JP2018184594A - Resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a resin composition that makes it possible to obtain a cured product being low in ten point average roughness (Rz) and linear thermal expansion coefficient, high in peel strength, and having improved fragility, even when using an inorganic filler with a small average particle size or a large specific surface.SOLUTION: A resin composition contains (A) an epoxy resin, (B) an active ester curing agent, (C) a polyimide resin having a polycyclic aromatic hydrocarbon skeleton, and (D) an inorganic filler with an average particle size of 100 nm or less.SELECTED DRAWING: None

Description

  The present invention relates to a resin composition. Furthermore, the present invention relates to a resin sheet containing the resin composition, a printed wiring board containing an insulating layer formed of a cured product of the resin composition, and a semiconductor device.

  As a manufacturing technique of a printed wiring board, a manufacturing method by a build-up method in which insulating layers and conductor layers are alternately stacked is known. In the manufacturing method by the build-up method, the insulating layer is generally formed by curing a resin composition. For example, Patent Document 1 describes that an insulating layer is formed by curing a resin composition containing an epoxy resin, an active ester compound, a carbodiimide compound, a thermoplastic resin, and an inorganic filler.

JP 2016-27097 A

  When the present inventors further examined the resin composition, the following knowledge was obtained. When a large amount of the inorganic filler is contained in the resin composition, the surface area of the inorganic filler increases and the area of the interface of the inorganic filler also increases. As a result, it was found that the cured product of the resin composition becomes brittle and the rough surface after the roughening treatment becomes rough. In addition, from the viewpoint of thinning and the like, even when an inorganic filler having a small average particle size or a large specific surface area is contained in the resin composition, the cured product of the resin composition has a large surface area. I found that it became more brittle.

  An object of the present invention is to obtain a cured product having a low ten-point average roughness (Rz) and a linear thermal expansion coefficient and a high peel strength even when an inorganic filler having a small average particle size or a large specific surface area is used. An object of the present invention is to provide a resin composition, a resin sheet containing the resin composition, a printed wiring board including an insulating layer formed using the resin composition, and a semiconductor device.

  In order to achieve the object of the present invention, the present inventors have intensively studied. As a result, a thermoplastic resin containing a phenoxy resin or an aliphatic group is excellent in flexibility, and a component having a high polarity such as alcohol is easily generated at the time of curing. It was found that the ten-point average roughness (Rz) may be increased when the roughening treatment is performed as a result of poor resistance. Based on this finding, the present inventors conducted further diligent studies. As a result, when the resin composition contains the (C) component having a rigid and highly hydrophobic polycyclic aromatic hydrocarbon skeleton, the average particle size is small or Even when an inorganic filler having a large specific surface area is used, a resin composition capable of obtaining a cured product having a low ten-point average roughness (Rz) and a coefficient of linear thermal expansion, a high peel strength, and an improved brittleness is obtained. As a result, the present invention has been completed.

