Method for manufacturing printed wiring board

Abstract

[Project] Provision of a method for manufacturing a printed circuit board capable of suppressing the occurrence of cracks after desmear treatment (harmonization treatment) [Solution] A method for manufacturing a printed circuit board comprising, in this order, (A) a process of heat-curing a resin composition layer of a laminate having an inner layer substrate and a resin composition layer bonded on the inner layer substrate to form an insulating layer having a glass transition temperature of T1 (°C), (B) a process of heat-treating the insulating layer to T2 (°C), and (C) a process of desmearing the insulating layer with an oxidizing agent solution, wherein the resin composition layer comprises an epoxy resin and an active ester-based curing agent, and also satisfies the following formulas (1) and (2). -20≤T1-T2≤20 (1) 60≤T2≤150 (2)

Description

Technology Field

[0001] The present invention relates to a method for manufacturing a printed circuit board. Background Technology

[0002] As a manufacturing technology for multilayer printed circuit boards, a manufacturing method by a build-up method in which insulating layers and conductive layers are alternately stacked on an inner layer substrate is known. The insulating layer is generally formed by curing a resin composition. For example, Patent Document 1 discloses forming an insulating layer in a printed circuit board using a resin composition comprising a cyanate ester resin, a specific epoxy resin, and an active ester curing agent. Prior art literature

[0003] [Patent Document 1] Japanese Published Patent Application No. JP 2011-144361 The problem to be solved

[0004] Recently, the miniaturization of electronic devices and components has become significant, and accordingly, there is a need to make the insulating layer of printed circuit boards thinner in order to make printed circuit boards even thinner.

[0005] However, it is known that when the insulating layer is thinned, cracks following the shape of the lower copper layer, such as wiring or pads in the inner layer substrate, and cracks around holes drilled by a laser, etc., increase after the desmearing process (discoloration process) in the printed circuit board process.

[0006] The objective of the present invention is to provide a method for manufacturing a printed circuit board that can suppress the occurrence of cracks after desmear treatment (harmonization treatment). means of solving the problem

[0007] In order to achieve the objectives of the present invention, the inventors, after careful consideration, discovered that by using an active ester-based curing agent for the formation of an insulating layer and then heat-treating the insulating layer at a temperature T2 (°C) near its glass transition temperature T1 (°C) (within ±20°C) after the formation of the insulating layer, the occurrence of cracks after desmear treatment (harmonization treatment) can be suppressed, and thus the present invention was completed.

[0008] That is, the present invention includes the following contents.

[0009] [1] (A) A process of heat-curing a resin composition layer of a laminate having 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 T1 (°C).

[0010] (B) A process of heating the insulating layer to T2(°C), and

[0011] (C) Process of desmearing the insulating layer with an oxidizing agent solution

[0012] Includes in this order,

[0013] The resin composition layer comprises an epoxy resin and an active ester-based curing agent, and also

[0014] A method for manufacturing a printed circuit board that satisfies the following formulas (1) and (2).

[0015] -20≤T1-T2≤20 (1)

[0016] 60≤T2≤150 (2)

[0017] [2] (A) The process,

[0018] (A-1) A process for preparing a resin sheet having a support and a resin composition layer provided on the support,

[0019] (A-2) A process of obtaining a laminate by laminating resin sheets so that a resin composition layer is bonded to an inner layer substrate, and

[0020] (A-3) A process of heat-curing a resin composition layer to form an insulating layer with a glass transition temperature T1 (°C).

[0021] A method for manufacturing a printed circuit board as described in [1] above, comprising the above in this order.

[0022] [3] (A-3) The process,

[0023] (A-31) A process of preheating a resin composition layer to a preheating temperature lower than the curing heating temperature, and

[0024] (A-32) A process of heating a resin composition layer to a curing heating temperature to heat-cure the resin composition layer and forming an insulating layer having a glass transition temperature T1 (°C).

[0025] A method for manufacturing a printed circuit board as described in [2] above, comprising the above in this order.

[0026] [4] A method for manufacturing a printed circuit board as described in [3], wherein the curing heating temperature is 150°C to 210°C and the preheating temperature is 100°C to 150°C.

[0027] [5] (A) process, (A-3) after process,

[0028] (A-4) Process of cooling the insulation layer to 30℃ or below

[0029] A method for manufacturing a printed circuit board as described in any one of [2] to [4], further comprising

[0030] [6] (A) The process,

[0031] (A-5) Process of perforating an insulating layer or a resin composition layer

[0032] A method for manufacturing a printed circuit board as described in any one of [1] to [5], further comprising

[0033] [7] (A-5) A method for manufacturing a printed circuit board as described in [6] above, wherein the process is carried out using a laser.

[0034] [8] (A-5) A method for manufacturing a printed circuit board as described in [6] or [7], wherein the holes formed by the process include a top diameter of 100 μm or less.

[0035] [9] (B) A method for manufacturing a printed circuit board as described in any one of [1] to [8], wherein the heat treatment time of the process is 10 minutes or more.

[0036]

[10] (B) A method for manufacturing a printed circuit board as described in any one of [1] to [9], wherein the heat treatment of the process is performed by heating the insulating layer under a gas atmosphere.

[0037]

[11] A method for manufacturing a printed circuit board as described in any one of [1] to

[10] , further comprising (C) a process of forming a conductive layer on the surface of an insulating layer after the process (D).

[0038]

[12] A method for manufacturing a printed circuit board as described in any one of [1] to

[11] , wherein T2(℃) is 100(℃) or higher.

[0039]

[13] A method for manufacturing a printed circuit board as described in any one of [1] to

[12] , wherein T1-T2(℃) is -5(℃) to 10(℃).

[0040]

[14] A method for manufacturing a printed circuit board as described in any one of [1] to

[13] , wherein the resin composition layer further comprises an inorganic filler.

[0041]

[15] A method for manufacturing a printed circuit board as described in

[14] , wherein the content of the inorganic filler is 50 mass% or more when the non-volatile component in the resin composition layer is 100 mass%.

[0042]

[16] A method for manufacturing a printed circuit board as described in any one of [1] to

[15] , wherein the resin composition layer further comprises phenoxy resin.

[0043]

[17] A method for manufacturing a printed circuit board as described in any one of [1] to

[16] , wherein the resin composition layer further comprises a radical polymerizable compound.

[0044]

[18] A method for manufacturing a printed circuit board as described in any one of [1] to

[17] , wherein the resin composition layer further comprises a cyanate ester-based curing agent. Effects of the invention

[0045] According to the present invention, a method for manufacturing a printed circuit board that can suppress the occurrence of cracks after desmear treatment (harmonization treatment) can be provided. Specific details for implementing the invention

[0046] The present invention will be described in detail below based on suitable embodiments. However, the present invention is not limited to the following embodiments and examples, and may be implemented with arbitrary modifications without departing from the scope of the claims of the present invention and the scope of equivalents.

[0047] Method for manufacturing a printed circuit board

[0048] The method for manufacturing a printed circuit board of the present invention is,

[0049] (A) A process of heat-curing a resin composition layer of a laminate having 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 T1(°C),

[0050] (B) A process of heating the insulating layer to T2(°C), and

[0051] (C) Process of desmearing the insulating layer with an oxidizing agent solution

[0052] Includes in this order,

[0053] The resin composition layer comprises an epoxy resin and an active ester-based curing agent, and also

[0054] The following equations (1) and (2) are satisfied together.

[0055] -20≤T1-T2≤20 (1)

[0056] 60≤T2≤150 (2)

[0057] Here, "≤" indicates that the left value is less than or equal to the right value.

[0058] According to this manufacturing method, the occurrence of cracks after desmear treatment (harmonization treatment) can be suppressed. This is presumed to be due to the stress accumulated inside the insulating layer being gradually relieved by the thermal curing of the resin composition layer by heating the insulating layer to a temperature T2 (°C) near its glass transition temperature T1 (°C) (within ±20°C) after forming the insulating layer.

[0059] Hereinafter, each process in the method for manufacturing a printed circuit board of the present invention will be described.

[0060] <(A) Process>

[0061] (A) In the process, the resin composition layer of a laminate comprising an inner layer substrate and a resin composition layer bonded to the inner layer substrate is heat-cured to form an insulating layer having a glass transition temperature of T1 (°C).

[0062] (A) The process preferably includes the following processes (A-1) to (A-3) in this order.

[0063] (A-1) A process for preparing a resin sheet having a support and a resin composition layer provided on the support.

[0064] (A-2) A process of obtaining a laminate by laminating resin sheets so that a resin composition layer is bonded to an inner layer substrate.

[0065] (A-3) A process of heat-curing a resin composition layer to form an insulating layer with a glass transition temperature T1 (°C).

[0066] (A-1) In the process, a resin sheet is prepared having a support and a resin composition layer formed on the support.

[0067] A resin sheet can be manufactured, for example, by applying a varnish-like resin composition onto a support using a coating device such as a die coater, and further drying it as needed to form a resin composition layer.

[0068] Drying may be carried out by known methods such as heating or hot air spraying. Although the drying conditions are not particularly limited, drying is performed so that the content of the organic solvent in the resin composition layer is 10 mass% or less, preferably 5 mass% or less. Depending on the boiling point of the organic solvent in the varnish-type resin composition, for example, when using a resin composition containing 30 mass% to 60 mass% of organic solvent, a resin composition layer can be formed by drying at 50°C to 150°C (preferably 80°C to 120°C) for 1 minute to 10 minutes.

[0069] Examples of supports used for resin sheets include films made of plastic materials, metal foils, and release papers, and films made of plastic materials and metal foils are preferred.

[0070] When a film made of a plastic material is used as a support, examples of plastic materials include polyesters such as polyethylene terephthalate (hereinafter abbreviated as "PET") and polyethylene naphthalate (hereinafter abbreviated as "PEN"), acrylics such as polymethyl methacrylate (PMMA), cyclic polyolefins, triacetylcellulose (TAC), polyether sulfide (PES), polyether ketone, and polyimide. Among these, polyethylene terephthalate and polyethylene naphthalate are preferred, and inexpensive polyethylene terephthalate is particularly preferred.

[0071] When using a metal foil as a support, examples of metal foils include copper foil and aluminum foil, and copper foil is preferred. As for the copper foil, a foil made of copper may be used, or a foil made of an alloy of copper and other metals (e.g., tin, chromium, silver, magnesium, nickel, zirconium, silicon, titanium, etc.) may be used.

[0072] The support may be subjected to mat treatment, corona treatment, or antistatic treatment on the surface bonded to the resin composition layer.

[0073] In addition, as a support, a support with a release layer attached having a release layer on the surface bonded to the resin composition layer may be used. As for the release agent used in the release layer of the support with the release layer attached, for example, one or more release agents selected from the group consisting of alkyd resin, polyolefin resin, urethane resin, and silicone resin may be used. As for the support with the release layer attached, commercially available products may be used, and examples include PET films having a release layer mainly composed of an alkyd resin-based release agent, such as "SK-1," "AL-5," and "AL-7" manufactured by Lintec, "Lumira T60" manufactured by Tore, "Purex" manufactured by Teijin, and "Unifil" manufactured by Unitica.

[0074] The thickness of the support is not particularly limited, but a range of 5㎛ to 75㎛ is preferred, and a range of 10㎛ to 60㎛ is more preferred. In addition, when using a support with a release layer attached, it is preferable that the total thickness of the support with the release layer attached is within the above range.

[0075] In the resin sheet, a protective film equivalent to the support may be additionally laminated on the side of the resin composition layer that is not bonded to the support (i.e., the side opposite to the support). The thickness of the protective film is not particularly limited, but for example, it is 1 μm to 40 μm. By laminating the protective film, the adhesion of dust or the like to the surface of the resin composition layer and scratches can be prevented. Such a resin sheet can be stored by winding it into a roll shape. If the resin sheet has a protective film, the protective film is peeled off and then laminated onto an inner layer substrate.

[0076] (A-2) In the process, resin sheets are laminated so that a resin composition layer is bonded to an inner layer substrate, thereby obtaining a laminate.

[0077] An inner layer substrate is a material that serves as a substrate for a printed circuit board, and examples include glass epoxy substrates, metal substrates, polyester substrates, polyimide substrates, BT resin substrates, thermosetting polyphenylene ether substrates, etc. In addition, the substrate may have a conductive layer on one or both sides thereof, and the conductive layer may be patterned. Furthermore, intermediate products on which an insulating layer and / or a conductive layer must be additionally formed when manufacturing a printed circuit board are also included in the inner layer substrate. When the printed circuit board is a component-embedded circuit board, an inner layer substrate with embedded components may be used.

