoxy resin) manufactured by Nippon Kayaku Co., Ltd.; These may be used individually by 1 type, and may be used in combination of 2 or more types.

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

(a) The epoxy equivalent of the epoxy resin is preferably 50 g/eq. ~5,000g/eq. , more preferably 60 g/eq. ~2,000 g/eq. , more preferably 70 g/eq. ~1,000g/eq. , even more preferably 80 g/eq. ~500 g/eq. is. Epoxy equivalent weight is the mass of resin per equivalent of epoxy groups. This epoxy equivalent can be measured according to JIS K7236.

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

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

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

(b) Active ester-based curing agents generally contain two highly reactive ester groups per molecule, such as phenol esters, thiophenol esters, N-hydroxyamine esters, and esters of heterocyclic hydroxy compounds. A compound having one or more is preferably used. The active ester compound is preferably obtained by a condensation reaction between a carboxylic acid compound and/or a thiocarboxylic acid compound and a hydroxy compound and/or a thiol compound. In particular, from the viewpoint of improving heat resistance, an active ester compound obtained from a carboxylic acid compound and a hydroxy compound is preferred, and an active ester compound obtained from a carboxylic acid compound and a phenol compound and/or a naphthol compound is more preferred. Examples of carboxylic acid compounds include benzoic acid, acetic acid, succinic acid, maleic acid, itaconic acid, phthalic acid, isophthalic acid, terephthalic acid, and pyromellitic acid. Examples of phenol compounds or naphthol compounds include hydroquinone, resorcinol, bisphenol A, bisphenol F, bisphenol S, phenolphthalin, 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, phloroglucine, Benzenetriol, dicyclopentadiene-type diphenol compound, phenol novolak, and the like. Here, the term "dicyclopentadiene-type diphenol compound" refers to a diphenol compound obtained by condensing one molecule of dicyclopentadiene with two molecules of phenol.

(b) Active ester-based curing agents include, specifically, dicyclopentadiene-type active ester compounds, naphthalene-type active ester compounds containing a naphthalene structure, active ester compounds containing acetylated phenol novolacs, and benzoylated phenol novolacs. Among them, at least one selected from dicyclopentadiene-type active ester compounds and naphthalene-type active ester compounds is more preferable. As the dicyclopentadiene-type active ester compound, an active ester compound containing a dicyclopentadiene-type diphenol structure is preferable.

(b) Commercially available active ester curing agents include "EXB9451", "EXB9460", "EXB9460S", "HPC-8000L-65TM", and "HPC- 8000-65T", "HPC-8000H", "HPC-8000H-65TM" (manufactured by DIC); active ester compounds containing naphthalene structures: "HP-B-8151-62T", "EXB-8100L-65T", "EXB-9416-70BK", "HPC-8150-62T", "EXB-8" (manufactured by DIC Corporation); "EXB9401" (manufactured by DIC Corporation) as a phosphorus-containing active ester compound, which is an acetylated product of phenol novolac "DC808" (manufactured by Mitsubishi Chemical Corporation) as an active ester compound, "YLH1026", "YLH1030" and "YLH1048" (manufactured by Mitsubishi Chemical Corporation) as active ester compounds that are benzoyl compounds of phenol novolak, styryl groups and naphthalene structures. Examples of active ester compounds include "PC1300-02-65MA" (manufactured by Air Water).

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

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

<(b') other curing agents>
The resin composition layer may optionally contain (b') other curing agents in addition to (b) the active ester curing agent. The (b') other curing agent described here is a component other than the (b) active ester curing agent described above. (b') Other curing agents may be used singly or in any combination of two or more. The (b') other curing agent is an epoxy resin curing agent that can react with (a) the epoxy resin to cure it, similar to the (b) active ester curing agent.

(b') Other curing agents include, but are not limited to, phenol-based curing agents, carbodiimide-based curing agents, acid anhydride-based curing agents, amine-based curing agents, benzoxazine-based curing agents, Examples include cyanate ester-based curing agents and thiol-based curing agents. The resin composition layer preferably contains one or more curing agents selected from phenol-based curing agents, carbodiimide-based curing agents, and cyanate ester-based curing agents as (b′) other curing agents. and a cyanate ester-based curing agent, more preferably containing a cyanate ester-based curing agent.

As the phenolic curing agent, a phenolic curing agent having a novolac structure is preferable from the viewpoint of heat resistance and water resistance. From the viewpoint of adhesion to adherends, 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 adhesion. Specific examples of the phenol-based curing agent include, for example, Meiwa Chemical Co., Ltd. "MEH-7700", "MEH-7810", "MEH-7851", Nippon Kayaku Co., Ltd. "NHN", "CBN", " GPH", "SN-170", "SN-180", "SN-190", "SN-475", "SN-485", "SN-495", "SN- 375", "SN-395", DIC's "LA-7052", "LA-7054", "LA-3018", "LA-3018-50P", "LA-1356", "TD2090", " KA-1160” and the like.

Examples of carbodiimide-based curing agents include curing agents having one or more, preferably two or more carbodiimide structures in one molecule. biscarbodiimides such as aromatic biscarbodiimides such as phenylene-bis(xylylcarbodiimide); polyhexamethylenecarbodiimide, polytrimethylhexamethylenecarbodiimide, polycyclohexylenecarbodiimide, poly(methylene biscyclohexylenecarbodiimide), poly(isophoronecarbodiimide) and other aliphatic polycarbodiimides; poly(phenylenecarbodiimide), poly(naphthylenecarbodiimide), poly(tylenecarbodiimide), poly(methyldiisopropylphenylenecarbodiimide), poly(triethylphenylene carbodiimide), poly(diethylphenylenecarbodiimide), poly(triisopropylphenylenecarbodiimide), poly(diisopropylphenylenecarbodiimide), poly(xylylenecarbodiimide), poly(tetramethylxylylenecarbodiimide), poly(methylenediphenylenecarbodiimide), poly Examples include polycarbodiimides such as aromatic polycarbodiimides such as [methylenebis(methylphenylene)carbodiimide].

Examples of commercially available carbodiimide curing agents include "Carbodilite V-02B", "Carbodilite V-03", "Carbodilite V-04K", "Carbodilite V-07" and "Carbodilite V-09" manufactured by Nisshinbo Chemical Co., Ltd. "Stabaxol P", "Stabaxol P400", and "Hykasil 510" manufactured by Rhein Chemie.