That is, the present invention includes the following contents.
[1] (A) epoxy resin,
(B) an active ester curing agent,
(C) a polyimide resin having a polycyclic aromatic hydrocarbon skeleton, and (D) an inorganic filler,
(D) The resin composition whose average particle diameter of a component is 100 nm or less.
[2] (A) epoxy resin,
(B) an active ester curing agent,
(C) a polyimide resin having a polycyclic aromatic hydrocarbon skeleton, and (D) an inorganic filler,
(D) The resin composition whose specific surface area of a component is 15 m < ² > / g or more.
[3] The resin composition according to [1] or [2], wherein the polycyclic aromatic hydrocarbon skeleton is an aromatic hydrocarbon skeleton in which a 5-membered ring compound and an aromatic ring are condensed.
[4] The resin composition according to any one of [1] to [3], wherein the polycyclic aromatic hydrocarbon skeleton is at least one of an indane skeleton and a fluorene skeleton.
[5] The resin composition according to any one of [1] to [4], wherein the component (C) has a weight average molecular weight of 5000 or more.
[6] The resin composition according to any one of [1] to [5], wherein the component (C) has a repeating unit having a polycyclic aromatic hydrocarbon skeleton and a repeating unit having an imide structure.
[7] Mass ratio of the repeating unit having a polycyclic aromatic hydrocarbon skeleton to the repeating unit having an imide structure (mass of repeating unit having a polycyclic aromatic hydrocarbon skeleton / mass of repeating unit having an imide structure) ) Is 0.5 or more and 2 or less, the resin composition according to [6].
[8] Any of [1] to [7], wherein the content of the component (C) is 0.1% by mass or more and 3% by mass or less when the nonvolatile component in the resin composition is 100% by mass. The resin composition described in 1.
[9] The content of the component (B) is any one of [1] to [8], which is 1% by mass or more and 25% by mass or less when the nonvolatile component in the resin composition is 100% by mass. Resin composition.
[10] The content of the component (D) is any one of [1] to [9], which is 30% by mass or more and 80% by mass or less when the nonvolatile component in the resin composition is 100% by mass. Resin composition.
[11] The resin composition according to any one of [1] to [10], further comprising (E) a curing agent.
[12] The resin composition according to [11], wherein (E) the curing agent is a phenol-based curing agent.
[13] The resin composition according to any one of [1] to [12], which is for forming an insulating layer for forming a conductor layer.
[14] The resin composition according to any one of [1] to [13], which is used for forming an insulating layer of a printed wiring board.
[15] The resin composition according to any one of [1] to [14], which is for forming an interlayer insulating layer of a printed wiring board.
[16] A resin sheet comprising a support and the resin composition layer according to any one of [1] to [15] provided on the support.
[17] A printed wiring board including a first conductor layer, a second conductor layer, and an insulating layer formed between the first conductor layer and the second conductor layer,
The insulating layer is a printed wiring board which is a cured product of the resin composition according to any one of [1] to [15].
[18] A semiconductor device comprising the printed wiring board according to [17].

  According to the present invention, even when an inorganic filler having a small average particle size or a large specific surface area is used, the ten-point average roughness (Rz) and the coefficient of linear thermal expansion are low, the peel strength is high, and the brittleness is improved. A resin composition capable of obtaining a cured product; a resin sheet containing the resin composition; a printed wiring board including an insulating layer formed using the resin composition, and a semiconductor device can be provided.

FIG. 1 is a partial cross-sectional view schematically showing an example of a printed wiring board.

  Hereinafter, the resin composition, resin sheet, printed wiring board, and semiconductor device of the present invention will be described in detail.

[Resin composition]
The resin composition of the first embodiment of the present invention includes (A) an epoxy resin, (B) an active ester curing agent, (C) a polyimide resin having a polycyclic aromatic hydrocarbon skeleton, and (D) an inorganic filling. The average particle diameter of (D) component is 100 nm or less. The resin composition of the second embodiment of the present invention includes (A) an epoxy resin, (B) an active ester curing agent, (C) a polyimide resin having a polycyclic aromatic hydrocarbon skeleton, and (D). An inorganic filler is contained, and the specific surface area of the component (D) is 15 m ² / g or more. Even if the resin composition of 1st Embodiment contains the inorganic filler whose average particle diameter is 100 nm or less by containing the polyimide resin which has (C) polycyclic aromatic hydrocarbon frame | skeleton, A resin composition capable of obtaining a cured product having a low ten-point average roughness (Rz) and a coefficient of linear thermal expansion, high peel strength, and improved brittleness can be obtained. Similarly, the resin composition of the second embodiment includes (C) a polyimide resin having a polycyclic aromatic hydrocarbon skeleton, and (D) an inorganic filler having a specific surface area of 15 m ² / g or more. Even if it contains, the resin composition which can obtain the hardened | cured material with low ten-point average roughness (Rz) and a linear thermal expansion coefficient, high peel strength, and improved brittleness can be obtained.

  If necessary, the resin composition may further include (E) a curing agent (excluding an active ester curing agent), (F) a curing accelerator, (G) a thermoplastic resin, and (H) other additives. Ingredients may be included. Hereinafter, each component contained in the resin composition of 1st and 2nd embodiment of this invention is demonstrated in detail. Here, the resin composition of the first embodiment and the resin composition of the second embodiment may be collectively referred to as “resin composition”.