[0078] A resin sheet is laminated onto an inner layer substrate so that the resin composition layer is bonded to the inner layer substrate, thereby obtaining a laminate. In one embodiment, the lamination of the inner layer substrate and the resin sheet can be performed, for example, by heat-pressing the resin sheet onto the inner layer substrate from the support side. As a member for heat-pressing the resin sheet onto the inner layer substrate (hereinafter also referred to as a "heat-pressing member"), examples include a heated metal plate (such as a SUS hard plate) or a metal roll (such as a SUS roll). Furthermore, rather than pressing the heat-pressing member directly onto the resin sheet, it is preferable to press with an elastic material such as heat-resistant rubber in between so that the resin sheet sufficiently follows the surface irregularities of the inner layer substrate.

[0079] Lamination of the inner layer substrate and the resin sheet may be carried out by a vacuum lamination method. In the vacuum lamination method, the heat pressing temperature is preferably in the range of 60°C to 160°C, more preferably in the range of 80°C to 140°C, the heat pressing pressure is preferably in the range of 0.098 MPa to 1.77 MPa, more preferably in the range of 0.29 MPa to 1.47 MPa, and the heat pressing time is preferably in the range of 10 seconds to 400 seconds, more preferably in the range of 20 seconds to 300 seconds.

[0080] Lamination can be performed using commercially available vacuum laminators. Examples of commercially available vacuum laminators include vacuum pressure laminators manufactured by Meiki Seisakusho Co., Ltd., vacuum applicators manufactured by Nikko Materials Co., Ltd., and batch vacuum pressure laminators.

[0081] After lamination, a smoothing treatment of the laminated resin sheets may be performed under atmospheric pressure, for example, by pressing a heat-pressing member from the support side. The pressing conditions for the smoothing treatment may be the same as the heat-pressing conditions for the lamination. The smoothing treatment may be performed using a commercially available laminator. Furthermore, lamination and the smoothing treatment may be performed continuously using the commercially available vacuum laminator mentioned above.

[0082] (A-3) In the process, the resin composition layer is heat-cured to form an insulating layer with a glass transition temperature of T1 (°C).

[0083] The curing heating temperature of the resin composition layer varies depending on the type of resin composition, but is preferably 100°C or higher, more preferably 150°C or higher, and even 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.

[0084] The curing heating time of the resin composition layer varies depending on the type of resin composition, but is preferably 5 minutes or more, more preferably 10 minutes or more, and even more preferably 15 minutes or more. The upper limit is not particularly limited, but is preferably 120 minutes or less, more preferably 100 minutes or less, and even more preferably 90 minutes or less. The curing heating time of the resin composition layer refers to the time for maintaining the curing heating temperature of the resin composition layer. Thermal curing is typically performed under a gas atmosphere (e.g., air, argon gas, nitrogen gas, or a mixture thereof) and is performed under a pressure of, for example, 0.05 MPa to 0.15 MPa, preferably 0.08 to 0.12 MPa.

[0085] (A-3) It is preferable that the following (A-31) and (A-32) processes be included in this order.

[0086] (A-31) A process of preheating a resin composition layer to a preheating temperature lower than the curing heating temperature, and

[0087] (A-32) A process of heating a resin composition layer to a curing heating temperature to heat-cure the resin composition layer and forming an insulating layer having a glass transition temperature T1 (°C).

[0088] The preheating temperature of the resin composition layer is preferably 50°C or higher, more preferably 100°C or higher, even more preferably 120°C or higher, preferably 160°C or lower, more preferably 150°C or lower, and even more preferably 140°C or lower. The preheating time of the resin composition layer is preferably 5 minutes or more, more preferably 10 minutes or more, even more preferably 15 minutes or more, preferably 150 minutes or less, more preferably 130 minutes or less, and even more preferably 120 minutes or less. Preheating is typically performed under a gaseous atmosphere (e.g., air, argon gas, nitrogen gas, or a mixture thereof) and under a pressure of, for example, 0.05 MPa to 0.15 MPa, preferably 0.08 to 0.12 MPa.

[0089] The glass transition temperature (T1) of the insulating layer formed by heat curing may be preferably 60°C or higher, more preferably 70°C or higher, even more preferably 80°C or higher, even more preferably 90°C or higher, even more preferably 100°C or higher, particularly preferably 110°C or higher, with respect to the heat resistance of the insulating layer, and the upper limit may be preferably 160°C or lower, more preferably 150°C or lower, although the upper limit is not particularly limited.

[0090] Between process (A-31) and process (A-32), heating may be performed continuously without returning to room temperature (preferably by raising the temperature from the preheating temperature to the curing temperature), or a process of additionally cooling the insulating layer (A-33) to 30°C or lower may be included after process (A-31) and before process (A-32). The cooling temperature of process (A-33) may preferably be 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 cooled by air cooling, or by blowing cold air onto the insulating layer, or by bringing the insulating layer into contact with a cooled roll. Cooling of process (A-33) is typically performed under a gas atmosphere (e.g., air, argon gas, nitrogen gas, or a mixture thereof) and under a pressure of, for example, 0.05 MPa to 0.15 MPa, preferably 0.08 to 0.12 MPa.

[0091] (A-3) The thickness of the insulating layer formed by the heat curing of the process depends on the thickness of the resin composition layer of the prepared resin sheet, but for example, it is 200 μm or less, preferably 100 μm or less, more preferably 80 μm or less, even more preferably 60 μm or less, particularly preferably 50 μm or less, and the lower limit is not particularly limited, but can be 1 μm or more, 5 μm or more, 10 μm or more, etc.

[0092] (A) The process preferably includes an additional process of cooling the (A-4) insulating layer to 30°C or lower after the (A-3) process.

[0093] By performing process (A-4), the stress generated by the thermal curing of the resin composition can be suppressed. Therefore, the residual stress in the insulating layer during process (B) can be further suppressed, thereby effectively suppressing the occurrence of cracks. The cooling temperature of process (A-4) may preferably be 10°C to 30°C, more preferably 20°C to 30°C. The cooling method is not particularly limited; the insulating layer may be cooled by air cooling, or by blowing cold air onto the insulating layer, or by bringing the insulating layer into contact with a cooled roll. Cooling of process (A-4) is typically performed under a gas atmosphere (e.g., air, argon gas, nitrogen gas, or a mixture thereof) and under a pressure of, for example, 0.05 MPa to 0.15 MPa, preferably 0.08 to 0.12 MPa.

[0094] (A) The process preferably further includes (A-5) a process of perforating the insulating layer or the resin composition layer. (A-5) may be included, for example, after process (A-31) (preferably after process (A-33) if process (A-33) is included) or before process (A-32) or after process (A-3) (preferably after process (A-4) if process (A-4) is included).

[0095] (A-5) The process may be carried out according to various methods known to those skilled in the art used in the manufacture of printed circuit boards. Through the process (A-5), via holes and through holes can be formed in the insulating layer (resin composition layer). The process (A-5) may be carried out using, for example, a drill, a laser (CO2 laser, YAG laser, etc.), plasma, etc. It is preferable that the process (A-5) be carried out using a laser.

[0096] (A-5) The hole (via hole, through hole) formed by the process may be in a shape that penetrates the insulating layer (resin composition layer). (A-5) The shape of the hole (via hole, through hole) formed by the process is not particularly limited, but may be, for example, circular (approximately circular). (A-5) The hole (via hole, through hole) formed by the process may include 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).

[0097] <(B) Process>

[0098] (B) Process heat-treats the insulating layer to T2 (°C). By performing process (B), the occurrence of cracks after process (C) can be suppressed. This is presumed to be because stress dependent on the pattern shape of the inner layer substrate can be relieved.

[0099] (B) The heat treatment temperature (T2) of the process is preferably a temperature lower than the curing temperature of the resin composition layer in process (A). The heat treatment temperature (T2) is 60°C or higher and 150°C or lower, and from the view of further suppressing the occurrence of cracks, it is preferably 70°C or higher, more preferably 80°C or higher, even more preferably 90°C or higher, and particularly preferably 100°C or higher.

[0100] The difference (T1-T2) between the glass transition temperature (T1) of the insulating layer and the heat treatment temperature (T2) is 20°C or less, preferably 15°C or less, more preferably 10°C or less, particularly preferably 5°C or less, and the lower limit of T1-T2 is -20°C or more, preferably -15°C or more, more preferably -10°C or more, even more preferably -5°C or more, and particularly preferably 0°C or more.

[0101] (B) The heat treatment time of the process is preferably 1 minute or more, more preferably 10 minutes or more, and even more preferably 20 minutes or more, from the perspective of suppressing the occurrence of cracks. The upper limit is not specifically limited, but, for example, 120 minutes or less, 90 minutes or less, etc. The heat treatment time refers to the time for maintaining the heat treatment temperature.

[0102] (B) The heat treatment of the process may be performed by heating the insulating layer in a gaseous atmosphere or by heating the insulating layer by immersing it in a liquid, but it is preferable to perform it by heating the insulating layer in a gaseous atmosphere. The heat treatment is performed under a pressure of, for example, 0.05 MPa to 0.15 MPa, preferably 0.08 to 0.12 MPa.

[0103] As the gas used when heating under a gaseous atmosphere, air, argon gas, nitrogen gas, or a mixture thereof may be used.

[0104] As the liquid used for heating in a liquid, a liquid with a boiling point higher than the heat treatment temperature (T2) may be used. For example, the swelling liquid described below may be used as such a liquid. When using the swelling liquid, the heating temperature may be set to the heat treatment temperature (T2), and the pH may be preferably 6 or higher, more preferably 6.5 or higher, even more preferably 7 or higher, preferably 14 or lower, even more preferably 13.5 or lower, 12 or lower, 12.5 or lower, 11 or lower, 10 or lower, 8 or lower, or 7.5 or lower.

[0105] (B) The process may include a process of heating the insulating layer to T2 (°C) and then cooling the insulating layer to 30°C or lower. The cooling temperature of the process may preferably be 10°C to 30°C, more preferably 20°C to 30°C. The method of cooling is not particularly limited and may be cooled by blowing cold air onto the insulating layer, or by bringing the insulating layer into contact with a cooled roll. The cooling of the process is typically performed under a gas atmosphere (e.g., air, argon gas, nitrogen gas, or a mixture thereof) and under a pressure of, for example, 0.05 MPa to 0.15 MPa, preferably 0.08 to 0.12 MPa.

[0106] The heat treatment may be performed once or twice. In the case of performing the heat treatment twice, as an example of one embodiment, the first heat treatment of the insulating layer is performed at T2 (°C), then the insulating layer is cooled to 30°C or lower, and then the heat treatment of the insulating layer is performed again at T2 (°C). The cooling temperature and the cooling method are the same as above. The temperature and time of the second heat treatment may be different from those of the first.

[0107] <(C) Process>

[0108] (C) The process involves desmearing the insulating layer with an oxidizing agent solution. The order and conditions of the desmearing treatment are not particularly limited, and known order and conditions commonly used when forming an insulating layer of a printed circuit board may be adopted. The desmearing treatment can be performed, for example, by immersing the insulating layer in an oxidizing agent solution.

[0109] As an oxidizing agent solution, an oxidizing agent solution used in conventional desmear treatment may be used. Examples of such oxidizing agent solutions include an alkaline permanganate solution in which potassium permanganate or sodium permanganate is dissolved as an oxidizing agent in an aqueous solution of sodium hydroxide. In addition, the oxidizing agent concentration of the oxidizing agent solution is preferably 3 mass% or more, more preferably 5 mass% or more, and even more preferably 7 mass% or more; preferably 20 mass% or less, more preferably 15 mass% or less, and even more preferably 10 mass% or less.

[0110] For the oxidizing agent solution, commercially available products may be used. Examples of commercially available oxidizing agent solutions include alkaline permanganate solutions such as "Concentrate Compact CP" and "Dosing Solution Securigans P" manufactured by Atotech Japan.

[0111] It is preferable to heat the oxidizing agent solution when immersing the insulating layer. The heating temperature of the oxidizing agent solution is preferably 60°C or higher, more preferably 65°C or higher, even more preferably 70°C or higher, preferably 100°C or lower, more preferably 95°C or lower, and even more preferably 90°C or lower.

[0112] The immersion time of the insulating layer in the oxidizing agent solution is preferably 5 minutes or more, more preferably 10 minutes or more, even more preferably 15 minutes or more, preferably 40 minutes or less, more preferably 30 minutes or less, and even more preferably 25 minutes or less.

[0113] (C) In the process, before desmearing the insulating layer with an oxidizing agent solution, the insulating layer may be immersed in a swelling solution to perform swelling treatment.

[0114] Examples of swelling solutions include water, aqueous sodium hydroxide solution, aqueous potassium hydroxide solution, etc. Among these, water is preferred as the swelling solution, and water is more preferred. Commercially available products may be used as the swelling solution. Examples of commercially available products include "Swelling Deep Securigans P" and "Swelling Deep Securigans SBU" manufactured by Atotech Japan.

[0115] It is preferable to heat the swelling liquid when immersing the insulating layer. The heating temperature of the swelling liquid is preferably 30°C or higher, more preferably 35°C or higher, even more preferably 40°C or higher, preferably 100°C or lower, more preferably 95°C or lower, and even more preferably 90°C or lower.