Acid anhydride curing agents include curing agents having one or more acid anhydride groups in one molecule, and curing agents having two or more acid anhydride groups in one molecule are preferred. Specific examples of acid anhydride curing agents include phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methylhexahydrophthalic anhydride, methylnadic anhydride, and hydrogenated methylnadic acid. anhydride, trialkyltetrahydrophthalic anhydride, dodecenylsuccinic anhydride, 5-(2,5-dioxotetrahydro-3-furanyl)-3-methyl-3-cyclohexene-1,2-dicarboxylic anhydride, trianhydride mellitic acid, pyromellitic anhydride, benzophenonetetracarboxylic dianhydride, biphenyltetracarboxylic dianhydride, naphthalenetetracarboxylic dianhydride, oxydiphthalic dianhydride, 3,3'-4,4'- Diphenylsulfonetetracarboxylic dianhydride, 1,3,3a,4,5,9b-hexahydro-5-(tetrahydro-2,5-dioxo-3-furanyl)-naphtho[1,2-C]furan-1 , 3-dione, ethylene glycol bis(anhydrotrimellitate), polymer-type acid anhydrides such as styrene/maleic acid resin obtained by copolymerizing styrene and maleic acid. Commercially available acid anhydride-based curing agents include "HNA-100", "MH-700", "MTA-15", "DDSA" and "OSA" manufactured by Shin Nippon Rika Co., Ltd., and " YH-306", "YH-307", Hitachi Chemical "HN-2200", "HN-5500", Clay Valley "EF-30", "EF-40" "EF-60", "EF -80” and the like.

Amine-based curing agents include curing agents having one or more, preferably two or more amino groups in one molecule. Examples include aliphatic amines, polyether amines, alicyclic amines, Aromatic amines and the like can be mentioned, and among them, aromatic amines are preferable from the viewpoint of achieving the desired effects of the present invention. Amine-based curing agents are preferably primary amines or secondary amines, more preferably primary amines. Specific examples of amine curing agents include 4,4'-methylenebis(2,6-dimethylaniline), 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylsulfone, and 3,3'-diaminodiphenylsulfone. , 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)sulfone, bis(4- (3-aminophenoxy)phenyl)sulfone, and the like. Commercially available amine-based curing agents may be used, for example, Seika "SEIKACURE-S", Nippon Kayaku "KAYABOND C-200S", "KAYABOND C-100", "KAYAHARD AA". , “Kayahard AB”, “Kayahard AS”, “Epicure W” manufactured by Mitsubishi Chemical Corporation, and the like.

Specific examples of benzoxazine-based curing agents include "JBZ-OP100D" and "ODA-BOZ" manufactured by JFE Chemical Co., Ltd.; "HFB2006M" manufactured by Showa Polymer Co., Ltd.; Examples include "Fa".

Examples of cyanate ester curing agents include bisphenol A dicyanate, polyphenolcyanate (oligo(3-methylene-1,5-phenylenecyanate)), 4,4'-methylenebis(2,6-dimethylphenylcyanate), 4, 4′-ethylidene diphenyl dicyanate, hexafluorobisphenol A dicyanate, 2,2-bis(4-cyanate)phenylpropane, 1,1-bis(4-cyanatophenylmethane), bis(4-cyanate-3,5- Difunctional cyanate resins such as dimethylphenyl)methane, 1,3-bis(4-cyanatophenyl-1-(methylethylidene))benzene, bis(4-cyanatophenyl)thioether, and bis(4-cyanatophenyl)ether, Polyfunctional cyanate resins derived from phenol novolak, cresol novolak, etc., and prepolymers obtained by partially triazine-forming these cyanate resins. Specific examples of cyanate ester curing agents include "PT30" and "PT60" (both phenol novolac type polyfunctional cyanate ester resins), "BA230" and "BA230S75" (part of bisphenol A dicyanate) manufactured by Lonza Japan Co., Ltd. or a prepolymer that is entirely triazined to form a trimer), and the like.

Examples of thiol curing agents include trimethylolpropane tris(3-mercaptopropionate), pentaerythritol tetrakis(3-mercaptobutyrate), tris(3-mercaptopropyl)isocyanurate and the like.

(b') The reactive group equivalent of other curing agents is preferably 50 g/eq. ~3000g/eq. , more preferably 100 g/eq. ~1000g/eq. , more preferably 100 g/eq. ~500 g/eq. , particularly preferably 100 g/eq. ~300 g/eq. is. Reactive group equivalents are the mass of (b') other curing agent per equivalent of reactive groups.

The content of (b′) other curing agent in the resin composition layer is not particularly limited, but is preferably 50% by mass or less when the non-volatile component in the resin composition layer is 100% by mass. , more preferably 30% by mass or less, still more preferably 20% by mass or less, and particularly preferably 10% by mass or less. The lower limit of the content of (b′) other curing agent in the resin composition layer is not particularly limited, but when the nonvolatile component in the resin composition layer is 100% by mass, for example, 0 mass % or more, or 0.01 mass % or more, preferably 0.1 mass % or more, more preferably 0.5 mass % or more, and particularly preferably 1 mass % or more.

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

(c) An inorganic compound is used as the material for the inorganic filler. (c) Examples of inorganic filler materials include silica, alumina, glass, cordierite, silicon oxide, barium sulfate, barium carbonate, talc, clay, mica powder, zinc oxide, hydrotalcite, boehmite, and water. Aluminum oxide, magnesium hydroxide, calcium carbonate, magnesium carbonate, magnesium oxide, boron nitride, aluminum nitride, manganese nitride, aluminum borate, strontium carbonate, strontium titanate, calcium titanate, magnesium titanate, bismuth titanate, titanium oxide , zirconium oxide, barium titanate, barium zirconate titanate, barium zirconate, calcium zirconate, zirconium phosphate, and zirconium tungstate phosphate. Among these, silica is particularly suitable. Examples of silica include amorphous silica, fused silica, crystalline silica, synthetic silica, and hollow silica. As silica, spherical silica is preferable. (c) The inorganic filler may be used singly or in combination of two or more at any ratio.

(c) Commercially available inorganic fillers include, for example, "SP60-05" and "SP507-05" manufactured by Nippon Steel Chemical &Materials; "YC100C", "YA050C" and "YA050C-" manufactured by Admatechs MJE", "YA010C"; "UFP-30" manufactured by Denka; "Silfil NSS-3N", "Silfil NSS-4N", "Silfil NSS-5N" manufactured by Tokuyama; "SC2500SQ" manufactured by Admatechs , “SO-C4”, “SO-C2”, “SO-C1”; and “DAW-03” and “FB-105FD” manufactured by Denka.