<(A) Epoxy resin>
The resin composition includes (A) an epoxy resin. Examples of the epoxy resin include 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 novolac type epoxy resin, phenol novolac type epoxy resin, tert-butyl-catechol type epoxy resin, naphthalene type epoxy resin, naphthol type epoxy resin, anthracene type epoxy resin, glycidylamine type epoxy resin, glycidyl ester type epoxy resin, cresol novolak Type epoxy resin, biphenyl type epoxy resin, linear aliphatic epoxy resin, epoxy resin having butadiene structure, alicyclic epoxy resin, complex Wherein the epoxy resin, spiro ring-containing epoxy resin, cyclohexane type epoxy resin, cyclohexanedimethanol type epoxy resins, naphthylene ether type epoxy resin, trimethylol type epoxy resin, tetraphenyl ethane epoxy resin and the like. An epoxy resin may be used individually by 1 type, and may be used in combination of 2 or more type.

  The epoxy resin preferably contains an epoxy resin having two or more epoxy groups in one molecule. When the nonvolatile component of the epoxy resin is 100% by mass, at least 50% by mass or more is preferably an epoxy resin having two or more epoxy groups in one molecule. In particular, the resin composition is a combination of a liquid epoxy resin (hereinafter referred to as “liquid epoxy resin”) at a temperature of 20 ° C. and a solid epoxy resin (hereinafter also referred to as “solid epoxy resin”) at a temperature of 20 ° C. It is preferable to include. The liquid epoxy resin is preferably a liquid epoxy resin having two or more epoxy groups in one molecule, and more preferably an aromatic liquid epoxy resin having two or more epoxy groups in one molecule. The solid epoxy resin is preferably a solid epoxy resin having 3 or more epoxy groups in one molecule, and more preferably an aromatic solid epoxy resin having 3 or more epoxy groups in one molecule. In the present invention, the aromatic epoxy resin means an epoxy resin having an aromatic ring in the molecule.

  Liquid epoxy resins include bisphenol A type epoxy resins, bisphenol F type epoxy resins, bisphenol AF type epoxy resins, naphthalene type epoxy resins, glycidyl ester type epoxy resins, glycidyl amine type epoxy resins, phenol novolac type epoxy resins, and ester skeletons. Preferred are alicyclic epoxy resin, cyclohexane type epoxy resin, cyclohexanedimethanol type epoxy resin, glycidylamine type epoxy resin, and epoxy resin having butadiene structure, bisphenol A type epoxy resin, bisphenol F type epoxy resin and cyclohexane type epoxy. A resin is more preferable, and a bisphenol A type epoxy resin is more preferable. Specific examples of the liquid epoxy resin include “HP4032”, “HP4032D”, “HP4032SS” (naphthalene type epoxy resin) manufactured by DIC, “828US”, “jER828EL”, “825”, “Epicoat” manufactured by Mitsubishi Chemical Corporation. 828EL "(bisphenol A type epoxy resin)," jER807 "," 1750 "(bisphenol F type epoxy resin)," jER152 "(phenol novolac type epoxy resin)," 630 "," 630LSD "(glycidylamine type epoxy resin) "ZX1059" (mixed product of bisphenol A type epoxy resin and bisphenol F type epoxy resin) manufactured by Nippon Steel & Sumikin Chemical Co., Ltd., "EX-721" (glycidyl ester type epoxy resin) manufactured by Nagase ChemteX, manufactured by Daicel Corporation "Celoxide 20 1P "(alicyclic epoxy resin having an ester skeleton)," PB-3600 "(epoxy resin having a butadiene structure)," ZX1658 "," ZX1658GS "(liquid 1,4-glycidylcyclohexane type) manufactured by Nippon Steel & Sumikin Chemical Co., Ltd. Epoxy resin), “630LSD” (glycidylamine type epoxy resin) manufactured by Mitsubishi Chemical Corporation, and the like. These may be used alone or in combination of two or more.