[0116] The immersion time of the insulating layer in the swelling liquid is preferably 1 minute or more, more preferably 3 minutes or more, even more preferably 5 minutes or more, preferably 40 minutes or less, more preferably 30 minutes or less, and even more preferably 25 minutes or less.

[0117] The pH of the swelling solution is preferably 6 or higher, more preferably 6.5 or higher, even more preferably 7 or higher, preferably 14 or lower, even more preferably 13.5 or lower, 12 or lower, 12.5 or lower, 11 or lower, 10 or lower, 8 or lower, and 7.5 or lower.

[0118] (C) In the process, after desmearing the insulating layer with an oxidizing agent solution, the insulating layer may be immersed in a neutralizing solution to perform neutralization treatment in order to remove residues of the oxidizing agent salt.

[0119] It is preferable to use an acidic aqueous solution as the neutralizing solution. Commercially available products may be used as the neutralizing solution; examples of commercially available neutralizing solutions include "Reduction Solution Securigant P" manufactured by Atotech Japan.

[0120] It is preferable to heat the neutralizing solution when immersing the insulating layer. The heating temperature of the neutralizing solution is preferably 30°C or higher, more preferably 35°C or higher, preferably 80°C or lower, more preferably 70°C or lower, and even more preferably 60°C or lower, from the perspective of removing residues of the oxidizing agent salt.

[0121] The immersion time of the insulating layer in the neutralizing solution is preferably 1 minute or more, more preferably 3 minutes or more, from the perspective of removing residues of the oxidizing agent salt, etc., and preferably 30 minutes or less, more preferably 20 minutes or less.

[0122] (C) In the process, the insulating layer may be desmeared with an oxidizing agent solution (or the insulating layer may be neutralized by immersing it in a neutralizing solution), and then dried in the atmosphere.

[0123] The drying temperature is preferably 40°C or higher, more preferably 60°C or higher, preferably 120°C or lower, more preferably 100°C or lower. The drying time is preferably 10 minutes or more, more preferably 20 minutes or more, preferably 60 minutes or less, more preferably 40 minutes or less.

[0124] <(D) Process>

[0125] The method for manufacturing a printed circuit board of the present invention may further include, after process (C), a process of forming a conductor layer on the surface of an insulating layer (D).

[0126] (D) The conductor material used in the conductor layer in the process is not particularly limited. In a suitable embodiment, the conductor layer comprises one or more metals selected from the group consisting of gold, platinum, palladium, silver, copper, aluminum, cobalt, chromium, zinc, nickel, titanium, tungsten, iron, tin, and indium. The conductor layer may be a single metal layer or an alloy layer, and as an alloy layer, for example, a layer formed of an alloy of two or more metals selected from the above group (e.g., nickel-chromium alloy, copper-nickel alloy, and copper-titanium alloy) may be used. Among these, from the perspective of ease of forming a conductor layer, cost, and ease of pattern processing, a single metal layer of chromium, nickel, titanium, aluminum, zinc, gold, palladium, silver, or copper, or an alloy layer of a nickel-chromium alloy, a copper-nickel alloy, or a copper-titanium alloy is preferred, a single metal layer of chromium, nickel, titanium, aluminum, zinc, gold, palladium, silver, or copper, or an alloy layer of a nickel-chromium alloy is more preferred, and a single metal layer of copper is even more preferred.

[0127] The conductor layer may have a single-layer structure, or a multilayer structure in which two or more single-metal layers or alloy layers made of different types of metals or alloys are stacked. In the case where 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.

[0128] The thickness of the conductor layer is, depending on the design of the desired printed circuit board, generally 3㎛ to 35㎛, preferably 5㎛ to 30㎛.

[0129] In one embodiment, the conductor layer may be formed by plating. For example, a conductor layer having a desired wiring pattern can be formed by plating on the surface of an insulating layer using conventionally known techniques such as the semi-additive method or the full-additive method; however, from the perspective of ease of manufacturing, it is preferable to form it by the semi-additive method. Below, an example of forming a conductor layer by the semi-additive method is shown.

[0130] First, a plating seed layer is formed on the surface of an 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 by electroplating on the exposed plating seed layer, the mask pattern is removed. Then, the unnecessary plating seed layer is removed by etching or the like to form a conductor layer having a desired wiring pattern.

[0131] The support may be removed during process (A) (e.g., between process (A-2) and process (A-3), between process (A-2) and process (A-3), between process (A-3) and process (A-4), or between process (A-4) and process (A-5), between process (A) and process (B), or between process (B) and process (C). It is preferable that the support be removed between process (B) and process (C). Additionally, after the completion of each process, a washing treatment may be performed as necessary.

[0132] <Resin composition layer>

[0133] Hereinafter, the components included 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) will be described.

[0134] The resin composition layer comprises (a) an epoxy resin and (b) an active ester-based curing agent.

[0135] <(a) Epoxy resin>

[0136] (a) Epoxy resin is a curable resin having epoxy groups. The epoxy resin (a) described herein has an epoxy equivalent of 5,000 g / eq. or less.

[0137] (a) As epoxy resins, 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, trisphenol-type epoxy resin, naphthol novolak-type epoxy resin, phenol novolak-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 novolak-type epoxy resin, phenol aralkil-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, Examples include tetraphenylethane-type epoxy resin, isocyanurite-type epoxy resin, phenolphthalimidine-type epoxy resin, etc. (a) The epoxy resin may be used as a single type or in combination of two or more types.

[0138] The resin composition layer preferably comprises (a) an epoxy resin having two or more epoxy groups in one molecule. With respect to 100 mass% of the non-volatile component of (a) the epoxy resin, the ratio of the epoxy resin having two or more epoxy groups in one molecule is preferably 50 mass% or more, more preferably 60 mass% or more, and particularly preferably 70 mass% or more.

[0139] Epoxy resins include liquid epoxy resin at a temperature of 20°C (hereinafter referred to as "liquid epoxy resin") and solid epoxy resin at a temperature of 20°C (hereinafter referred to as "solid epoxy resin"). The resin composition layer may contain only liquid epoxy resin, or only solid epoxy resin, or both liquid epoxy resin and solid epoxy resin, but it is preferable to contain both liquid epoxy resin and solid epoxy resin.

[0140] As for the liquid epoxy resin, a liquid epoxy resin having two or more epoxy groups in one molecule is preferred.

[0141] As liquid epoxy resins, glycirol-type epoxy resin, bisphenol A-type epoxy resin, bisphenol F-type epoxy resin, bisphenol AF-type epoxy resin, naphthalene-type epoxy resin, glycidyl ester-type epoxy resin, glycidylamine-type epoxy resin, phenol novolak-type epoxy resin, alicyclic epoxy resin having an ester backbone, cyclohexanedimethanol-type epoxy resin, cyclic aliphatic glycidyl ether, and epoxy resin having a butadiene structure are preferred.

[0142] Specific examples of liquid epoxy resins include “EX-992L” manufactured by Nagase Chemtex, “YX7400” manufactured by Mitsubishi Chemical, “HP4032”, “HP4032D”, and “HP4032SS” manufactured by DIC (naphthalene-type epoxy resin); “828US”, “828EL”, “825”, and “Epicote 828EL” manufactured by Mitsubishi Chemical (bisphenol A-type epoxy resin); “jER807” and “1750” manufactured by Mitsubishi Chemical (bisphenol F-type epoxy resin); “jER152” manufactured by Mitsubishi Chemical (phenol novolak-type epoxy resin); and “630”, “630LSD”, and “604” manufactured by Mitsubishi Chemical (glycidylamine-type epoxy resin). "ED-523T" (glycirol-type epoxy resin) manufactured by ADEKA; "EP-3950L" and "EP-3980S" (glycidylamine-type epoxy resins) manufactured by ADEKA; "EP-4088S" (dicyclopentadiene-type epoxy resin) manufactured by ADEKA; "ZX1059" (mixture of bisphenol A-type epoxy resin and bisphenol F-type epoxy resin) manufactured by Nittetsu Chemical & Materials; "EX-721" (glycidyl ester-type epoxy resin) manufactured by Nagase Chemtex; "EX-991L" (epoxy resin containing alkyleneoxy skeleton and butadiene skeleton) manufactured by Nagase Chemtex; "Celoxide 2021P" (alicycloepoxy resin having an ester skeleton) manufactured by Daicel; Examples include “PB-3600” manufactured by Daicel, “JP-100”, “JP-200”, and “JP-400” (epoxy resin having a butadiene structure) manufactured by Nippon Soda; “ZX1658” and “ZX1658GS” (liquid 1,4-glycidylcyclohexane type epoxy resin) manufactured by Nittetsu Chemical & Material; “EG-280” (epoxy resin containing a fluorene structure) manufactured by Osaka Gas Chemical; and “EX-201” (cyclic aliphatic glycidyl ether) manufactured by Nagase Chemtex.

[0143] As for the solid epoxy resin, a solid epoxy resin having three or more epoxy groups in one molecule is preferred, and an aromatic solid epoxy resin having three or more epoxy groups in one molecule is more preferred.

[0144] As for solid epoxy resins, 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, naphtylene 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, and phenolphthalimidine-type epoxy resin are preferred.

[0145] Specific examples of solid-phase epoxy resins include “HP4032H” (naphthalene-type epoxy resin) manufactured by DIC; “HP-4700” and “HP-4710” (naphthalene-type tetrafunctional epoxy resins) manufactured by DIC; “N-690” (cresol novolak-type epoxy resin) manufactured by DIC; “N-695” (cresol novolak-type epoxy resin) manufactured by DIC; and “HP-7200”, “HP-7200HH”, “HP-7200H”, and “HP-7200L” (dicyclopentadiene-type epoxy resins) manufactured by DIC. "EXA-7311", "EXA-7311-G3", "EXA-7311-G4", "EXA-7311-G4S", "HP6000", "HP6000L" (naphtylene ether type epoxy resin) manufactured by DIC; "EPPN-502H" (trisphenol type epoxy resin) manufactured by Nihon Kayaku; "NC7000L" (naphthol novolac type epoxy resin) manufactured by Nihon Kayaku; "NC3000H", "NC3000", "NC3000L", "NC3000FH", "NC3100" (biphenyl type epoxy resin) manufactured by Nippon Kayaku; "ESN475V", "ESN4100V" (naphthalene type epoxy resin) manufactured by Nittetsu Chemical & Materials; "ESN485" (naphthol-type epoxy resin) manufactured by Nittetsu Chemical & Materials; "ESN375" (dihydroxynaphthalene-type epoxy resin) manufactured by Nittetsu Chemical & Materials; "YX4000H", "YX4000", "YX4000HK", "YL7890" (bicylenol-type epoxy resin) manufactured by Mitsubishi Chemical; "YL6121" (biphenyl-type epoxy resin) manufactured by Mitsubishi Chemical; "YX8800" (anthracene-type epoxy resin) manufactured by Mitsubishi Chemical; "YX7700" (phenol-aralkyl-type epoxy resin) manufactured by Mitsubishi Chemical; "PG-100", "CG-500" manufactured by Osaka Gas Chemical; "YL7760" (Bisphenol AF type epoxy resin) manufactured by Mitsubishi Chemical Corporation; "YL7800" (Fluorene type epoxy resin) manufactured by Mitsubishi Chemical Corporation; "jER1010" (Bisphenol A type epoxy resin) manufactured by Mitsubishi Chemical Corporation;Examples include "jER1031S" (tetraphenylethane-type epoxy resin) manufactured by Mitsubishi Chemical Corporation and "WHR991S" (phenolphthalimidine-type epoxy resin) manufactured by Nippon Kayaku Corporation. These may be used individually or in combination of two or more types.

[0146] (a) When a combination of solid epoxy resin and liquid epoxy resin is used as the epoxy resin, the mass ratio of the two (solid epoxy resin:liquid epoxy resin) is preferably 10:1 to 1:50, more preferably 2:1 to 1:20, and particularly preferably 1:1 to 1:10.

[0147] (a) The epoxy equivalent of the epoxy resin is preferably 50 g / eq. to 5,000 g / eq., more preferably 60 g / eq. to 2,000 g / eq., even more preferably 70 g / eq. to 1,000 g / eq., and even more preferably 80 g / eq. to 500 g / eq. The epoxy equivalent is the mass of the resin per epoxy group equivalent. This epoxy equivalent can be measured according to JIS K7236.

[0148] (a) The weight average molecular weight (Mw) of the epoxy resin is preferably 100 to 5,000, more preferably 250 to 3,000, and even more preferably 400 to 1,500. The weight average molecular weight of the resin can be measured as a polystyrene equivalent value by gel permeation chromatography (GPC).