(c) The average particle size of the inorganic filler is not particularly limited, but is preferably 10 μm or less, more preferably 5 μm or less, still more preferably 3 μm or less, even more preferably 2 μm or less, and particularly preferably 1.0 μm or less. 5 μm or less. (c) The lower limit of the average particle size of the inorganic filler is not particularly limited. .2 μm or more. (c) The average particle size of the inorganic filler can be measured by a laser diffraction/scattering method based on Mie scattering theory. Specifically, the particle size distribution of the inorganic filler is prepared on a volume basis using a laser diffraction/scattering type particle size distribution measuring device, and the median diameter can be used as the average particle size for measurement. A measurement sample can be obtained by weighing 100 mg of an inorganic filler and 10 g of methyl ethyl ketone in a vial and dispersing them with ultrasonic waves for 10 minutes. A measurement sample is measured using a laser diffraction particle size distribution measuring device, the wavelengths of the light source used are blue and red, the volume-based particle size distribution of the inorganic filler is measured by the flow cell method, and from the obtained particle size distribution The average particle diameter was calculated as the median diameter. Examples of the laser diffraction particle size distribution analyzer include "LA-960" manufactured by Horiba, Ltd., and the like.

(c) The specific surface area of the inorganic filler is not particularly limited, but is preferably 0.1 m ² /g or more, more preferably 0.5 m ² /g or more, still more preferably 1 m ² /g or more, Particularly preferably, it is 3 m ² /g or more. (c) The upper limit of the specific surface area of the inorganic filler is not particularly limited, but is preferably 100 m ² /g or less, more preferably 70 m ² /g or less, still more preferably 50 m ² /g or less, and even more preferably 50 m 2 /g or less. It is preferably 30 m ² /g or less, particularly preferably 10 m ² /g or less. The specific surface area of the inorganic filler is determined by adsorbing nitrogen gas on the sample surface using a specific surface area measuring device (Macsorb HM-1210 manufactured by Mountech) according to the BET method, and calculating the specific surface area using the BET multipoint method. obtained by

(c) The inorganic filler is preferably treated with a surface treatment agent from the viewpoint of enhancing 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, organosilazane compounds, and titanate compounds. A coupling agent etc. are mentioned. Moreover, one type of surface treatment agent may be used alone, or two or more types may be used in combination.

Examples of commercially available surface treatment agents include "KBM403" (3-glycidoxypropyltrimethoxysilane) manufactured by Shin-Etsu Chemical Co., Ltd., "KBM803" (3-mercaptopropyltrimethoxysilane) manufactured by Shin-Etsu Chemical Co., Ltd., Shin-Etsu Chemical Industry 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 type silane coupling agent), Shin-Etsu Chemical Co., Ltd. "KBM- 7103” (3,3,3-trifluoropropyltrimethoxysilane).

From the viewpoint of improving the dispersibility of the inorganic filler, the degree of surface treatment with the surface treatment agent is preferably within a predetermined range. Specifically, 100% by mass of the inorganic filler is preferably surface-treated with a surface treatment agent of 0.2% to 5% by mass, and is surface-treated with 0.2% to 3% by mass. more preferably 0.3 mass % to 2 mass % of the 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. The above is more preferable. On the other hand, from the viewpoint of preventing an increase in the melt viscosity of the resin composition and the melt viscosity in the form of a sheet, it is preferably 1.0 mg/m ² or less, more preferably 0.8 mg/m ² or less, and 0.5 mg/m ² or less. More preferred are:

(c) The amount of carbon per unit surface area of the inorganic filler can be measured after the surface-treated inorganic filler is washed with a solvent (eg, methyl ethyl ketone (MEK)). Specifically, a sufficient amount of MEK as a solvent is added to the inorganic filler surface-treated with the surface treatment agent, and ultrasonic cleaning is performed at 25° C. for 5 minutes. After removing the supernatant liquid and drying the solid content, a carbon analyzer can be used to measure the amount of carbon per unit surface area of the inorganic filler. As a carbon analyzer, "EMIA-320V" manufactured by Horiba Ltd. can be used.

The content of (c) the inorganic filler in the resin composition layer is not particularly limited. It is preferably 90% by mass or less, more preferably 85% by mass or less, and particularly preferably 80% by mass or less. The lower limit of the content of the (c) inorganic filler in the resin composition layer is not particularly limited, but from the viewpoint of keeping the dielectric loss tangent lower, the nonvolatile component in the resin composition layer is set to 100% by mass. For example, it may be 0% by mass or more, 1% by mass or more, or 5% by mass or more, preferably 10% by mass or more, more preferably 30% by mass or more, still more preferably 40% by mass or more, and even more preferably 50 mass % or more, particularly preferably 60 mass % or more.

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

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

(d) In the first embodiment, the radically polymerizable compound preferably contains a thermoplastic resin having a vinylphenyl group and/or a (meth)acryloyl group. A (meth)acryloyl group means an acryloyl group or a methacryloyl group. Vinylphenyl groups include 2-vinylphenyl groups, 3-vinylphenyl groups, 4-vinylphenyl groups, and those in which these aromatic carbon atoms are further substituted with one or more alkyl groups. It is preferable to have two or more vinylphenyl groups and/or (meth)acryloyl groups in one molecule. Examples of thermoplastic resins include phenoxy resins, polyvinyl acetal resins, polystyrene resins, polyethylene resins, polypropylene resins, polybutadiene resins, polyimide resins, polyamideimide resins, polyetherimide resins, polysulfone resins, polyethersulfone resins, and polyphenylene ether resins. , polyetheretherketone resins, polyester resins, etc., and (d) radically polymerizable compounds include modified resins having vinylphenyl groups and/or (meth)acryloyl groups of these resins in this embodiment.

(d) Radically polymerizable compound, in the first embodiment, more preferably a modified polyphenylene ether resin having a vinylphenyl group and/or (meth)acryloyl group, and a vinylphenyl group and/or (meth)acryloyl group more preferably a modified polyphenylene ether resin having a vinylphenyl group and/or (meth)acryloyl group, particularly preferably the formula (B-1):

[wherein R ¹¹ and R ¹² each independently represent an alkyl group; R ¹³ , R ¹⁴ , R ²¹ , R ²² , R ²³ and R ²⁴ each independently represent a hydrogen atom or an alkyl R ³¹ and R ³² each independently represent a vinylphenyl group or (meth)acryloyl group; Y ¹ is a single bond, —C(R ^y ) ₂ —, —O—, —CO -, -S-, -SO-, or -SO ₂ -; R ^y each independently represents a hydrogen atom or an alkyl group; Y ² represents a single bond or an alkylene group; represents 0 or 1; q and r each independently represents an integer of 1 or more. ]
Including the resin represented by. 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.