  Solid epoxy resins include bixylenol type epoxy resin, naphthalene type epoxy resin, naphthalene type tetrafunctional epoxy resin, cresol novolac type epoxy resin, dicyclopentadiene type epoxy resin, trisphenol type epoxy resin, naphthol type epoxy resin, biphenyl Type epoxy resin, naphthylene ether type epoxy resin, anthracene type epoxy resin, bisphenol A type epoxy resin, bisphenol AF type epoxy resin, tetraphenylethane type epoxy resin are preferable, bixylenol type epoxy resin, naphthalene type epoxy resin, bisphenol AF Type epoxy resin, naphthol type epoxy resin, biphenyl type epoxy resin and naphthylene ether type epoxy resin are more preferred, and bixylenol type epoxy resin Naphthol type epoxy resin, more preferably a biphenyl-type epoxy resin. Specific examples of the solid epoxy resin include “HP4032H” (naphthalene type epoxy resin), “HP-4700”, “HP-4710” (naphthalene type tetrafunctional epoxy resin), “N-690” (manufactured by DIC) Cresol novolac type epoxy resin), "N-695" (cresol novolac type epoxy resin), "HP-7200" (dicyclopentadiene type epoxy resin), "HP-7200HH", "HP-7200H", "EXA-7311 ”,“ EXA-7311-G3 ”,“ EXA-7311-G4 ”,“ EXA-7311-G4S ”,“ HP6000 ”(naphthylene ether type epoxy resin),“ EPPN-502H ”(manufactured by Nippon Kayaku Co., Ltd.) Trisphenol type epoxy resin), "NC7000L" (naphthol novolac type epoxy) Fat), “NC3000H”, “NC3000”, “NC3000L”, “NC3100” (biphenyl type epoxy resin), “ESN475V” (naphthalene type epoxy resin), “ESN485” (naphthol novolak type epoxy resin) manufactured by Nippon Steel & Sumikin Chemical Co., Ltd. ), “YX4000H”, “YX4000”, “YL6121” (biphenyl type epoxy resin), “YX4000HK” (bixylenol type epoxy resin), “YX8800” (anthracene type epoxy resin), manufactured by Mitsubishi Chemical Corporation, Osaka Gas Chemical Company "PG-100", "CG-500" manufactured by Mitsubishi Chemical Corporation, "YL7760" (bisphenol AF type epoxy resin) manufactured by Mitsubishi Chemical Corporation, "YL7800" (fluorene type epoxy resin), "jER1010" manufactured by Mitsubishi Chemical Corporation (solid) Bisphenol A type Epoxy resin), "jER1031S" (tetraphenyl ethane epoxy resin) and the like. These may be used alone or in combination of two or more.

  When the liquid epoxy resin and the solid epoxy resin are used in combination as the component (A), the quantitative ratio thereof (liquid epoxy resin: solid epoxy resin) is 1: 0.1 to 1:20 by mass ratio. A range is preferred. By making the quantity ratio of the liquid epoxy resin and the solid epoxy resin within such a range, i) suitable adhesiveness is obtained when used in the form of a resin sheet, ii) when used in the form of a resin sheet Sufficient flexibility can be obtained, handling properties can be improved, and iii) a cured product having sufficient breaking strength can be obtained. From the viewpoint of the effects i) to iii), the quantitative ratio of the liquid epoxy resin to the solid epoxy resin (liquid epoxy resin: solid epoxy resin) is in the range of 1: 0.3 to 1:10 by mass ratio. Is more preferable, and the range of 1: 0.5 to 1: 1.5 is more preferable.

  The content of the component (A) in the resin composition is preferably 15 masses when the nonvolatile component in the resin composition is 100 mass% from the viewpoint of obtaining an insulating layer exhibiting good mechanical strength and insulation reliability. % Or more, more preferably 20% by mass or more, and further preferably 25% by mass or more. The upper limit of the content of the epoxy resin is not particularly limited as long as the effect of the present invention is exhibited, but is preferably 60% by mass or less, more preferably 45% by mass or less, 40% by mass or less, or 35% by mass or less. is there.

  The epoxy equivalent of (A) component becomes like this. Preferably it is 50-5000, More preferably, it is 50-3000, More preferably, it is 80-2000, More preferably, it is 110-1000. By becoming this range, the crosslinked density of hardened | cured material becomes sufficient and it can bring about an insulating layer with small surface roughness. The epoxy equivalent can be measured according to JIS K7236, and is the mass of a resin containing 1 equivalent of an epoxy group.

  (A) The weight average molecular weight of a component becomes like this. Preferably it is 100-5000, More preferably, it is 250-3000, More preferably, it is 400-1500. Here, the weight average molecular weight of the epoxy resin is a weight average molecular weight in terms of polystyrene measured by a gel permeation chromatography (GPC) method.

<(B) Active ester curing agent>
The resin composition contains (B) an active ester curing agent. The active ester curing agent is an active ester compound having one or more active ester groups in one molecule. The active ester curing agent is preferably an active ester curing agent having two or more active ester groups in one molecule, such as phenol esters, thiophenol esters, N-hydroxyamine esters, and heterocyclic hydroxy compounds. An active ester curing agent having two or more ester groups with high reaction activity in one molecule, such as these esters, is preferably used. An active ester hardening agent may be used individually by 1 type, and may be used in combination of 2 or more type.