[0149] The content of (a) epoxy resin in the resin composition layer is not particularly limited, but when the non-volatile component in the resin composition layer is 100 mass%, it is preferably 70 mass% or less, more preferably 50 mass% or less, even more preferably 30 mass% or less, and particularly preferably 20 mass% or less. The lower limit of the content of (a) epoxy resin in the resin composition layer is not particularly limited, but when the non-volatile component in the resin composition layer is 100 mass%, it is preferably 0.1 mass% or more, more preferably 1 mass% or more, even more preferably 5 mass% or more, and particularly preferably 10 mass% or more.

[0150] <(b) Active ester-based curing agent>

[0151] (b) The active ester-based curing agent is an epoxy resin curing agent capable of reacting with and curing the epoxy resin (a). (b) The active ester-based curing agent may be used as a single type, or two or more types may be used in combination.

[0152] (b) As an active ester-based curing agent, compounds having two or more highly reactive ester groups in one molecule, such as phenol esters, thiophenol esters, N-hydroxyamine esters, and esters of heterocyclic hydroxy compounds, are 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. Particularly, from the perspective 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 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, pyromellitic acid, etc. Examples of phenol compounds or naphthol compounds include hydroquinone, resorcinol, bisphenol A, bisphenol F, bisphenol S, phenolphthalein, methylated bisphenol A, methylated bisphenol F, methylated bisphenol S, phenol, o-cresol, m-cresol, p-cresol, catechol, α-naphthol, β-naphthol, 1,5-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, dihydroxybenzophenone, trihydroxybenzophenone, tetrahydroxybenzophenone, phloroglucine, benzenetriol, dicyclopentadiene-type diphenol compounds, phenol novolac, etc. Here, "dicyclopentadiene-type diphenol compound" refers to a diphenol compound obtained by condensing two molecules of phenol with one molecule of dicyclopentadiene.

[0153] (b) As an active ester-based curing agent, specifically, a dicyclopentadiene-type active ester compound, a naphthalene-type active ester compound containing a naphthalene structure, an active ester compound containing an acetylated compound of phenol novolac, and an active ester compound containing a benzoylated compound of phenol novolac are preferred, and among these, at least one selected from a dicyclopentadiene-type active ester compound and a naphthalene-type active ester compound is more preferred. As a dicyclopentadiene-type active ester compound, an active ester compound containing a dicyclopentadiene-type diphenol structure is preferred.

[0154] (b) As commercially available active ester-based curing agents, active ester compounds containing a dicyclopentadiene-type diphenol structure include “EXB9451”, “EXB9460”, “EXB9460S”, “HPC-8000L-65TM”, “HPC-8000-65T”, “HPC-8000H”, “HPC-8000H-65TM” (manufactured by DIC); active ester compounds containing a naphthalene structure include “HP-B-8151-62T”, “EXB-8100L-65T”, “EXB-9416-70BK”, “HPC-8150-62T”, “EXB-8” (manufactured by DIC); Examples of phosphorus-containing active ester compounds include “EXB9401” (manufactured by DIC Corporation), active ester compounds that are acetylated compounds of phenol novolak such as “DC808” (manufactured by Mitsubishi Chemical Corporation), active ester compounds that are benzoylated compounds of phenol novolak such as “YLH1026”, “YLH1030”, and “YLH1048” (manufactured by Mitsubishi Chemical Corporation), and active ester compounds containing styryl groups and naphthalene structures such as “PC1300-02-65MA” (manufactured by Air Water Corporation).

[0155] (b) The active ester group equivalent of the active ester-based curing agent is preferably 50 g / eq. to 500 g / eq., more preferably 50 g / eq. to 400 g / eq., and even more preferably 100 g / eq. to 300 g / eq. The active ester group equivalent is the mass of (b) the active ester-based curing agent per 1 equivalent of the active ester group.

[0156] The content of (b) active ester-based curing agent in the resin composition layer is not particularly limited, but when the non-volatile component in the resin composition layer is 100 mass%, it is preferably 70 mass% or less, more preferably 50 mass% or less, even more preferably 30 mass% or less, and particularly preferably 25 mass% or less. The lower limit of the content of (b) active ester-based curing agent in the resin composition layer is not particularly limited, but when the non-volatile component in the resin composition layer is 100 mass%, it may be preferably 1 mass% or more, more preferably 3 mass% or more, even more preferably 5 mass% or more, and particularly preferably 7 mass% or more.

[0157] <(b') Other curing agents>

[0158] The resin composition layer may contain (b') other curing agents as optional components in addition to (b) active ester-based curing agents. The (b') other curing agents described herein are components other than those corresponding to the (b) active ester-based curing agents described above. (b') other curing agents may be used as a single type or in a combination of two or more types. (b') other curing agents are epoxy resin curing agents that, like (b) active ester-based curing agents, can have the function of reacting with (a) epoxy resin to cure it.

[0159] (b') Other curing agents are not particularly limited, but examples include phenolic curing agents, carbodiimide curing agents, acid anhydride curing agents, amine curing agents, benzoxazine curing agents, cyanate ester curing agents, and thiol curing agents. The resin composition layer preferably includes one or more curing agents selected from phenolic curing agents, carbodiimide curing agents, and cyanate ester curing agents as (b') other curing agents, more preferably includes one or more curing agents selected from phenolic curing agents and cyanate ester curing agents, and particularly preferably includes a cyanate ester curing agent.

[0160] As for phenolic curing agents, a phenolic curing agent having a novolak structure is preferred in terms of heat resistance and water resistance. In addition, a nitrogen-containing phenolic curing agent is preferred in terms of adhesion to the substrate, and a triazine-frame-containing phenolic curing agent is more preferred. Among these, a triazine-frame-containing phenol novolak resin is preferred in terms of highly satisfying heat resistance, water resistance, and adhesion. Specific examples of phenolic curing agents include, for instance, “MEH-7700”, “MEH-7810”, “MEH-7851” manufactured by Meiwa Kasei Co., Ltd., “NHN”, “CBN”, “GPH” manufactured by Nippon Kayaku Co., Ltd., “SN-170”, “SN-180”, “SN-190”, “SN-475”, “SN-485”, “SN-495”, “SN-375”, “SN-395” manufactured by Nittetsu Chemical & Material Co., Ltd., and “LA-7052”, “LA-7054”, “LA-3018”, “LA-3018-50P”, “LA-1356”, “TD2090”, “KA-1160” manufactured by DIC Co., Ltd.

[0161] As a carbodiimide-based curing agent, examples include a curing agent having one or more, preferably two or more, carbodiimide structures within one molecule, such as aliphatic biscarbodiimides such as tetramethylene-bis(t-butylcarbodiimide) and cyclohexanebis(methylene-t-butylcarbodiimide); biscarbodiimides such as aromatic biscarbodiimides such as phenylene-bis(xylcarbodiimide); and aliphatic polycarbodiimides such as polyhexamethylenecarbodiimide, polytrimethylhexamethylenecarbodiimide, polycyclohexylenecarbodiimide, poly(methylenebiscyclohexylenecarbodiimide), and poly(isophoronecarbodiimide). Examples of polycarbodiimides include aromatic polycarbodiimides such as poly(phenylenecarbodiimide), poly(naphthylenecarbodiimide), poly(tolylenecarbodiimide), poly(methyldiisopropylphenylenecarbodiimide), poly(triethylphenylenecarbodiimide), poly(diethylphenylenecarbodiimide), poly(triisopropylphenylenecarbodiimide), poly(diisopropylphenylenecarbodiimide), poly(xylylenecarbodiimide), poly(tetramethylxylylenecarbodiimide), poly(methylenediphenylenecarbodiimide), and poly[methylenebis(methylphenylene)carbodiimide].

[0162] Examples of commercially available carbodiimide-based 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.; and “Starvacol P,” “Starvacol P400,” and “Hycardil 510” manufactured by Rhein Chem.

[0163] As for acid anhydride-based curing agents, a curing agent having one or more acid anhydride groups in one molecule may be cited, and a curing agent having two or more acid anhydride groups in one molecule is preferred. Specific examples of acid anhydride-based curing agents include phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methylhexahydrophthalic anhydride, methylnadic anhydride, hydrogenated methylnadic anhydride, trialkyltetrahydrophthalic anhydride, dodecenyl anhydride succinic acid, 5-(2,5-dioxotetrahydro-3-furanyl)-3-methyl-3-cyclohexene-1,2-dicarboxylic anhydride, trimellitic anhydride, pyromellitic anhydride, benzophenonetetracarboxylic acid dihydride, biphenyltetracarboxylic acid dihydride, naphthalenetetracarboxylic acid dihydride, oxydiphthalic acid dihydride, 3,3'-4,4'-diphenylsulfonetetracarboxylic acid dihydride, Examples include 1,3,3a,4,5,9b-hexahydro-5-(tetrahydro-2,5-dioxo-3-furanyl)-naphtho[1,2-C]furan-1,3-dione, ethylene glycolbis(anhydrotrimellitate), and polymeric acid anhydrides such as styrene-maleic acid resin copolymerized with styrene and maleic acid. Examples of commercially available acid anhydride curing agents include “HNA-100”, “MH-700”, “MTA-15”, “DDSA”, and “OSA” manufactured by Shin Nippon Ricca; “YH-306” and “YH-307” manufactured by Mitsubishi Chemical; “HN-2200” and “HN-5500” manufactured by Hitachi Kasei; and “EF-30”, “EF-40”, “EF-60”, and “EF-80” manufactured by Clay Valley.

[0164] As an amine-based curing agent, a curing agent having one or more, preferably two or more, amino groups in one molecule may be cited. Examples include aliphatic amines, polyetheramines, alicyclic amines, aromatic amines, etc. Among these, aromatic amines are preferred from the viewpoint of exhibiting the desired effect of the present invention. The amine-based curing agent is preferably a primary amine or a secondary amine, and a primary amine is more preferred. Specific examples of amine-based curing agents include 4,4'-methylenebis(2,6-dimethylaniline), 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylsulfone, 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, Examples include 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, etc. Commercially available amine-based curing agents may be used, for example, "SEIKACURE-S" manufactured by Seika Co., Ltd., "KAYABOND C-200S", "KAYABOND C-100", "KAYABOND AA", "KAYABOND AB", "KAYABOND AS" manufactured by Nihon Kayaku Co., Ltd., and "Epicure W" manufactured by Mitsubishi Chemical Co., Ltd.

[0165] Specific examples of benzoxazine-based curing agents include “JBZ-OP100D” and “ODA-BOZ” manufactured by JFE Chemical Co., Ltd.; “HFB2006M” manufactured by Showa Kobunshi Co., Ltd.; and “Pd” and “Fa” manufactured by Shikoku Kasei Kogyo Co., Ltd.

[0166] Examples of cyanate ester-based curing agents include, for instance, bisphenol A dicyanate, polyphenol cyanate (oligo(3-methylene-1,5-phenylene cyanate)), 4,4'-methylenebis(2,6-dimethylphenylcyanate), 4,4'-ethylidene diphenyl dicyanate, hexafluorobisphenol A dicyanate, 2,2-bis(4-cyanate)phenylpropane, 1,1-bis(4-cyanatephenylmethane), bis(4-cyanate-3,5-dimethylphenyl)methane, 1,3-bis(4-cyanatephenyl-1-(methylethylidene))benzene, bis(4-cyanatephenyl)thioether, and bis(4-cyanatephenyl)ether; polyfunctional cyanate resins derived from phenol novolak and cresol novolak; and prepolymers in which these cyanate resins are partially triazinated. Specific examples of cyanate ester-based curing agents include “PT30” and “PT60” manufactured by Lonza Japan (both phenol-novolak type polyfunctional cyanate ester resins), “BA230”, and “BA230S75” (a prepolymer in which part or all of bisphenol A dicyanate is triazinated and becomes a trimer).

[0167] Examples of thiol-based curing agents include trimethylolpropane tris(3-mercaptopropionate), pentaerythritol tetrakis(3-mercaptobutylate), and tris(3-mercaptopropyl)isocyanurate.

[0168] (b') The reactor equivalent of other curing agent is preferably 50 g / eq. to 3000 g / eq., more preferably 100 g / eq. to 1000 g / eq., even more preferably 100 g / eq. to 500 g / eq., and particularly preferably 100 g / eq. to 300 g / eq. The reactor equivalent is the mass of (b') other curing agent per reactor equivalent.

[0169] The content of (b') other curing agent in the resin composition layer is not particularly limited, but when the non-volatile component in the resin composition layer is 100 mass%, it is preferably 50 mass% or less, more preferably 30 mass% or less, even more preferably 20 mass% or less, and particularly preferably 10 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 non-volatile component in the resin composition layer is 100 mass%, it may be, 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.

[0170] <(c) Inorganic Filler>

[0171] The resin composition layer may contain (c) an inorganic filler as an optional component. (c) The inorganic filler is included in the resin composition layer in a particulate state.