An alkyl group means a linear, branched and/or cyclic monovalent saturated aliphatic 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 even more preferably an alkyl group having 1 to 6 carbon atoms. Examples of alkyl groups include methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, sec-butyl group, tert-butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group, cyclopentyl group, cyclohexyl group, methylcyclohexyl group, dimethylcyclohexyl group, trimethylcyclohexyl group, cyclopentylmethyl group, cyclohexylmethyl group and the like.

R ³¹ and R ³² each independently represent a vinylphenyl group or a (meth)acryloyl group, and Y ² represents a single bond or an alkylene group. An alkylene group means a linear, branched and/or cyclic divalent saturated aliphatic hydrocarbon group. The alkylene group is preferably an alkylene group having 1 to 14 carbon atoms, preferably an alkylene group having 1 to 10 carbon atoms, and 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 - and the like. Preferably, R ³¹ and R ³² are vinylphenyl groups and Y ² is an alkylene group (especially -CH ₂ -), or R ³¹ and R ³² are (meth)acryloyl groups. and Y ² is a single bond.

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-. Each R ^y independently represents 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 1-200, more preferably an integer of 1-100.

Commercially available products of (d) the radically polymerizable compound in the first embodiment include, for example, Mitsubishi Gas Chemical Company's "OPE-2St 1200" and "OPE-2St 2200" (vinylbenzyl-modified polyphenylene ether resin); SABIC "SA9000" and "SA9000-111" (methacrylic-modified polyphenylene ether resin) manufactured by Innovative Plastics Co., Ltd., and the like can be mentioned.

The content of (d) the radically polymerizable compound in the resin composition layer is not particularly limited, but is preferably 50% by mass or less when the non-volatile component in the resin composition layer is 100% by mass. More preferably 30% by mass or less, still more preferably 20% by mass or less, and particularly preferably 10% by mass or less. The lower limit of the content of the (d) radically polymerizable compound in the resin composition layer is not particularly limited, but from the viewpoint of keeping the dielectric loss tangent lower, the nonvolatile component in the resin composition layer is 100% by mass. In the case of, for example, it may be 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, still 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 a component that does not correspond to (a) epoxy resins, (b) other curing agents, and (d) radically polymerizable compounds.

(e) Thermoplastic resins include, for example, polyimide resins, phenoxy resins, polyvinyl acetal resins, polyolefin resins, polybutadiene resins, polyamideimide resins, polyetherimide resins, polysulfone resins, polyethersulfone resins, polyphenylene ether resins, and polycarbonate resins. , polyether ether ketone resin, polyester resin, and the like. In one embodiment, the resin composition layer preferably contains a thermoplastic resin selected from the group consisting of polyimide resin and phenoxy resin, and more preferably contains phenoxy resin. Further, the thermoplastic resin may be used singly or in combination of two or more.

Specific examples of the polyimide resin include “SLK-6100” manufactured by Shin-Etsu Chemical Co., Ltd., “Likacoat SN20” and “Ricacoat PN20” manufactured by Shin Nippon Rika Co., Ltd., and the like.

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

Specific examples of the phenoxy resin include Mitsubishi Chemical's "1256" and "4250" (both bisphenol A skeleton-containing phenoxy resins); Mitsubishi Chemical's "YX8100" (bisphenol S skeleton-containing phenoxy resin); Mitsubishi Chemical "YX6954" (bisphenolacetophenone skeleton-containing phenoxy resin) manufactured by Nippon Steel & Sumikin Chemical Co., Ltd.; "FX280" and "FX293" manufactured by Nippon Steel & Sumikin Chemical Co., Ltd.; "YL7769BH30", "YL6794", "YL7213", "YL7290", "YL7482" and "YL7891BH30";

Examples of polyvinyl acetal resins include polyvinyl formal resins and polyvinyl butyral resins, and polyvinyl butyral resins are preferred. Specific examples of polyvinyl acetal resins include Denka Butyral 4000-2, Denka Butyral 5000-A, Denka Butyral 6000-C, and Denka Butyral 6000-EP manufactured by Sekisui Chemical Co., Ltd. S-LEC BH series, BX series (eg BX-5Z), KS series (eg KS-1), BL series, BM series;

Examples of polyolefin resins include ethylene-based copolymers 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. Resin: polyolefin polymers such as polypropylene and ethylene-propylene block copolymers.

Examples of polybutadiene resins include hydrogenated polybutadiene skeleton-containing resins, hydroxyl group-containing polybutadiene resins, phenolic hydroxyl group-containing polybutadiene resins, carboxy group-containing polybutadiene resins, acid anhydride group-containing polybutadiene resins, epoxy group-containing polybutadiene resins, and isocyanate group-containing resins. Examples include polybutadiene resin, urethane group-containing polybutadiene resin, polyphenylene ether-polybutadiene resin, and the like.

Specific examples of polyamide-imide resins include "VYLOMAX HR11NN" and "VYLOMAX HR16NN" manufactured by Toyobo Co., Ltd. Specific examples of polyamideimide resins include modified polyamideimides such as "KS9100" and "KS9300" (polysiloxane skeleton-containing polyamideimides) 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 polysulfone resin include polysulfone "P1700" and "P3500" manufactured by Solvay Advanced Polymers.

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

Examples of polycarbonate resins include hydroxyl group-containing carbonate resins, phenolic hydroxyl group-containing carbonate resins, carboxy group-containing carbonate resins, acid anhydride group-containing carbonate resins, isocyanate group-containing carbonate resins, and urethane group-containing carbonate resins. Specific examples of polycarbonate resins include "FPC0220" manufactured by Mitsubishi Gas Chemical Co., Ltd., "T6002" and "T6001" (polycarbonate diol) manufactured by Asahi Kasei Chemicals, "C-1090" and "C-2090" manufactured by Kuraray Co., Ltd. , “C-3090” (polycarbonate diol) and the like. Specific examples of the polyetheretherketone resin include "Sumiproy K" manufactured by Sumitomo Chemical Co., Ltd., and the like.

Examples of polyester resins include polyethylene terephthalate resin, polyethylene naphthalate resin, polybutylene terephthalate resin, polybutylene naphthalate resin, polytrimethylene terephthalate resin, polytrimethylene naphthalate resin, polycyclohexanedimethyl terephthalate resin, and the like.

(e) The weight-average molecular weight (Mw) of the thermoplastic resin is preferably 5,000 or more, more preferably 8,000 or more, still more preferably 10,000 or more, particularly preferably 10,000 or more, from the viewpoint of significantly obtaining the effects of the present invention. is 20,000 or more, preferably 100,000 or less, more preferably 70,000 or less, even more preferably 60,000 or less, and particularly preferably 50,000 or less.