  From the viewpoint of improving heat resistance, an active ester curing agent 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 is preferable. Among them, an active ester curing agent obtained by reacting a carboxylic acid compound with at least one selected from a phenol compound, a naphthol compound, and a thiol compound is more preferable, and an aromatic having a carboxylic acid compound and a phenolic hydroxyl group. More preferred is an aromatic compound having two or more active ester groups in one molecule obtained by reacting the compound, a carboxylic acid compound having at least two or more carboxy groups in one molecule, and a phenolic hydroxyl group. An aromatic compound obtained by reacting with an aromatic compound having an aromatic compound having two or more active ester groups in one molecule is even more preferable. The active ester curing agent may be linear or branched. Moreover, if the carboxylic acid compound having at least two or more carboxy groups in a molecule is a compound containing an aliphatic chain, the compatibility with the resin composition can be increased, and if it is a compound having an aromatic ring. Heat resistance can be increased.

  Examples of the carboxylic acid compound include aliphatic carboxylic acids having 1 to 20 carbon atoms and aromatic carboxylic acids having 7 to 20 carbon atoms. The aliphatic carboxylic acid preferably has 1 to 20 carbon atoms, more preferably 2 to 10 carbon atoms, still more preferably 2 to 8 carbon atoms, specifically, acetic acid, malonic acid, succinic acid, maleic acid. An acid, itaconic acid, etc. are mentioned. The aromatic carboxylic acid preferably has 1 to 20 carbon atoms, more preferably 7 to 10 carbon atoms, and specific examples include benzoic acid, phthalic acid, isophthalic acid, terephthalic acid, and pyromellitic acid. . Among these, succinic acid, maleic acid, itaconic acid, phthalic acid, isophthalic acid, and terephthalic acid are preferable from the viewpoint of heat resistance, and isophthalic acid and terephthalic acid are more preferable.

  The thiocarboxylic acid compound is not particularly limited, and examples thereof include thioacetic acid and thiobenzoic acid.

  As a phenol compound, C6-C40 is preferable, C6-C30 is more preferable, C6-C23 is still more preferable, C6-C22 is still more preferable, for example. Preferable specific examples of the phenol compound include hydroquinone, resorcin, bisphenol A, bisphenol F, bisphenol S, phenolphthaline, methylated bisphenol A, methylated bisphenol F, methylated bisphenol S, phenol, o-cresol, m- Examples include cresol, p-cresol, catechol, dihydroxybenzophenone, trihydroxybenzophenone, tetrahydroxybenzophenone, phloroglucin, benzenetriol, and dicyclopentadiene type diphenol. As the phenol compound, a phenol novolak or a phosphorus atom-containing oligomer having a phenolic hydroxyl group described in JP2013-40270A may be used.

  As a naphthol compound, C10-C40 is preferable, for example, C10-C30 is more preferable, and C10-C20 is further more preferable. Preferable specific examples of the naphthol compound include α-naphthol, β-naphthol, 1,5-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 2,6-dihydroxynaphthalene and the like. A naphthol novolak may also be used as the naphthol compound.

  Among them, bisphenol A, bisphenol F, bisphenol S, methylated bisphenol A, methylated bisphenol F, methylated bisphenol S, catechol, α-naphthol, β-naphthol, 1,5-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, dihydroxybenzophenone, trihydroxybenzophenone, tetrahydroxybenzophenone, phloroglucin, benzenetriol, dicyclopentadiene type diphenol, phenol novolac, and a phosphorus atom-containing oligomer having a phenolic hydroxyl group are preferred, catechol, 1,5 -Dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, dihydroxybenzophenone, trihydride Roxybenzophenone, tetrahydroxybenzophenone, phloroglucin, benzenetriol, dicyclopentadiene type diphenol, phenol novolac, and a phosphorus atom-containing oligomer having a phenolic hydroxyl group are more preferable, 1,5-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 2 , 6-dihydroxynaphthalene, dihydroxybenzophenone, trihydroxybenzophenone, tetrahydroxybenzophenone, dicyclopentadiene type diphenol, phenol novolac, and a phosphorus atom-containing oligomer having a phenolic hydroxyl group are more preferred, 1,5-dihydroxynaphthalene, 1,6 -Dihydroxynaphthalene, 2,6-dihydroxynaphthalene, dicyclopentadiene diphenol, phenol More preferred are phosphorus, phosphorus atom-containing oligomers having phenolic hydroxyl groups, 1,5-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, dicyclopentadiene type diphenols, phosphorus having phenolic hydroxyl groups Atom-containing oligomers are particularly preferred, and dicyclopentadiene type diphenols are particularly preferred.