[0172] (c) Inorganic compounds are used as materials for inorganic fillers. (c) Examples of materials for inorganic fillers include silica, alumina, glass, cordierite, silicon oxide, barium sulfate, barium carbonate, talc, clay, mica powder, zinc oxide, hydrotalcite, boehmite, aluminum hydroxide, magnesium hydroxide, calcium carbonate, magnesium carbonate, magnesium oxide, boron nitride, aluminum nitride, manganese nitride, aluminum borate, strontium carbonate, strontium titanate, calcium titanate, magnesium titanate, bismuth titanate, titanium oxide, zirconium oxide, barium titanate, barium zirconate titanate, barium zirconate, calcium zirconate, zirconium phosphate, and zirconium tungstate phosphate. Among these, silica is particularly suitable. Examples of silica include amorphous silica, fused silica, crystalline silica, synthetic silica, hollow silica, etc. In addition, spherical silica is preferred as silica. (c) The inorganic filler may be used as a single type, or two or more types may be used in combination in any ratio.

[0173] (c) Examples of commercially available inorganic fillers include, for instance, “SP60-05” and “SP507-05” manufactured by Nittetsu Chemical & Material; “YC100C”, “YA050C”, “YA050C-MJE” and “YA010C” manufactured by Adomatex; “UFP-30” manufactured by Denka; “Silfil NSS-3N”, “Silfil NSS-4N” and “Silfil NSS-5N” manufactured by Tokuyama Corporation; “SC2500SQ”, “SO-C4”, “SO-C2” and “SO-C1” manufactured by Adomatex; and “DAW-03” and “FB-105FD” manufactured by Denka.

[0174] (c) The average particle diameter of the inorganic filler is not particularly limited, but preferably 10 μm or less, more preferably 5 μm or less, even more preferably 3 μm or less, even more preferably 2 μm or less, and particularly preferably 1.5 μm or less. (c) The lower limit of the average particle diameter of the inorganic filler is not particularly limited, but preferably 0.01 μm or more, more preferably 0.05 μm or more, even more preferably 0.1 μm or more, and particularly preferably 0.2 μm or more. (c) The average particle diameter of the inorganic filler can be measured by a laser diffraction scattering method based on the Mie scattering theory. Specifically, it can be measured by creating a particle diameter distribution of the inorganic filler on a volume basis using a laser diffraction scattering particle diameter distribution measuring device, and taking the median diameter as the average particle diameter. As a measurement sample, 100 mg of inorganic filler and 10 g of methyl ethyl ketone can be measured and placed in a vial, and dispersed by ultrasound for 10 minutes. Using a laser diffraction particle diameter distribution measuring device, the wavelengths of the light source used were set to blue and red, and the volume-based particle diameter distribution of the inorganic filler was measured using a flow cell method. From the obtained particle diameter distribution, the average particle diameter was calculated as the median diameter. Examples of laser diffraction particle diameter distribution measuring devices include the "LA-960" manufactured by Horiba Seisakusho Co., Ltd.

[0175] (c) The specific surface area of ​​the inorganic filler is not particularly limited, but preferably 0.1 m² / g or more, more preferably 0.5 m² / g or more, even more preferably 1 m² / g or more, and particularly preferably 3 m² / g or more. (c) The upper limit of the specific surface area of ​​the inorganic filler is not particularly limited, but preferably 100 m² / g or less, more preferably 70 m² / g or less, even more preferably 50 m² / g or less, even more preferably 30 m² / g or less, and particularly preferably 10 m² / g or less. The specific surface area of ​​the inorganic filler is obtained by adsorbing nitrogen gas onto the surface of a sample using a specific surface area measuring device (Macsorb HM-1210 manufactured by Mounttech) according to the BET method, and calculating the specific surface area using the BET multi-point method.

[0176] (c) It is preferable that the inorganic filler be treated with a surface treatment agent to improve moisture resistance and dispersibility. Examples of surface treatment agents include fluorine-containing silane coupling agents, aminosilane-based coupling agents, epoxysilane-based coupling agents, mercaptosilane-based coupling agents, silane-based coupling agents, alkoxysilanes, organosilazanes, titanate-based coupling agents, etc. Additionally, the surface treatment agent may be used as a single type or may be used in combination of two or more types.

[0177] As commercially available surface treatment agents, for example, "KBM403" (3-glycidoxypropyltrimethoxysilane) manufactured by Shin-Etsu Kagaku Kogyo Co., Ltd., "KBM803" (3-mercaptopropyltrimethoxysilane) manufactured by Shin-Etsu Kagaku Kogyo Co., Ltd., "KBE903" (3-aminopropyltriethoxysilane) manufactured by Shin-Etsu Kagaku Kogyo Co., Ltd., "KBM573" (N-phenyl-3-aminopropyltrimethoxysilane) manufactured by Shin-Etsu Kagaku Kogyo Co., Ltd., "SZ-31" (hexamethyldisilazane) manufactured by Shin-Etsu Kagaku Kogyo Co., Ltd., "KBM103" (phenyltrimethoxysilane) manufactured by Shin-Etsu Kagaku Kogyo Co., Ltd., "KBM-4803" (long-chain epoxy-type silane coupling agent) manufactured by Shin-Etsu Kagaku Kogyo Co., Ltd. Examples include “KBM-7103” (3,3,3-trifluoropropyltrimethoxysilane).

[0178] The degree of surface treatment by the surface treatment agent is preferably within a predetermined range from the perspective of improving the dispersibility of the inorganic filler. Specifically, 100 mass% of the inorganic filler is preferably surface-treated with a surface treatment agent in an amount of 0.2 mass% to 5 mass%, more preferably surface-treated with an amount of 0.2 mass% to 3 mass%, and even more preferably surface-treated with an amount of 0.3 mass% to 2 mass%.

[0179] The degree of surface treatment by a surface treatment agent can be evaluated by the carbon content per unit surface area of ​​the inorganic filler. From the perspective of improving the dispersibility of the inorganic filler, the carbon content per unit surface area of ​​the inorganic filler is preferably 0.02 mg / m² or more, more preferably 0.1 mg / m² or more, and even more preferably 0.2 mg / m² or more. Meanwhile, from the perspective of preventing an increase in the melt viscosity of the resin composition or the melt viscosity in sheet form, it is preferably 1.0 mg / m² or less, more preferably 0.8 mg / m² or less, and even more preferably 0.5 mg / m² or less.

[0180] (c) The carbon content per unit surface area of ​​the inorganic filler can be measured after the inorganic filler is cleaned with a solvent (e.g., methyl ethyl ketone (MEK)) following surface treatment. Specifically, a sufficient amount of MEK as a solvent is added to the inorganic filler surface-treated with a surface treatment agent, and ultrasonically cleaned at 25°C for 5 minutes. After removing the supernatant and drying the solids, the carbon content per unit surface area of ​​the inorganic filler can be measured using a carbon analyzer. As a carbon analyzer, the "EMIA-320V" manufactured by Horiba Seisakusho Co., Ltd. can be used.

[0181] The content of (c) inorganic filler in the resin composition layer is not particularly limited, but when the non-volatile component in the resin composition layer is 100 mass%, it may preferably be 95 mass% or less, more preferably 90 mass% or less, even more preferably 85 mass% or less, and particularly preferably 80 mass% or less. The lower limit of the content of (c) inorganic filler in the resin composition layer is not particularly limited, but from the viewpoint of suppressing the dielectric loss tangent to a lower value, when the non-volatile component in the resin composition layer is 100 mass%, it may be, for example, 0 mass% or more, 1 mass% or more, or 5 mass% or more, and preferably 10 mass% or more, more preferably 30 mass% or more, even more preferably 40 mass% or more, even more preferably 50 mass% or more, and particularly preferably 60 mass% or more.

[0182] <(d) Radical polymerizable compounds>

[0183] The resin composition layer may contain (d) a radical polymerizable compound as an optional component. (d) The radical polymerizable compound may be used as a single type or may be used in combination of two or more types.

[0184] (d) In one embodiment, the radical polymerizable compound is a radical polymerizable compound having an ethylenically unsaturated bond. (d) The radical polymerizable compound is not particularly limited, but may have, for example, unsaturated hydrocarbon groups such as an allyl group, a 3-cyclohexenyl group, a 3-cyclopentenyl group, a 2-vinylphenyl group, a 3-vinylphenyl group, a 4-vinylphenyl group; or α,β-unsaturated carbonyl groups such as an acryloyl group, a methacryloyl group, or a maleimide group (2,5-dihydro-2,5-dioxo-1H-pyrrole-1-yl group). (d) It is preferable that the radical polymerizable compound has two or more radical polymerizable groups.

[0185] (d) The radical polymerizable compound, in the first embodiment, preferably comprises a thermoplastic resin having a vinylphenyl group and / or a (meth)acryloyl group. The (meth)acryloyl group means an acryloyl group or a methacryloyl group. The vinylphenyl group comprises a 2-vinylphenyl group, a 3-vinylphenyl group, a 4-vinylphenyl group, or an aromatic carbon atom thereof 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 resin, polyvinyl acetal resin, polystyrene resin, polyethylene resin, polypropylene resin, polybutadiene resin, polyimide resin, polyamideimide resin, polyetherimide resin, polysulfone resin, polyethersulfone resin, polyphenylene ether resin, polyether ether ketone resin, polyester resin, etc., and (d) the radical polymerizable compound comprises, in the present embodiment, a modified resin having vinylphenyl groups and / or (meth)acryloyl groups of such resins.

[0186] (d) The radical polymerizable compound, in the first embodiment, more preferably comprises a resin selected from a modified polyphenylene ether resin having a vinylphenyl group and / or (meth)acryloyl group and a modified polystyrene resin having a vinylphenyl group and / or (meth)acryloyl group, more preferably comprises a modified polyphenylene ether resin having a vinylphenyl group and / or (meth)acryloyl group, and particularly preferably, formula (B-1):

[0187]

[0188] [In chemical formula (B-1), R 11 and R 12 , each independently, represents an alkyl group; R 13 , R 14 , R 21 , R 22 , R 23 and R 24 represents, respectively, a hydrogen atom or an alkyl group; R 31 and R 32 represents, respectively, a vinylphenyl group or a (meth)acryloyl group; Y 1 silver, single bond, -C(R y Representing )2-, -O-, -CO-, -S-, -SO-, or -SO2-; R y represents, respectively, a hydrogen atom or an alkyl group; Y 2 represents a single bond or an alkylene group; p represents 0 or 1; and q and r each independently represent an integer greater than or equal to 1.

[0189] Includes the resin represented by . The q unit and r unit may be the same or different for each unit.

[0190] R 11 and R 12 Each independently represents an alkyl group, preferably a methyl group. R 13 and R 14Each independently represents a hydrogen atom or an alkyl group, preferably a hydrogen atom or an alkyl group, and more preferably a hydrogen atom. R 21 and R 22 Each independently represents a hydrogen atom or an alkyl group, preferably a hydrogen atom or a methyl group, and more preferably a methyl group. R 23 and R 24 Each independently represents a hydrogen atom or an alkyl group, preferably a hydrogen atom or a methyl group.

[0191] An alkyl group refers to a monovalent aliphatic saturated hydrocarbon group of straight chain, branched chain, and / or cyclic form. 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 a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group, a decyl group, a cyclopentyl group, a cyclohexyl group, a methylcyclohexyl group, a dimethylcyclohexyl group, a trimethylcyclohexyl group, a cyclopentylmethyl group, a cyclohexylmethyl group, the like.

[0192] R 31 and R 32 Each independently represents a vinylphenyl group or a (meth)acryloyl group, and Y 2represents a single bond or an alkylene group. An alkylene group refers to a straight-chain, branched-chain, and / or cyclic divalent aliphatic saturated 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 preferably an alkylene group having 1 to 6 carbon atoms. Examples of alkylene groups include -CH2-, -CH2-CH2-, -CH(CH3)-, -CH2-CH2-CH2-, -CH2-CH(CH3)-, -CH(CH3)-CH2-, -C(CH3)2-, etc. Preferably, R 31 and R 32 a, is a vinylphenyl group, and also Y 2 a, an alkylene group (particularly preferably -CH2-), or R 31 and R 32 a, (meth)acryloyl group, and also Y 2 is a single bond.

[0193] Y 1 silver, single bond, -C(R y Representing )2-, -O-, -CO-, -S-, -SO-, or -SO2-, preferably, a single bond, -C(R y )2-, or -O-. R y Each 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 from 1 to 200, and more preferably an integer from 1 to 100.

[0194] Examples of commercially available radical polymerizable compounds (d) in the first embodiment include “OPE-2St 1200” and “OPE-2St 2200” (vinylbenzyl modified polyphenylene ether resin) manufactured by Mitsubishi Gas Chemical Co., Ltd.; and “SA9000” and “SA9000-111” (methacrylate modified polyphenylene ether resin) manufactured by SABIC Innovative Plastics Co., Ltd.