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

<(f) Curing accelerator>
The resin composition layer may further contain (f) a curing accelerator as an optional component. (f) The curing accelerator functions as a curing catalyst that accelerates the curing of (a) the epoxy resin.

(f) Curing accelerators include, for example, 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 curing accelerator preferably contains a curing accelerator selected from imidazole-based curing accelerators and amine-based curing accelerators. (f) Curing accelerators may be used singly or in combination of two or more.

Phosphorus curing accelerators include, for example, tetrabutylphosphonium bromide, tetrabutylphosphonium chloride, tetrabutylphosphonium acetate, tetrabutylphosphonium decanoate, tetrabutylphosphonium laurate, bis(tetrabutylphosphonium) pyromellitate, tetrabutylphosphonium hydro Aliphatic phosphonium salts such as genhexahydrophthalate, tetrabutylphosphonium 2,6-bis[(2-hydroxy-5-methylphenyl)methyl]-4-methylphenolate, di-tert-butylmethylphosphonium tetraphenylborate; methyltriphenylphosphonium bromide, ethyltriphenylphosphonium bromide, propyltriphenylphosphonium bromide, butyltriphenylphosphonium bromide, benzyltriphenylphosphonium chloride, tetraphenylphosphonium bromide, p-tolyltriphenylphosphonium tetra-p-tolylborate, tetraphenyl phosphonium tetraphenylborate, tetraphenylphosphonium tetra-p-tolylborate, triphenylethylphosphonium tetraphenylborate, tris(3-methylphenyl)ethylphosphonium tetraphenylborate, tris(2-methoxyphenyl)ethylphosphonium tetraphenylborate, (4 -methylphenyl)triphenylphosphonium thiocyanate, tetraphenylphosphonium thiocyanate, aromatic phosphonium salts such as butyltriphenylphosphonium thiocyanate; aromatic phosphine/borane complexes such as triphenylphosphine/triphenylborane; triphenylphosphine/p-benzoquinone Aromatic phosphine/quinone addition reaction products such as addition reaction products; 2-butenyl)phosphine, aliphatic phosphines such as tricyclohexylphosphine; - tolylphosphine, tri-m-tolylphosphine, tri-p-tolylphosphine Sphines, Tris(4-ethylphenyl)phosphine, Tris(4-propylphenyl)phosphine, Tris(4-isopropylphenyl)phosphine, Tris(4-butylphenyl)phosphine, Tris(4-tert-butylphenyl)phosphine, Tris (2,4-dimethylphenyl)phosphine, tris(2,5-dimethylphenyl)phosphine, tris(2,6-dimethylphenyl)phosphine, tris(3,5-dimethylphenyl)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(diphenylphosphino)ethane, 1,3-bis(diphenylphosphino)propane, 1,4-bis(diphenylphosphino) Aromatic phosphines such as butane, 1,2-bis(diphenylphosphino)acetylene, 2,2'-bis(diphenylphosphino)diphenyl ether, and the like can be mentioned.

Urea-based curing accelerators include, for example, 1,1-dimethylurea; 1,1,3-trimethylurea, 3-ethyl-1,1-dimethylurea, 3-cyclohexyl-1,1-dimethylurea, 3- Aliphatic dimethylurea such as cyclooctyl-1,1-dimethylurea; 3-phenyl-1,1-dimethylurea, 3-(4-chlorophenyl)-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- methoxyphenyl)-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) Aromatic dimethylurea such as bis(N',N'-dimethylurea), N,N-(4-methyl-1,3-phenylene)bis(N',N'-dimethylurea) [toluenebisdimethylurea] etc.

Guanidine curing accelerators include, for example, 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 and the like.

Examples of imidazole curing accelerators include 2-methylimidazole, 2-undecylimidazole, 2-heptadecylimidazole, 1,2-dimethylimidazole, 2-ethyl-4-methylimidazole, 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, 2,4-diamino-6-[2'-methylimidazolyl-(1')]-ethyl-s-triazine, 2,4-diamino-6-[2'-undecyl imidazolyl-(1′)]-ethyl-s-triazine, 2,4-diamino-6-[2′-ethyl-4′-methylimidazolyl-(1′)]-ethyl-s-triazine, 2,4- Diamino-6-[2'-methylimidazolyl-(1')]-ethyl-s-triazine isocyanurate, 2-phenylimidazole isocyanurate, 2-phenyl-4,5-dihydroxymethylimidazole, 2- Phenyl-4-methyl-5-hydroxymethylimidazole, 2,3-dihydro-1H-pyrrolo[1,2-a]benzimidazole, 1-dodecyl-2-methyl-3-benzylimidazolium chloride, 2-methylimidazoline , 2-phenylimidazoline and other imidazole compounds, and adducts of imidazole compounds and epoxy resins.

As the imidazole-based curing accelerator, a commercially available product may be used, for example, "1B2PZ", "2MZA-PW", "2PHZ-PW" manufactured by Shikoku Kasei Co., Ltd., "P200-H50" manufactured by Mitsubishi Chemical Corporation. etc.

Metal-based curing accelerators include, for example, 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, organocopper complexes such as copper (II) acetylacetonate, and zinc (II) acetylacetonate. organic zinc complexes such as iron (III) acetylacetonate; organic nickel complexes such as nickel (II) acetylacetonate; organic manganese complexes such as manganese (II) acetylacetonate; Examples of organic metal salts include zinc octoate, tin octoate, zinc naphthenate, cobalt naphthenate, tin stearate, and zinc stearate.

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

As the amine-based curing accelerator, a commercially available product may be used, such as "MY-25" manufactured by Ajinomoto Fine-Techno Co., Ltd., and the like.

The content of the (f) curing accelerator in the resin composition layer is not particularly limited. It is preferably 1% by mass or less, more preferably 0.5% by mass or less, and particularly preferably 0.2% by mass or less. The lower limit of the content of the (f) curing accelerator in the resin composition layer is not particularly limited, but when the non-volatile component in the resin composition layer is 100% by mass, for example, 0% by mass or more. , 0.01% by mass or more, 0.1% by mass or more, and the like.