  The thiol compound is not particularly limited, and examples thereof include benzene dithiol and triazine dithiol.

  Preferred specific examples of the active ester curing agent include an active ester curing agent having a dicyclopentadiene type diphenol structure, an active ester curing agent having a naphthalene structure, and an active ester curing agent having an acetylated product of phenol novolac. , Active ester-based curing agents containing phenol novolac benzoylates, active ester-based curing agents obtained by reacting aromatic carboxylic acids with phosphorus atom-containing oligomers having phenolic hydroxyl groups, among others, dicyclopentadiene type An active ester type curing agent containing a diphenol structure, an active ester type curing agent containing a naphthalene structure, and an active ester type curing agent obtained by reacting an aromatic carboxylic acid with a phosphorus atom-containing oligomer having a phenolic hydroxyl group are more preferred. . In the present invention, the “dicyclopentadiene type diphenol structure” represents a divalent structural unit composed of phenylene-dicyclopentylene-phenylene.

  As the active ester curing agent, active ester curing agents disclosed in JP-A Nos. 2004-277460 and 2013-40270 may be used, or commercially available active ester curing agents may be used. You can also. Commercially available products of the active ester curing agent include, for example, “EXB9451”, “EXB9460”, “EXB9460S”, “HPC-8000-65T”, “HPC-8000L-65M” (dicyclopentadiene-type diethylene manufactured by DIC). Active ester-based curing agent containing a phenol structure), "EXB9416-70BK" (active ester-based curing agent containing a naphthalene structure) manufactured by DIC, "DC808" (active ester containing an acetylated product of phenol novolak) Type curing agent), "YLH1026" (active ester type curing agent containing a benzoylated phenol novolak) manufactured by Mitsubishi Chemical Corporation, and "EXB9050L-62M" (phosphorus atom-containing active ester type curing agent) manufactured by DIC. .

  The content of the active ester-based curing agent is preferably 1% by mass or more, preferably 5% by mass when the nonvolatile component in the resin composition is 100% by mass from the viewpoint of lowering the linear thermal expansion coefficient and increasing the peel strength. % Or more is more preferable, and 10 mass% or more is more preferable. Although the upper limit of content of an active ester hardening agent is not specifically limited, 25 mass% or less is preferable, 20 mass% or less is more preferable, 15 mass% or less is further more preferable.

  In addition, when the number of epoxy groups in the (A) epoxy resin is 1, from the viewpoint of obtaining an insulating layer with good mechanical strength, the number of reactive groups in the (B) active ester curing agent is preferably 0.1 to 10, and 0 0.1 to 5 is more preferable, and 0.1 to 1 is more preferable. Here, “the number of epoxy groups of the epoxy resin” is a value obtained by totaling the values obtained by dividing the solid mass of each epoxy resin present in the resin composition by the epoxy equivalent for all epoxy resins. In addition, “reactive group” means a functional group capable of reacting with an epoxy group, and “the number of reactive groups of the active ester curing agent” means the active ester curing agent present in the resin composition. This is the total value of the values obtained by dividing the solid content mass by the reactive group equivalent.

<(C) Polyimide resin having a polycyclic aromatic hydrocarbon skeleton>
The resin composition includes (C) a polyimide resin having a polycyclic aromatic hydrocarbon skeleton. By having a polycyclic aromatic hydrocarbon skeleton which is a rigid skeleton, even if an inorganic filler with a small average particle size or a large specific surface area is used, the ten-point average roughness (Rz) and the linear thermal expansion coefficient are low. A cured product having high peel strength can be obtained. As described above, a thermoplastic resin containing a phenoxy resin, an aliphatic group, or the like is inferior in desmear resistance because of its high polarity, and as a result, the ten-point average roughness (Rz) may be increased. In addition to the rigid imide resin, the component (C) has a polycyclic aromatic hydrocarbon skeleton that is a rigid skeleton having excellent hydrophobicity. The cured product of the resin composition containing such a component (C) has a lower polarity than the case of containing a thermoplastic resin such as a phenoxy resin, and as a result, the roughness after the roughening treatment can be lowered. Therefore, the ten-point average roughness (Rz) can be lowered. In addition, since the component (C) has a rigid skeleton, it is difficult for the resin to break down, and thus the peel strength is increased. Furthermore, since the component (C) has a rigid skeleton, it is difficult to expand, so the linear thermal expansion coefficient is considered to be low.