[0195] The content of (d) radical polymerizable compound in the resin composition layer is not particularly limited, but when the non-volatile component in the resin composition layer is 100 mass%, it may preferably be 50 mass% or less, more preferably 30 mass% or less, even more preferably 20 mass% or less, and particularly preferably 10 mass% or less. The lower limit of the content of (d) radical polymerizable compound in the resin composition layer is not particularly limited, but from the viewpoint of suppressing the dielectric loss tangent to a lower value, when the non-volatile component in the resin composition layer is 100 mass%, it may be, for example, 0 mass% or more, 0.01 mass% or more, preferably 0.1 mass% or more, more preferably 1 mass% or more, even more preferably 1 mass% or more, and particularly preferably 3 mass% or more.

[0196] <(e) Thermoplastic resin>

[0197] The resin composition layer may additionally contain (e) a thermoplastic resin as an optional component. The thermoplastic resin (e) described herein is a component that does not correspond to (a) epoxy resin, (b) other curing agents, and (d) radical polymerizable compounds.

[0198] (e) Examples of thermoplastic resins include polyimide resin, phenoxy resin, polyvinyl acetal resin, polyolefin resin, polybutadiene resin, polyamideimide resin, polyetherimide resin, polysulfone resin, polyethersulfone resin, polyphenylene ether resin, polycarbonate resin, polyetheretherketone resin, polyester resin, etc. In one embodiment, the resin composition layer preferably comprises a thermoplastic resin selected from the group consisting of polyimide resin and phenoxy resin, and more preferably comprises a phenoxy resin. In addition, the thermoplastic resin may be used as a single type or in combination of two or more types.

[0199] Specific examples of polyimide resins include “SLK-6100” manufactured by Shin-Etsu Kagaku Kogyo Co., Ltd., and “Ricacoat SN20” and “Ricacoat PN20” manufactured by Shin-Nippon Ricca Co., Ltd.

[0200] Examples of phenoxy resins include phenoxy resins having one or more skeletons selected from the group consisting of bisphenol A skeleton, bisphenol F skeleton, bisphenol S skeleton, bisphenol acetophenone skeleton, novolac skeleton, biphenyl skeleton, fluorene skeleton, dicyclopentadiene skeleton, norbornene skeleton, naphthalene skeleton, anthracene skeleton, adamantane skeleton, terpene skeleton, and trimethylcyclohexane skeleton. The terminals of the phenoxy resin may be any functional group, such as phenolic hydroxyl groups or epoxy groups.

[0201] Specific examples of phenoxy resins include “1256” and “4250” manufactured by Mitsubishi Chemical Corporation (both phenoxy resins containing a bisphenol A backbone); “YX8100” manufactured by Mitsubishi Chemical Corporation (phenoxy resin containing a bisphenol S backbone); “YX6954” manufactured by Mitsubishi Chemical Corporation (phenoxy resin containing a bisphenol acetophenone backbone); and “FX280” and “FX293” manufactured by Shin-Nippon Steel Sumikin Chemical Co., Ltd.; Examples include “YL7500BH30”, “YX6954BH30”, “YX7553”, “YX7553BH30”, “YL7769BH30”, “YL6794”, “YL7213”, “YL7290”, “YL7482”, and “YL7891BH30” manufactured by Mitsubishi Chemical Corporation.

[0202] Examples of polyvinyl acetal resins include polyvinyl formal resin and polyvinyl butyral resin, and polyvinyl butyral resin is 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 Denki Kagaku Kogyo Co., Ltd.; and the S-Rec BH series, BX series (e.g., BX-5Z), KS series (e.g., KS-1), BL series, and BM series manufactured by Sekisui Kagaku Kogyo Co., Ltd.

[0203] Examples of polyolefin resins include ethylene-based copolymer resins such as low-density polyethylene, ultra-low-density polyethylene, high-density polyethylene, ethylene-vinyl acetate copolymer, ethylene-ethyl acrylate copolymer, and ethylene-methyl acrylate copolymer; and polyolefin-based polymers such as polypropylene and ethylene-propylene block copolymer.

[0204] Examples of polybutadiene resins include, for instance, a resin containing a hydrogenated polybutadiene backbone, a polybutadiene resin containing a hydroxyl group, a polybutadiene resin containing a phenolic hydroxyl group, a polybutadiene resin containing a carboxyl group, a polybutadiene resin containing an acid anhydride group, a polybutadiene resin containing an epoxy group, a polybutadiene resin containing an isocyanate group, a polybutadiene resin containing a urethane group, and a polyphenylene ether-polybutadiene resin.

[0205] Specific examples of polyamideimide resins include "Viromax HR11NN" and "Viromax HR16NN" manufactured by Toyobo Corporation. Specific examples of polyamideimide resins also include modified polyamideimides such as "KS9100" and "KS9300" (polyamideimide containing a polysiloxane backbone) manufactured by Hitachi Kasei Corporation.

[0206] Specific examples of polyethersulfone resins include "PES5003P" manufactured by Sumitomo Chemicals.

[0207] Specific examples of polysulfone resins include the polysulfones "P1700" and "P3500" manufactured by Solvay Advanced Polymers.

[0208] Specific examples of polyphenylene ether resins include "NORYL SA90" manufactured by SABIC. Specific examples of polyetherimide resins include "Ultem" manufactured by GE.

[0209] Examples of polycarbonate resins include hydroxyl group-containing carbonate resins, phenolic hydroxyl group-containing carbonate resins, carboxyl group-containing carbonate resins, acid anhydride group-containing carbonate resins, isocyanate group-containing carbonate resins, urethane group-containing carbonate resins, etc. Specific examples of polycarbonate resins include “FPC0220” manufactured by Mitsubishi Gas Chemicals, “T6002” and “T6001” (polycarbonate diol) manufactured by Asahi Kasei Chemicals, and “C-1090”, “C-2090” and “C-3090” (polycarbonate diol) manufactured by Curare. Specific examples of polyetheretherketone resins include “Sumiproi K” manufactured by Sumitomo Chemicals.

[0210] 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, etc.

[0211] (e) The weight average molecular weight (Mw) of the thermoplastic resin is preferably 5,000 or more, more preferably 8,000 or more, even more preferably 10,000 or more, particularly preferably 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, from the view of obtaining the effect of the present invention significantly.

[0212] 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 mass%, it may preferably be 20 mass% or less, more preferably 10 mass% or less, even more preferably 5 mass% or less, and particularly preferably 2 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 mass%, it may be, for example, 0 mass% or more, preferably 0.001 mass% or more, more preferably 0.01 mass% or more, even more preferably 0.1 mass% or more, and particularly preferably 0.5 mass% or more.

[0213] <(f) Curing Accelerator>

[0214] The resin composition layer may additionally include (f) a curing accelerator as an optional component. (f) The curing accelerator functions as a curing catalyst that promotes the curing of (a) the epoxy resin.

[0215] (f) Examples of curing accelerators include phosphorus-based curing accelerators, urea-based curing accelerators, guanidine-based curing accelerators, imidazole-based curing accelerators, metal-based curing accelerators, amine-based curing accelerators, etc. (f) It is preferable that the curing accelerators include curing accelerators selected from imidazole-based curing accelerators and amine-based curing accelerators. (f) The curing accelerators may be used as a single type or in combination of two or more types.

[0216] As phosphorus-based curing accelerators, for example, aliphatic phosphonium salts such as tetrabutylphosphonium bromide, tetrabutylphosphonium chloride, tetrabutylphosphonium acetate, tetrabutylphosphonium decanoate, tetrabutylphosphonium laurate, bis(tetrabutylphosphonium)pyromellitate, tetrabutylphosphonium hydrogen hexahydrophthalate, tetrabutylphosphonium 2,6-bis[(2-hydroxy-5-methylphenyl)methyl]-4-methylphenolate, and di-tert-butylmethylphosphonium tetraphenylborate; Aromatic phosphonium salts such as methyltriphenylphosphonium bromide, ethyltriphenylphosphonium bromide, propyltriphenylphosphonium bromide, butyltriphenylphosphonium bromide, benzyltriphenylphosphonium chloride, tetraphenylphosphonium bromide, p-tolyltriphenylphosphonium tetra-p-tolylborate, tetraphenylphosphonium tetraphenylborate, tetraphenylphosphonium tetrap-tolylborate, triphenylethylphosphonium tetraphenylborate, tris(3-methylphenyl)ethylphosphonium tetraphenylborate, tris(2-methoxyphenyl)ethylphosphonium tetraphenylborate, (4-methylphenyl)triphenylphosphonium thiocyanate, tetraphenylphosphonium thiocyanate, butyltriphenylphosphonium thiocyanate, etc.; aromatic phosphine-borane complexes such as triphenylphosphine-triphenylborane; Aromatic phosphine-quinone addition products such as triphenylphosphine·p-benzoquinone addition products; aliphatic phosphines such as tributylphosphine, tri-tert-butylphosphine, trioctylphosphine, di-tert-butyl(2-butenyl)phosphine, di-tert-butyl(3-methyl-2-butenyl)phosphine, tricyclohexylphosphine;Dibutylphenylphosphine, di-tert-butylphenylphosphine, methyldiphenylphosphine, ethyldiphenylphosphine, butyldiphenylphosphine, diphenylcyclohexylphosphine, triphenylphosphine, tri-o-tolylphosphine, tri-m-tolylphosphine, tri-p-tolylphosphine, 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, Examples include aromatic phosphines such as 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)butane, 1,2-bis(diphenylphosphino)acetylene, and 2,2'-bis(diphenylphosphino)diphenyl ether.

[0217] As urea-based curing accelerators, for example, 1,1-dimethylurea; aliphatic dimethylureas such as 1,1,3-trimethylurea, 3-ethyl-1,1-dimethylurea, 3-cyclohexyl-1,1-dimethylurea, 3-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, Examples of aromatic dimethylureas include 3-[3-(trifluoromethyl)phenyl]-1,1-dimethylurea, N,N-(1,4-phenylene)bis(N',N'-dimethylurea), N,N-(4-methyl-1,3-phenylene)bis(N',N'-dimethylurea) [toluenebisdimethylurea].

[0218] As guanidine-based curing accelerators, 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]deca-5-en, 7-methyl-1,5,7-triazabicyclo[4.4.0]deca-5-en, 1-methylbiguanide, 1-ethylbiguanide, 1-n-butylbiguanide, 1-n-octadecylbiguanide, 1,1-dimethylbiguanide, 1,1-diethylbiguanide, 1-cyclohexylbiguanide, 1-allylbiguanide, Examples include 1-phenylbiguanide, 1-(o-tolyl)biguanide, etc.

[0219] As imidazole-based curing accelerators, for example, 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'-undecylimidazolyl-(1')]-ethyl-s-triazine, 2,4-diamino-6-[2'-ethyl-4'-methylimidazolyl-(1')]-ethyl-s-triazine, 2,4-diamino-6-[2'-methylimidazolyl-(1')]-ethyl-s-triazine isocyanuric acid adduct, 2-phenylimidazole isocyanuric acid adduct, 2-phenyl-4,5-dihydroxymethylimidazole, 2-phenyl-4-methyl-5-hydroxymethylimidazole, Examples include imidazole compounds such as 2,3-dihydro-1H-pyrrolo[1,2-a]benzimidazole, 1-dodecyl-2-methyl-3-benzylimidazolium chloride, 2-methylimidazoline, and 2-phenylimidazoline, as well as adducts of imidazole compounds and epoxy resins.

[0220] As for imidazole-based curing accelerators, commercially available products may be used, for example, “1B2PZ”, “2MZA-PW”, “2PHZ-PW” manufactured by Shikoku Kasei Kogyo Co., Ltd., and “P200-H50” manufactured by Mitsubishi Chemical Co., Ltd.

[0221] Examples of metal-based hardening accelerators include organometallic complexes or organometallic salts of metals such as cobalt, copper, zinc, iron, nickel, manganese, and tin. Specific examples of organometallic complexes include organic cobalt complexes such as cobalt(II) acetylacetonate and cobalt(III) acetylacetonate, organic copper complexes such as copper(II) acetylacetonate, organic zinc complexes such as zinc(II) acetylacetonate, organic iron complexes such as iron(III) acetylacetonate, organic nickel complexes such as nickel(II) acetylacetonate, and organic manganese complexes such as manganese(II) acetylacetonate. Examples of organometallic salts include zinc octylate, tin octylate, zinc naphthenate, cobalt naphthenate, tin stearate, and zinc stearate.

[0222] Examples of amine-based curing accelerators include trialkylamines such as triethylamine and tributylamine, 4-dimethylaminopyridine, benzyldimethylamine, 2,4,6-tris(dimethylaminomethyl)phenol, and 1,8-diazabicyclo(5,4,0)-undecene.

[0223] As for amine-based curing accelerators, commercially available products may be used, for example, "MY-25" manufactured by Ajinomoto Fine Techno Co., Ltd.