<(g) other additives>
The resin composition of the present invention may further contain optional additives as non-volatile components. Examples of such additives include radical polymerization initiators such as peroxide radical polymerization initiators and azo radical polymerization initiators; epoxy acrylate resins, urethane acrylate resins, urethane resins, cyanate resins, benzoxazine resins, Thermosetting resins other than epoxy resins such as unsaturated polyester resins, phenolic resins, melamine resins and silicone resins; organic fillers such as rubber particles; organic metal compounds such as organic copper compounds, organic zinc compounds and organic cobalt compounds; Colorants such as blue, phthalocyanine green, iodine green, diazo yellow, crystal violet, titanium oxide, and carbon black; polymerization inhibitors such as hydroquinone, catechol, pyrogallol, and phenothiazine; silicone leveling agents, acrylic polymer leveling agents, etc. leveling agents; thickeners such as bentone and montmorillonite; UV absorbers; adhesion improvers such as urea silane; adhesion promoters such as triazole-based adhesion promoters, tetrazole-based adhesion promoters, and triazine-based adhesion promoters; oxidation such as hindered phenol-based antioxidants Inhibitors; fluorescent brighteners such as stilbene derivatives; surfactants such as fluorine-based surfactants and silicone-based surfactants; , flame retardants such as nitrogen flame retardants (e.g. melamine sulfate), halogen flame retardants, inorganic flame retardants (e.g. antimony trioxide); phosphate ester dispersants, polyoxyalkylene dispersants, acetylene dispersants, Dispersants such as silicone dispersants, anionic dispersants, cationic dispersants; borate stabilizers, titanate stabilizers, aluminate stabilizers, zirconate stabilizers, isocyanate stabilizers, carboxylic acid stabilizers , stabilizers such as carboxylic acid anhydride-based stabilizers, and the like. (g) Other additives may be used singly or in combination of two or more at any ratio. (g) The content of other additives can be appropriately set by those skilled in the art.

<(h) organic solvent>
The resin composition of the present invention may further contain an arbitrary organic solvent as a volatile component in addition to the non-volatile components described above. (h) As the organic solvent, a known solvent can be used as appropriate, and the type thereof is not particularly limited. (h) Examples of organic solvents include ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone; Ester-based solvents such as butyrolactone; Ether-based solvents such as tetrahydropyran, tetrahydrofuran, 1,4-dioxane, diethyl ether, diisopropyl ether, dibutyl ether, diphenyl ether, and anisole; Alcohol-based solvents such as methanol, ethanol, propanol, butanol, and ethylene glycol Solvent; Ether ester solvents such as 2-ethoxyethyl acetate, propylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, ethyl diglycol acetate, γ-butyrolactone, methyl methoxypropionate; methyl lactate, ethyl lactate, 2-hydroxyiso ester alcohol solvents such as methyl butyrate; ether alcohol solvents such as 2-methoxypropanol, 2-methoxyethanol, 2-ethoxyethanol, propylene glycol monomethyl ether, diethylene glycol monobutyl ether (butyl carbitol); N,N-dimethylformamide , N,N-dimethylacetamide, N-methyl-2-pyrrolidone and other amide solvents; dimethyl sulfoxide and other sulfoxide solvents; acetonitrile, propionitrile and other nitrile solvents; hexane, cyclopentane, cyclohexane, methylcyclohexane, etc. and aromatic hydrocarbon solvents such as benzene, toluene, xylene, ethylbenzene and trimethylbenzene. (h) The organic solvent may be used singly or in combination of two or more at any ratio.

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

<Semiconductor device>
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 appliances (eg, computers, mobile phones, digital cameras, televisions, etc.) and vehicles (eg, motorcycles, automobiles, trains, ships, aircraft, etc.).

A semiconductor device can be manufactured by mounting components (semiconductor chips) on conductive portions of a printed wiring board. A conductive portion is a portion of a printed wiring board that transmits an electric signal, and the portion may be a surface or an embedded portion. Also, the semiconductor chip is not particularly limited as long as it is an electric circuit element made of a semiconductor.

The method of mounting a semiconductor chip when manufacturing a semiconductor device is not particularly limited as long as the semiconductor chip functions effectively. (BBUL) mounting method, anisotropic conductive film (ACF) mounting method, non-conductive film (NCF) mounting method, and the like.

EXAMPLES Hereinafter, the present invention will be specifically described with reference to Examples. The invention is not limited to these examples. In the following, "parts" and "%" representing amounts mean "parts by mass" and "% by mass", respectively, unless otherwise specified. The temperature condition in the following description is normal temperature (25° C.) unless otherwise specified, and the pressure condition is normal pressure (0.1 MPa) unless otherwise specified.

<Production example A: Production of resin sheet A>
Biphenyl aralkyl type epoxy resin ("NC-3000H" manufactured by Nippon Kayaku Co., Ltd., epoxy equivalent of about 271 g / eq.) 5 parts, naphthalene type epoxy resin (DIC "HP4032SS", epoxy equivalent of about 145 g / eq.) 10 part, bisphenol A type epoxy resin and bisphenol F type epoxy mixture ("ZX1059" manufactured by Nippon Steel Chemical & Materials Co., Ltd., epoxy equivalent 165 g / eq.) 5 parts, active ester curing agent (manufactured by DIC Corporation "HPC-8150- 62T", active group equivalent of about 229 g / eq., solid content of 61.5 wt% toluene solution) 30 parts, phenolic curing agent (manufactured by DIC "LA-3018-50P", active group equivalent of about 151, solid content 50% 2-methoxypropanol solution) 5 parts, phenoxy resin (manufactured by Mitsubishi Chemical Corporation "YX7553BH30", 1:1 solution of MEK and cyclohexanone with a solid content of 30% by mass) 5 parts, 4-dimethylaminopyridine (solid content 5 mass % MEK solution), 30 parts of MEK, and spherical silica surface-treated with an amine-based alkoxysilane compound ("KBM573" manufactured by Shin-Etsu Chemical Co., Ltd.) ("SO-C2" manufactured by Admatechs, average particle size 0 0.5 μm) was uniformly dispersed using a mixer to obtain a varnish-like resin composition.

The resulting varnish-like resin composition was evenly coated on a PET film (“AL5” manufactured by Lintec, thickness 38 μm) with a die coater so that the thickness after drying was 25 μm. A resin sheet A was produced by drying at 120° C. (average 100° C.) for 4 minutes.

<Production example B: Production of resin sheet B>
The amount of spherical silica (“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 increased from 80 parts to 120 parts. Changed, instead of 30 parts of the active ester curing agent (DIC "HPC-8150-62T"), active ester curing agent (DIC "HPC-8000-65T", active group equivalent about 223 g / eq A resin sheet B was produced in the same manner as in Production Example A, except that 30 parts of a toluene solution having a solid content of 65 mass % was used.

<Production Example C: Production of Resin Sheet C>
The amount of spherical silica (“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 increased from 80 parts to 60 parts. A resin sheet C was produced in the same manner as in Production Example A, except that the amount of active ester curing agent ("HPC-8150-62T" manufactured by DIC) was changed from 30 parts to 45 parts.