  A polycyclic aromatic hydrocarbon refers to a hydrocarbon which contains two or more cyclic structures in one molecule, and at least one of the cyclic structures is an aromatic ring, and the two or more cyclic structures are condensed. It may or may not be condensed.

The polycyclic aromatic hydrocarbon skeleton may not have a substituent and may have a substituent. The substituent is not particularly limited, for example, a halogen atom, -OH, _{-O-C 1-6} alkyl group, -N _{(C 1-6 alkyl) 2, C 1-6 alkyl, C 6- 10} aryl group, —NH ₂ , —CN, —C (O) O—C _1-6 alkyl group, —COOH, —C (O) H, —NO _{2 and the} like, and C _1-6 alkyl group is Preferably, a methyl group is more preferable. Only one type of substituent may be included, or a plurality of substituents may be included.

Here, the term “C _pq ” (p and q are positive integers, satisfying p <q) means that the number of carbon atoms of the organic group described immediately after this term is p to q. Represents something. For example, the expression “C _1-6 alkyl group” refers to an alkyl group having 1 to 6 carbon atoms.

  Examples of the polycyclic aromatic hydrocarbon skeleton include an indane skeleton including a 1,1,3-trimethylindane skeleton, and an aromatic hydrocarbon skeleton obtained by condensing an aromatic ring with a 5-membered ring compound such as a fluorene skeleton. An aromatic hydrocarbon skeleton in which aromatics such as a naphthalene skeleton and an anthracene skeleton are condensed; an aromatic hydrocarbon skeleton having two or more aromatics such as a biphenyl skeleton without condensation (non-condensed aromatic hydrocarbon skeleton); From the viewpoint of lowering the ten-point average roughness (Rz), an aromatic hydrocarbon skeleton obtained by condensing a 5-membered ring compound and an aromatic ring is preferable. Among these, from the viewpoint of reducing the linear thermal expansion coefficient of the cured product of the resin composition and increasing the glass transition temperature and the peel strength, the polycyclic aromatic hydrocarbon skeleton is at least one of an indane skeleton and a fluorene skeleton. It is preferable.

  The component (C) is not particularly limited as long as it is an imide resin having a polycyclic aromatic hydrocarbon skeleton, but the linear thermal expansion coefficient of the cured product of the resin composition is lowered, and the glass transition temperature and the peel strength are increased. From the point of view, it is preferably a polyimide resin having a cyclic imide structure.

  Examples of the cyclic imide structure include phthalimide, succinimide, glutarimide, 3-methylglutarimide, maleimide, dimethylmaleimide, trimellitimide, and pyromelliticimide, preferably phthalimide and succinimide, and particularly has an aromatic imide structure. A polyimide resin is preferred, and phthalimide is more preferred.

  The component (C) has a repeating unit having a polycyclic aromatic hydrocarbon skeleton and an imide structure from the viewpoint of lowering the linear thermal expansion coefficient of the cured product of the resin composition and increasing the glass transition temperature and peel strength. It is preferable to have a repeating unit.

（式（１）中、Ａは多環式芳香族炭化水素骨格を表し、Ｄは単結合又は２価の連結基を表す。） As the repeating unit having a polycyclic aromatic hydrocarbon skeleton, for example, a repeating unit represented by the following general formula (1) is preferable.

(In formula (1), A represents a polycyclic aromatic hydrocarbon skeleton, and D represents a single bond or a divalent linking group.)

  A in Formula (1) represents a polycyclic aromatic hydrocarbon skeleton, and details of the polycyclic aromatic hydrocarbon skeleton are as described above.

  D in Formula (1) represents a single bond or a divalent linking group, and a divalent linking group is preferred. Examples of the divalent linking group include an oxygen atom, a sulfur atom, an alkylene group, an arylene group, —NH—, —C (═O) —, —SO—, or a group consisting of a combination of two or more thereof. Is mentioned.