[0224] The content of (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 mass%, it is preferably 5 mass% or less, more preferably 1 mass% or less, even more preferably 0.5 mass% or less, and particularly preferably 0.2 mass% or less. The lower limit of the content of (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 mass%, it may be, for example, 0 mass% or more, 0.01 mass% or more, 0.1 mass% or more, etc.

[0225] <(g) Other Additives>

[0226] The resin composition of the present invention may additionally include any additive as a non-volatile component. Examples of such additives include, for instance, radical polymerization initiators such as peroxide-based radical polymerization initiators and azo-based radical polymerization initiators; thermosetting resins other than epoxy resins such as epoxy acrylate resin, urethane acrylate resin, urethane resin, cyanate resin, benzoxazine resin, unsaturated polyester resin, phenolic resin, melamine resin, and silicone resin; organic fillers such as rubber particles; organometallic compounds such as organocopper compounds, organozinc compounds, and organocobalt compounds; coloring agents such as phthalocyanine blue, phthalocyanine green, iodine green, diazo yellow, crystal violet, titanium oxide, and carbon black; polymerization inhibitors such as hydroquinone, catechol, pyrogallol, and phenothiazine; leveling agents such as silicone-based leveling agents and acrylic polymer-based leveling agents; and thickeners such as bentonite and montmorillonite. Defoaming agents such as silicone-based defoaming agents, acrylic-based defoaming agents, fluorine-based defoaming agents, vinyl resin-based defoaming agents, etc.; UV absorbers such as benzotriazole-based UV absorbers; adhesion improvers such as urea silanes; adhesion promoters such as triazole-based adhesion promoters, tetrazole-based adhesion promoters, triazine-based adhesion promoters, etc.; antioxidants such as hindered phenol-based antioxidants; fluorescent whitening agents such as stilbene derivatives; surfactants such as fluorine-based surfactants, silicone-based surfactants, etc.; flame retardants such as phosphorus-based flame retardants (e.g., phosphate ester compounds, phosphazene compounds, phosphinic acid compounds, red phosphorus), nitrogen-based flame retardants (e.g., melamine sulfate), halogen-based flame retardants, inorganic flame retardants (e.g., antimony trioxide), etc.; dispersants such as phosphate ester-based dispersants, polyoxyalkylene-based dispersants, acetylene-based dispersants, silicone-based dispersants, anionic dispersants, cationic dispersants, etc.; Examples of stabilizers include borate-based stabilizers, titanate-based stabilizers, aluminate-based stabilizers, zirconate-based stabilizers, isocyanate-based stabilizers, carboxylic acid-based stabilizers, carboxylic acid anhydride-based stabilizers, etc.(g) Other additives may be used as a single type, or two or more types may be used in combination in any proportion. (g) The content of other additives can be appropriately set by a person skilled in the art.

[0227] <(h) Organic solvent>

[0228] The resin composition of the present invention may additionally contain any organic solvent as a volatile component in addition to the non-volatile component described above. (h) Known organic solvents may be appropriately used, and the type thereof is not particularly limited. (h) As organic solvents, for example, ketone-based solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone; ester-based solvents such as methyl acetate, ethyl acetate, butyl acetate, isobutyl acetate, isoamyl acetate, methyl propionate, ethyl propionate, γ-butyrolactone; ether-based solvents such as tetrahydropyran, tetrahydrofuran, 1,4-dioxane, diethyl ether, diisopropyl ether, dibutyl ether, diphenyl ether, anisole; alcohol-based solvents such as methanol, ethanol, propanol, butanol, ethylene glycol; 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, etc.; ester alcohol solvents such as methyl lactate, ethyl lactate, 2-methyl hydroxyisobutyrate, etc.; ether alcohol solvents such as 2-methoxypropanol, 2-methoxyethanol, 2-ethoxyethanol, propylene glycol monomethyl ether, diethylene glycol monobutyl ether (butyl carbitol), etc.; amide solvents such as N,N-dimethylformamide, N,N-dimethylacetamide, N-methyl-2-pyrrolidone, etc.; sulfoxide solvents such as dimethyl sulfoxide; nitrile solvents such as acetonitrile, propionitrile, etc.; Examples include aliphatic hydrocarbon solvents such as hexane, cyclopentane, cyclohexane, and methylcyclohexane; aromatic hydrocarbon solvents such as benzene, toluene, xylene, ethylbenzene, and trimethylbenzene. (h) Organic solvents may be used as a single type, or two or more types may be used in combination in any ratio.

[0229] The content of (h) organic solvent in the resin composition layer after drying is not particularly limited, but when the total component in the resin composition layer is 100 mass%, it is preferably 5 mass% or less, more preferably 3 mass% or less, even more preferably 2 mass% or less, and particularly preferably 1 mass% or less.

[0230] Semiconductor Device

[0231] A semiconductor device including a printed circuit board can be manufactured using a printed circuit board obtained by the manufacturing method of the present invention.

[0232] Examples of semiconductor devices include various semiconductor devices provided for electrical products (e.g., computers, mobile phones, digital cameras, and televisions) and vehicles (e.g., motorcycles, automobiles, trams, ships, and aircraft).

[0233] A semiconductor device can be manufactured by mounting components (semiconductor chips) at conductive points on a printed circuit board. A conductive point is a location on the printed circuit board that transmits electrical signals, and such a location can be on the surface or embedded. Furthermore, the semiconductor chip is not particularly limited as long as it is an electrical circuit element made of semiconductor material.

[0234] When manufacturing a semiconductor device, the mounting method of the semiconductor chip is not particularly limited as long as the semiconductor chip functions effectively, but specifically, wire bonding mounting method, flip-chip mounting method, mounting method using a bump-flush build-up layer (BBUL), mounting method using an anisotropic conductive film (ACF), mounting method using a non-conductive film (NCF), etc.

[0235] [Example]

[0236] The present invention will be described in detail below by way of examples. The present invention is not limited to these examples. Furthermore, in the following description, "parts" and "%" indicating amounts refer to "parts by mass" and "% by mass," respectively, unless otherwise specified. In the following description, the temperature condition is room temperature (25°C) unless a specific temperature is designated, and the pressure condition is atmospheric pressure (0.1 MPa) unless a specific pressure is designated.

[0237] <Production Example A: Production of Resin Sheet A>

[0238] 5 parts of biphenyl-aralkyl type epoxy resin (Nihon Kayaku Co., Ltd. “NC-3000H”, epoxy equivalent approx. 271 g / eq.), 10 parts of naphthalene type epoxy resin (DIC Corporation “HP4032SS”, epoxy equivalent approx. 145 g / eq.), 5 parts of a mixture of bisphenol A type epoxy resin and bisphenol F type epoxy (Nittettsu Chemical & Material Corporation “ZX1059”, epoxy equivalent 165 g / eq.), 30 parts of an active ester-based curing agent (DIC Corporation “HPC-8150-62T”, active group equivalent approx. 229 g / eq., toluene solution with 61.5 mass% solids), and a phenol-based curing agent (DIC Corporation “LA-3018-50P”, active group equivalent approx. 151, solids 50% 5 parts of 2-methoxypropanol solution, 5 parts of phenoxy resin ("YX7553BH30" manufactured by Mitsubishi Chemical, a 1:1 solution of MEK and cyclohexanone with a solid content of 30 mass%), 4 parts of 4-dimethylaminopyridine (MEK solution with a solid content of 5 mass%), 30 parts of MEK, and 80 parts of spherical silica ("SO-C2" manufactured by Adomatex, average particle diameter 0.5 μm) surface-treated with an amine-based alkoxysilane compound ("KBM573" manufactured by Shin-Etsu Chemical Co., Ltd.) were uniformly dispersed using a mixer to obtain a varnish-like resin composition.

[0239] The obtained varnish-like resin composition was uniformly coated onto a PET film (Lintec Co., Ltd. “AL5”, thickness 38 μm) using a die coater so that the thickness after drying was 25 μm, and resin sheet A was produced by drying at 80 to 120°C (average 100°C) for 4 minutes.

[0240] <Production Example B: Production of Resin Sheet B>

[0241] A resin sheet B was produced in the same manner as Example A, except that the amount of spherical silica (SO-C2 manufactured by Adomatex, average particle diameter 0.5 μm) surface-treated with an amine-based alkoxysilane compound (KBM573 manufactured by Shin-Etsu Kagaku Kogyo Co., Ltd.) was changed from 80 parts to 120 parts, and 30 parts of an active ester-based curing agent (HPC-8150-62T manufactured by DIC Co., Ltd.) was replaced with 30 parts of an active ester-based curing agent (HPC-8000-65T manufactured by DIC Co., Ltd., active group equivalent of about 223 g / eq., toluene solution with a solid content of 65 mass%) was used.

[0242] <Production Example C: Production of Resin Sheet C>

[0243] A resin sheet C was produced in the same manner as Example A, except that the amount of spherical silica (SO-C2, manufactured by Adomatex, with an average particle diameter of 0.5 μm) surface-treated with an amine-based alkoxysilane compound (KBM573 manufactured by Shin-Etsu Kagaku Kogyo Co., Ltd.) was changed from 80 parts to 60 parts, and the amount of active ester-based curing agent (HPC-8150-62T manufactured by DIC Co., Ltd.) was changed from 30 parts to 45 parts.

[0244] <Production Example D: Production of Resin Sheet D>

[0245] A resin sheet D was produced in the same manner as Example A, except that the amount of spherical silica (SO-C2 manufactured by Adomatex, average particle diameter 0.5 μm) surface-treated with an amine-based alkoxysilane compound (KBM573 manufactured by Shin-Etsu Kagaku Kogyo Co., Ltd.) was changed from 80 parts to 100 parts, the amount of active ester-based curing agent (HPC-8150-62T manufactured by DIC Co., Ltd.) was changed from 30 parts to 45 parts, and 5 parts of a carbodiimide-based curing agent (V-03 manufactured by Nisshinbo Chemical Co., Ltd., active group equivalent of about 216 g / eq., toluene solution with non-volatile content of 50 mass%) were additionally used.

[0246] <Production Example E: Production of Resin Sheet E>

[0247] A resin sheet E was produced in the same manner as Example A, except that the amount of spherical silica (SO-C2, manufactured by Adomatex, with an average particle diameter of 0.5 μm) surface-treated with an amine-based alkoxysilane compound (KBM573, manufactured by Shin-Etsu Kagaku Kogyo Co., Ltd.) was changed from 80 parts to 140 parts, the amount of phenol-based curing agent (LA-3018-50P, manufactured by DIC Co., Ltd.) was changed from 5 parts to 10 parts, and 15 parts of oligophenylene ether styrene resin (OPE-2St 1200, manufactured by Mitsubishi Gas Kagaku Co., Ltd., a toluene solution with a solid content of 65 mass%) were additionally used.

[0248] <Production Example F: Production of Resin Sheet F>

[0249] The amount of spherical silica (SO-C2 manufactured by Adomatex, average particle diameter 0.5 μm) surface-treated with an amine-based alkoxysilane compound ("KBM573" manufactured by Shin-Etsu Kagaku Kogyo Co., Ltd.) was changed from 80 parts to 140 parts, the amount of active ester-based curing agent ("HPC-8150-62T" manufactured by DIC) was changed from 30 parts to 25 parts, the phenol-based curing agent ("LA-3018-50P" manufactured by DIC) was not used, 15 parts of bisphenol A dicyanate ("BA230S75" manufactured by Lonza Japan, cyanate equivalent approx. 232 g / eq., MEK solution with 75 mass% solid content) were additionally used, and the amount of 4-dimethylaminopyridine (MEK solution with 5 mass% solid content) was changed from 4 parts to 2 parts. A resin sheet F was prepared in the same manner as Example A, except that 2 parts of 1-benzyl-2-phenylimidazole (MEK solution with a solid content of 5 mass%) were additionally used.

[0250] <Production Example G: Production of Resin Sheet G>

[0251] The amount of spherical silica (SO-C2 manufactured by Adomatex, average particle diameter 0.5 μm) surface-treated with an amine-based alkoxysilane compound ("KBM573" manufactured by Shin-Etsu Kagaku Kogyo Co., Ltd.) is changed from 80 parts to 120 parts, and an active ester-based curing agent ("HPC-8150-62T" manufactured by DIC) and a phenol-based curing agent ("LA-3018-50P" manufactured by DIC) are not used; 30 parts of bisphenol A dicyanate ("BA230S75" manufactured by Lonza Japan, cyanate equivalent approx. 232 g / eq., MEK solution with 75 mass% solid content) are additionally used, and 1-benzyl-2-phenylimidazole (MEK solution with 5 mass% solid content) is substituted for 4 parts of 4-dimethylaminopyridine (MEK solution with 5 mass% solid content) A resin sheet G was produced in the same manner as Production Example A, except that 4 parts were used.