<Production example D: Production of resin sheet D>
The amount of spherical silica (“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 increased from 80 parts to 100 parts. Changed, the amount of active ester curing agent (manufactured by DIC "HPC-8150-62T") was changed from 30 parts to 45 parts, and a carbodiimide curing agent (manufactured by Nisshinbo Chemical Co., Ltd. "V-03", active group A resin sheet D was produced in the same manner as in Production Example A, except that 5 parts of a toluene solution having an equivalent weight of about 216 g/eq. and a non-volatile content of 50% by mass) was further used.

<Production example E: Production of resin sheet E>
The amount of spherical silica (“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 increased from 80 parts to 140 parts. Changed, the amount of phenolic curing agent (DIC "LA-3018-50P") used was changed from 5 parts to 10 parts, oligophenylene ether styrene resin (Mitsubishi Gas Chemical Co., Ltd. "OPE-2St 1200" , a toluene solution having a solid content of 65% by mass) was used in the same manner as in Production Example A, except that 15 parts of the resin sheet E was produced.

<Production example F: Production of resin sheet F>
The amount of spherical silica (“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 increased from 80 parts to 140 parts. Changed, the amount of active ester curing agent ("HPC-8150-62T" manufactured by DIC) was changed from 30 parts to 25 parts, and the phenolic curing agent ("LA-3018-50P" manufactured by DIC) was added. Without using, bisphenol A dicyanate ("BA230S75" manufactured by Lonza Japan Co., Ltd., cyanate equivalent of about 232, g / eq., MEK solution with a solid content of 75% by mass) is further used, and 4-dimethylaminopyridine (solid content 5% by mass MEK solution) was changed from 4 parts to 2 parts, and 2 parts of 1-benzyl-2-phenylimidazole (5% by mass solids MEK solution) was used. A resin sheet F was produced in the same manner.

<Production example G: Production of resin sheet G>
The amount of spherical silica (“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 increased from 80 parts to 120 parts. Changed, without using an active ester curing agent ("HPC-8150-62T" manufactured by DIC), without using a phenolic curing agent ("LA-3018-50P" manufactured by DIC), without using bisphenol A dicyanate ( "BA230S75" manufactured by Lonza Japan Co., Ltd., cyanate equivalent of about 232 g / eq., MEK solution with a solid content of 75% by mass) 30 parts of 4-dimethylaminopyridine (MEK solution with a solid content of 5% by mass) 4 parts A resin sheet G was produced in the same manner as in Production Example A except that 4 parts of 1-benzyl-2-phenylimidazole (MEK solution with a solid content of 5% by mass) was used instead.

<Production example H: Production of resin sheet H>
Phenol novolac type polyfunctional cyanate ester without using an active ester curing agent ("HPC-8150-62T" manufactured by DIC) and without using a phenolic curing agent ("LA-3018-50P" manufactured by DIC) Resin (“PT30” manufactured by Lonza Japan Co., Ltd., cyanate equivalent of about 124 g / eq., MEK solution with a solid content of 80% by mass) 25 parts is further used, and 4-dimethylaminopyridine (MEK solution with a solid content of 5% by mass) 4 A resin sheet H was produced in the same manner as in Production Example A except that 4 parts of 1-benzyl-2-phenylimidazole (MEK solution with a solid content of 5% by mass) was used instead of 4 parts.

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

<Example 1>
(Step of preparing an inner layer substrate on which resin sheets are laminated)
A glass cloth-based epoxy resin double-sided copper clad laminate (copper layer thickness 18 μm, substrate thickness 0.8 mm, Panasonic Electric Works Co., Ltd. “R1515A”) having copper layers on both surfaces was prepared as an inner layer substrate. Both surfaces of the inner layer substrate were immersed in "CZ8100" manufactured by MEC to roughen the surface of the copper layer.

The resin sheet A produced in Production Example A was laminated on both surfaces of the roughened inner layer substrate so that the resin composition layer was bonded to the inner layer substrate. Lamination is performed using a vacuum pressurized laminator MVLP-500 manufactured by Meiki Seisakusho Co., Ltd., after vacuum suction at a temperature of 100 ° C. for 30 seconds, under the conditions of a temperature of 100 ° C. and a pressure of 7.0 kg / cm ² , from the PET film, It was carried out by pressing for 30 seconds through a heat-resistant rubber. Next, under atmospheric pressure, using a SUS panel, pressing was performed for 60 seconds at a temperature of 100° C. and a pressure of 5.5 kg/cm ² to fabricate an inner layer substrate on which resin sheets were laminated.

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

(Step of making holes in the insulating layer)
After forming the insulating layer, with the support still attached, the insulating layer on one main surface _side of the laminate was irradiated with a power: Three or more holes were drilled under the conditions of 1.35 W, number of shots: 2, and target top diameter: 30 μm. As a result, a plurality of via holes each having a substantially circular top view and a rectangular cross-section opening on the circuit conductor of the inner layer board were formed, and the conductor layer of the inner layer board was exposed at the bottom surface of each via hole.

(Step of heat-treating the insulating layer at T ₂ (°C))
After the laser drilling step, heat treatment (annealing treatment) was performed in air at normal pressure (0.1 MPa) under the conditions of a heat treatment temperature of 130° C. (T ₂ ) and a heat treatment time of 30 minutes. After that, the temperature was returned to room temperature (25° C.), and the support was removed.

(Step of desmearing with an oxidizing agent solution)
The insulating layer surface is immersed in Swelling Dip Security P (Swelling Dip Security P) manufactured by Atotech Japan Co., Ltd., which is a swelling liquid, at 80 ° C. for 10 minutes, and then a concentrate manufactured by Atotech Japan Co., Ltd. is used as an oxidizing agent. · Compact CP was immersed at 80°C for 20 minutes, and finally, it was immersed in Reduction Solution Securigant P manufactured by Atotech Japan Co., Ltd. as a neutralizing solution at 40°C for 5 minutes. After that, it was dried at 80° C. for 30 minutes to prepare an evaluation substrate.

<Example 2>
The inner layer substrate laminated with the resin sheet prepared in the same manner as in Example 1 was heated at 130° C. for 30 minutes (preheating conditions) with the support attached, and then returned to room temperature (25° C.). . After that, with the support attached, a CO ₂ laser processing machine (“LC-K212” manufactured by HITACHI) was used on the resin composition layer on one main surface side of the inner layer substrate on which the resin sheet was laminated. Then, under the conditions of power: 1.35 W, number of shots: 2, and target top diameter: 30 μm, holes were drilled at 10 or more locations. As a result, a plurality of via holes each having a substantially circular top view and a rectangular cross-section opening on the circuit conductor of the inner layer board were formed, and the conductor layer of the inner layer board was exposed at the bottom surface of each via hole. After that, the inner layer substrate on which the resin sheets having via holes are laminated is heated at 170° C. for 30 minutes (thermosetting conditions) to thermoset the resin composition layer, form an insulating layer, and obtain a laminate. rice field. Thereafter, heat treatment (annealing treatment) was performed in air at normal pressure under the conditions of a heat treatment temperature of 130° C. (T ₂ ) and a heat treatment time of 30 minutes. , the surface of the insulating layer was desmeared under the same conditions as in Example 1 and dried to prepare an evaluation substrate.