[0252] <Production Example H: Production of Resin Sheet H>

[0253] A resin sheet H was produced in the same manner as in Example A, except that an active ester-based curing agent ("HPC-8150-62T" manufactured by DIC) was not used, a phenol-based curing agent ("LA-3018-50P" manufactured by DIC) was not used, 25 parts of a phenol novolak-type polyfunctional cyanate ester resin ("PT30" manufactured by Lonza Japan, cyanate equivalent of about 124 g / eq., MEK solution with 80 mass% solid content) were additionally used, and 4 parts of 1-benzyl-2-phenylimidazole (MEK solution with 5 mass% solid content) were used instead of 4 parts of 4-dimethylaminopyridine (MEK solution with 5 mass% solid content).

[0254] The amount of raw materials and non-volatile components used to obtain a varnish-like resin composition in the example of production are summarized in Table 1 below.

[0255]

[0256] <Example 1>

[0257] (Process of preparing an inner layer substrate with laminated resin sheets)

[0258] A glass-based epoxy resin double-sided copper laminate having copper layers on both surfaces (copper layer thickness 18 μm, substrate thickness 0.8 mm, manufactured by Panasonic Denko "R1515A") was prepared as an inner layer substrate. Surface treatment of the copper layers was performed by immersing both sides of the inner layer substrate in "CZ8100" manufactured by Maxar.

[0259] A resin sheet A, prepared according to Example A, was laminated on both sides of an inner layer substrate that had undergone a bonding treatment, such that a layer of the resin composition was bonded to the inner layer substrate. Lamination was performed using a vacuum pressure laminator MVLP-500 manufactured by Meiki Seisakusho Co., Ltd., by vacuum suctioning for 30 seconds at a temperature of 100°C, and then pressing for 30 seconds from the PET film with a heat-resistant rubber in between under conditions of a temperature of 100°C and a pressure of 7.0 kg / ㎠. Next, under atmospheric pressure, a SUS plate was used to press for 60 seconds under conditions of a temperature of 100°C and a pressure of 5.5 kg / ㎠, thereby producing an inner layer substrate with the laminated resin sheet.

[0260] (Process of forming an insulating layer)

[0261] An inner layer substrate having a resin sheet laminated thereon was heated at 130°C for 30 minutes (preheating condition) with a support attached, and then heated at 180°C for 30 minutes (thermal curing condition) without returning to room temperature, thereby thermally curing the resin composition layer, returning to room temperature (25°C) to form an insulating layer, and obtaining a laminate. The maximum thickness of the obtained insulating layer (distance from the interface between the copper layer of the inner layer substrate and the insulating layer to the interface between the insulating layer and the support) was 25 μm. After thermal curing, it was returned to room temperature (25°C).

[0262] (Process of perforating the insulation layer)

[0263] After forming the insulating layer, with the support attached, at least three holes were drilled on the insulating layer on the main surface of one side of the laminate using a CO2 laser processing machine (HITACHI “LC-K212”) under conditions of power: 1.35W, number of shots: 2, and target saw diameter: 30㎛. As a result, multiple via holes approximately circular and rectangular in cross-section were formed on the upper surface opening over the circuit conductors of the inner layer substrate, and the conductor layer of the inner layer substrate was exposed on the bottom surface of each via hole.

[0264] (Process of heating the insulation layer to T2 (°C))

[0265] After the laser drilling process, heat treatment (annealing) was performed in air at atmospheric pressure (0.1 MPa) under conditions of a heat treatment temperature of 130°C (T2) and a heat treatment time of 30 minutes. After that, the temperature was returned to room temperature (25°C) and the support was removed.

[0266] (Desmearing process with oxidizing agent solution)

[0267] The surface of the insulating layer was immersed in Swelling Dip Securiganth P manufactured by Atotech Japan, a swelling solution, at 80°C for 10 minutes, then immersed in Concentrate Compact CP manufactured by Atotech Japan, an oxidizing agent, at 80°C for 20 minutes, and finally immersed in Reduction Solucine Securiganth P manufactured by Atotech Japan, a neutralizing solution, at 40°C for 5 minutes. After that, the surface was dried at 80°C for 30 minutes to produce an evaluation substrate.

[0268] <Example 2>

[0269] An inner layer substrate having a resin sheet laminated thereon, prepared in the same manner as in Example 1, was heated at 130°C for 30 minutes (preheating condition) with a support attached, and then returned to room temperature (25°C). After that, with the support attached, a resin composition layer on one side of the main surface of the inner layer substrate having the resin sheet laminated thereon was drilled at 10 or more locations using a CO2 laser processing machine (HITACHI “LC-K212”) under conditions of power: 1.35W, number of shots: 2, and target saw diameter: 30㎛. As a result, a plurality of via holes approximately circular and rectangular in cross-section were formed on the upper surface opening over the circuit conductor of the inner layer substrate, and the conductor layer of the inner layer substrate was exposed on the bottom surface of each via hole. After that, the inner layer substrate, on which a resin sheet having via holes is laminated, was heated at 170°C for 30 minutes (thermal curing conditions) to heat-cure the resin composition layer and form an insulating layer, thereby obtaining a laminate. Then, a heat treatment (annealing treatment) was performed in air at atmospheric pressure under conditions of a heat treatment temperature of 130°C (T2) and a heat treatment time of 30 minutes, returned to room temperature (25°C), the support was removed, and a desmearing treatment of the surface of the insulating layer was performed under the same conditions as in Example 1, and dried to produce an evaluation substrate.

[0270] <Example 3>

[0271] An evaluation substrate was prepared in the same manner as in Example 1, except that resin sheet B prepared in Example B was used instead of resin sheet A, and the heat treatment temperature (T2) in the heat treatment (annealing treatment) was changed from 130°C to 115°C.

[0272] <Example 4>

[0273] An evaluation substrate was prepared in the same manner as in Example 1, except that resin sheet C prepared in Example C was used instead of resin sheet A, the heat treatment temperature (T2) in the heat treatment (annealing treatment) was changed from 130°C to 115°C, and the heat treatment time was changed from 30 minutes to 60 minutes.

[0274] <Example 5>

[0275] An evaluation substrate was prepared in the same manner as in Example 1, except that resin sheet D prepared in Example D was used instead of resin sheet A, and the heat treatment temperature (T2) in the heat treatment (annealing treatment) was changed from 130°C to 140°C.

[0276] <Example 6>

[0277] An evaluation substrate was prepared in the same manner as in Example 1, except that resin sheet E prepared in Example E was used instead of resin sheet A, and the heat treatment temperature (T2) in the heat treatment (annealing treatment) was changed from 130°C to 120°C.

[0278] <Example 7>

[0279] An evaluation substrate was prepared in the same manner as in Example 1, except that resin sheet F prepared in Example F was used instead of resin sheet A, and the heat treatment temperature (T2) in the heat treatment (annealing treatment) was changed from 130°C to 145°C.

[0280] <Comparative Example 1>

[0281] An evaluation substrate was prepared in the same manner as in Example 1, except that after the perforation process of the insulating layer, a desmearing treatment was performed without performing a heat treatment (annealing treatment).

[0282] <Comparative Example 2>

[0283] An evaluation substrate was prepared in the same manner as in Example 1, except that the heat treatment temperature (T2) in the heat treatment (annealing treatment) was changed from 130°C to 80°C.

[0284] <Comparative Example 3>

[0285] An evaluation substrate was prepared in the same manner as in Example 1, except that the heat treatment temperature (T2) in the heat treatment (annealing treatment) was changed from 130°C to 150°C.

[0286] <Comparative Example 4>

[0287] An evaluation substrate was prepared in the same manner as in Example 1, except that resin sheet G prepared in Example G was used instead of resin sheet A, and the heat treatment temperature (T2) in the heat treatment (annealing treatment) was changed from 130°C to 150°C.

[0288] <Comparative Example 5>

[0289] An evaluation substrate was prepared in the same manner as in Example 1, except that resin sheet H prepared in Example H was used instead of resin sheet A, and the heat treatment temperature (T2) in the heat treatment (annealing treatment) was changed from 130°C to 170°C.

[0290] <Test Example 1: Measurement of Glass Transition Temperature (T1) of Insulating Layer>

[0291] Resin sheets A to H produced in each example were heat-cured under the preheating and heat-curing 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 as a thermomechanical analyzer (DMA). The measurements were performed in the range of 25°C to 240°C with a heating rate of 2°C / min. The value obtained by rounding to the first decimal place of the maximum value of the loss tangent (tanδ), which is calculated from the ratio of the storage modulus (E') and the loss modulus (E'') obtained from the measurement, was set as the glass transition temperature (T1) of the insulating layer.

[0292] <Test Example 2: Evaluation of Cracks>

[0293] In each example and comparative example, the surface layer around the via hole on the evaluation substrate was evaluated for cracks (via cracks) using a scanning electron microscope (S-4800 manufactured by Hitachi High-Tech). For 100 surface layers around via holes, it was confirmed whether cracks were occurring, the ratio of cases where cracks were not occurring was counted, and evaluated according to the following evaluation criteria.

[0294] metewand

[0295] "○": When the number of cracks is less than 20

[0296] "×": When the number of cracks is 20 or more

[0297] The manufacturing method of the resin sheet and evaluation substrate used in each example and comparative example, the measurement results and evaluation results of each test example are summarized in Table 2 below.

[0298]

[0299] Timing of the Sky

[0300] "I": (A-32) After process (A-4) Before process

[0301] "II": (A-31) After process (A-32) Before process

[0302] As shown in Table 2, it can be seen that by using an active ester-based curing agent to form an insulating layer and, after forming the insulating layer, heating the insulating layer to a temperature T2 (°C) near its glass transition temperature T1 (°C) (within ±20°C), the occurrence of cracks after desmear treatment (harmonization treatment) can be suppressed.

Claims

Claim 1 (A) a process of heat-curing a resin composition layer of a laminate having an inner layer substrate and a resin composition layer bonded on the inner layer substrate to form an insulating layer having a glass transition temperature T1 (°C), (B) a process of heat-treating the insulating layer to T2 (°C), and (C) a process of desmearing the insulating layer with an oxidizing agent solution, wherein the resin composition layer comprises an epoxy resin and an active ester-based curing agent, and also satisfies the following formulas (1) and (2). -20≤T1-T2≤20 (1)60≤T2≤150 (2) Claim 2 A method for manufacturing a printed circuit board according to claim 1, wherein the process comprises: (A) a process of preparing a resin sheet having a support and a resin composition layer provided on the support; (A-2) a process of laminating the resin sheet so that the resin composition layer is bonded to an inner layer substrate to obtain a laminate; and (A-3) a process of heat-curing the resin composition layer to form an insulating layer having a glass transition temperature T1 (°C) in this order. Claim 3 A method for manufacturing a printed circuit board according to claim 2, wherein the process (A-3) comprises, in this order, (A-31) a process of preheating a resin composition layer at a preheating temperature lower than a curing heating temperature, and (A-32) a process of heating a resin composition layer at a curing heating temperature to heat-cure the resin composition layer to form an insulating layer having a glass transition temperature T1 (°C). Claim 4 A method for manufacturing a printed circuit 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. Claim 5 A method for manufacturing a printed circuit board according to paragraph 2, wherein process (A) further comprises, after process (A-3), a process (A-4) of cooling the insulating layer to 30°C or lower. Claim 6 A method for manufacturing a printed circuit board according to claim 1, wherein (A) the process further comprises (A-5) a process of perforating an insulating layer or a resin composition layer. Claim 7 In claim 6, a method for manufacturing a printed circuit board in which the (A-5) process is carried out using a laser. Claim 8 A method for manufacturing a printed circuit board according to claim 6, wherein the hole formed by process (A-5) has a saw diameter of 100 μm or less. Claim 9 A method for manufacturing a printed circuit board according to claim 1, wherein the heating treatment time of process (B) is 10 minutes or more. Claim 10 A method for manufacturing a printed circuit board according to claim 1, wherein the heat treatment of process (B) is performed by heating the insulating layer under a gas atmosphere. Claim 11 A method for manufacturing a printed circuit board according to claim 1, further comprising, after process (C), a process of forming a conductor layer on the surface of an insulating layer (D). Claim 12 A method for manufacturing a printed circuit board according to claim 1, wherein T2(℃) is 100(℃) or higher. Claim 13 A method for manufacturing a printed circuit board according to claim 1, wherein T1-T2(℃) is -5(℃) to 10(℃). Claim 14 A method for manufacturing a printed circuit board according to claim 1, wherein the resin composition layer further comprises an inorganic filler. Claim 15 A method for manufacturing a printed circuit board according to claim 14, wherein the content of the inorganic filler is 50 mass% or more when the non-volatile component in the resin composition layer is 100 mass%. Claim 16 A method for manufacturing a printed circuit board according to claim 1, wherein the resin composition layer further comprises a phenoxy resin. Claim 17 A method for manufacturing a printed circuit board according to claim 1, wherein the resin composition layer further comprises a radical polymerizable compound. Claim 18 A method for manufacturing a printed circuit board according to claim 1, wherein the resin composition layer further comprises a cyanate ester-based curing agent.

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