<Example 3>
Same as Example 1, except that 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. An evaluation substrate was produced by the method of.

<Example 4>
The resin sheet C produced in Production Example C was used 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 30 minutes. An evaluation substrate was produced in the same manner as in Example 1, except that the time was changed to 60 minutes.

<Example 5>
Same as Example 1, except that the resin sheet D produced in Production Example D 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 140°C. An evaluation substrate was produced by the method of.

<Example 6>
Same as Example 1, except that the resin sheet E produced 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. An evaluation substrate was produced by the method of.

<Example 7>
Same as Example 1, except that 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. An evaluation substrate was produced by the method of.

<Comparative Example 1>
An evaluation substrate was produced in the same manner as in Example 1, except that desmear treatment was performed without performing heat treatment (annealing treatment) after the step of making 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>
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 150°C.

<Comparative Example 4>
Same as Example 1, except that 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. An evaluation substrate was produced by the method of.

<Comparative Example 5>
Same as Example 1, except that 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. An evaluation substrate was produced by the method of.

<Test Example 1: Measurement of glass transition temperature (T ₁ ) of insulating layer>
The resin sheets A to H produced in each production example were thermally cured under the preheating conditions and thermosetting conditions of the corresponding examples and comparative examples to obtain samples. The samples were measured in "tensile mode" using a Seiko Instruments Model DMS-6100 thermomechanical analyzer (DMA). Measurements were made in the range of 25°C to 240°C with a temperature increase of 2°C/min. The glass transition temperature of the insulating layer is the value obtained by rounding the maximum value of the loss tangent (tanδ) obtained by the ratio of the storage elastic modulus (E′) and the loss elastic modulus (E″) obtained by measurement to the first decimal place. (T ₁ ).

<Test Example 2: Evaluation of cracks>
A scanning electron microscope (S-4800, manufactured by Hitachi High-Tech Co., Ltd.) was used to evaluate cracks (via cracks) on the surface layers around the via holes in the evaluation substrates prepared in each of the examples and comparative examples. In the surface layer around 100 via holes, it was confirmed whether or not cracks had occurred, and the proportion of cracks not occurring was counted and evaluated according to the following evaluation criteria.

Evaluation criteria “○”: 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 methods for producing the resin sheets and evaluation substrates used in each example and comparative example, and the measurement results and evaluation results of each test example.

Drilling timing "I": (A-32) after process (A-4) before process "II": (A-31) after process (A-32) before process

As shown in Table 2, an active ester curing agent is used to form the insulating layer, and after forming the insulating layer, the insulating layer is heated to _a temperature T2 (°C) near its glass transition temperature T1 ₍ °C) (within ±20°C). ) can suppress the occurrence of cracks after the desmearing treatment (roughening treatment).

Claims (18)

(A) A step of thermally curing a resin composition layer of a laminate comprising an inner layer substrate and a resin composition layer bonded to the inner layer substrate to form an insulating layer having a glass transition temperature of T ₁ (° C.). ,
(B) heat-treating the insulating layer at T ₂ (°C); and (C) desmearing the insulating layer with an oxidant solution in this order,
A method for producing a printed wiring board, wherein the resin composition layer contains an epoxy resin and an active ester curing agent, and satisfies both the following formulas (1) and (2).
−20≦T ₁ −T ₂ ≦20 (1)
60≦T ₂ ≦150 (2) (A) the step is
(A-1) a step of preparing a resin sheet comprising a support and a resin composition layer provided on the support;
(A-2) a step of laminating resin sheets so that the resin composition layer is bonded to the inner layer substrate to obtain a laminate, and (A-3) thermosetting the resin composition layer so that the glass transition temperature is T ₁ 2. The method of manufacturing a printed wiring board according to claim 1, comprising the step of forming an insulating layer of (° C.) in this order. (A-3) step
(A-31) preheating the resin composition layer at a preheating temperature lower than the curing heating temperature; and (A-32) heating the resin composition layer at the curing heating temperature to form a resin composition layer. 3. The method for producing a printed wiring board according to claim 2, comprising the step of thermally curing and forming an insulating layer having a glass transition temperature of T ₁ (° C.) in this order. The method for producing a printed wiring board according to claim 3, wherein the curing heating temperature is 150°C to 210°C and the preheating temperature is 100°C to 150°C. (A) step is, after (A-3) step,
(A-4) The method for manufacturing the printed wiring board according to any one of claims 2 to 4, further comprising the step of cooling the insulating layer to 30°C or less. (A) the step is
(A-5) The method for manufacturing the printed wiring board according to any one of claims 1 to 5, further comprising the step of perforating the insulating layer or the resin composition layer. 7. The method for manufacturing a printed wiring board according to claim 6, wherein step (A-5) is performed using a laser. 8. The method for producing a printed wiring board according to claim 6, wherein the holes formed in the step (A-5) include those having a top diameter of 100 μm or less. The method for producing a printed wiring board according to any one of claims 1 to 8, wherein the heat treatment time in step (B) is 10 minutes or longer. The method for producing a printed wiring board according to any one of claims 1 to 9, wherein the heat treatment in step (B) is performed by heating the insulating layer in a gas atmosphere. The method for producing a printed wiring board according to any one of claims 1 to 10, further comprising (D) forming a conductor layer on the surface of the insulating layer after the step (C). The method for producing a printed wiring board according to any one of claims 1 to 11, wherein T ₂ (°C) is 100 (°C) or more. The method for producing a printed wiring board according to any one of claims 1 to 12, wherein T ₁ -T ₂ (°C) is -5 (°C) to 10 (°C). The method for producing a printed wiring board according to any one of claims 1 to 13, wherein the resin composition layer further contains an inorganic filler. 15. The method for producing 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 component in the resin composition layer is taken as 100% by mass. The method for producing a printed wiring board according to any one of claims 1 to 15, wherein the resin composition layer further contains a phenoxy resin. The method for producing a printed wiring board according to any one of claims 1 to 16, wherein the resin composition layer further contains a radically polymerizable compound. The method for producing a printed wiring board according to any one of claims 1 to 17, wherein the resin composition layer further contains a cyanate ester curing agent.