  As the alkylene group, an alkylene group having 1 to 10 carbon atoms is preferable, an alkylene group having 1 to 6 carbon atoms is more preferable, and an alkylene group having 1 to 3 carbon atoms is more preferable. The alkylene group may be linear, branched or cyclic. Examples of such an alkylene group include a methylene group, an ethylene group, a propylene group, a butylene group, a pentylene group, and a hexylene group, and a methylene group is preferable.

  As the arylene group, an arylene group having 6 to 14 carbon atoms is preferable, and an arylene group having 6 to 10 carbon atoms is more preferable. As an arylene group, a phenylene group, a naphthylene group, an anthracenylene group etc. are mentioned, for example, A phenylene group is preferable.

  The alkylene group and the arylene group may not have a substituent and may have a substituent. The substituent is the same as the substituent that the polycyclic aromatic hydrocarbon skeleton may have.

  The group consisting of a combination of two or more of these is preferably a group consisting of a combination of two or more of an oxygen atom, an arylene group, and an alkylene group. Examples of such a group include a group in which one or more arylene groups and one or more alkylene groups are bonded (a group comprising a combination of an arylene group and an alkylene group), one or more oxygen atoms, and one group. And a group in which the above arylene group is bonded (a group formed by a combination of an oxygen atom and an arylene group). Examples of the group in which one or more arylene groups and one or more alkylene groups are bonded include a divalent group composed of phenylene-methylene and a divalent group composed of phenylene-dimethylmethylene. Examples of the group in which one or more oxygen atoms and one or more arylene groups are bonded include, for example, a divalent group composed of phenylene-oxygen atom-phenylene, a divalent group composed of oxygen atom-phenylene, an oxygen atom— And divalent groups composed of naphthalene.

Preferable examples of the repeating unit having a polycyclic aromatic hydrocarbon skeleton include the following.

  The repeating unit having an imide structure is not particularly limited as long as it has an imide structure, but from the viewpoint of reducing the linear thermal expansion coefficient of the cured product of the resin composition and increasing the glass transition temperature and the peel strength, A repeating unit having an imide structure is preferred.

  Examples of the cyclic imide structure include phthalimide, succinimide, glutarimide, 3-methylglutarimide, maleimide, dimethylmaleimide, trimellitimide, and pyromelliticimide, preferably phthalimide and succinimide, and among them, an aromatic imide structure is preferable. More preferred is phthalimide. The repeating unit having an imide structure may be an embodiment in which the imide structure is bonded to a divalent linking group. The divalent linking group is the same as the divalent linking group represented by D in the general formula (1).

Preferable examples of the repeating unit having an imide structure include the following.

  As a mass ratio of the repeating unit having a polycyclic aromatic hydrocarbon skeleton and the repeating unit having an imide structure (mass of repeating unit having a polycyclic aromatic hydrocarbon skeleton / mass of repeating unit having an imide structure) Is preferably 0.5 or more, more preferably 0.6 or more, still more preferably 0.8 or more, preferably 2 or less, more preferably 1.8 or less, and still more preferably 1.5 or less. By setting the mass ratio within such a range, the linear thermal expansion coefficient of the cured product of the resin composition can be lowered, and the glass transition temperature and the peel strength can be increased.

  The manufacturing method of (C) component is not specifically limited, It can manufacture according to various methods. As a preferred embodiment, it can be obtained by polymerization using a monomer that becomes a repeating unit having an imide structure and a monomer that becomes a repeating unit having a polycyclic aromatic hydrocarbon skeleton. . When performing polymerization, a polymerization initiator or the like may be used as necessary.

  The weight average molecular weight of the component (C) is preferably 5000 or more, more preferably 10,000 or more, and still more preferably from the viewpoint of obtaining a cured product having a low ten-point average roughness (Rz) and a low coefficient of linear thermal expansion and high peel strength. Is 11,000 or more, preferably 100,000 or less, more preferably 50000 or less, and still more preferably 30000 or less. Here, the weight average molecular weight of the component (C) is a polystyrene equivalent weight average molecular weight measured by a gel permeation chromatography (GPC) method.

  When the content of the component (C) is such that the ten-point average roughness (Rz) and linear thermal expansion coefficient are low and a cured product having high peel strength is obtained, the nonvolatile component in the resin composition is 100% by mass. The content is preferably 0.1% by mass or more, more preferably 0.3% by mass or more, and further preferably 0.5% by mass or more. The upper limit is preferably 3% by mass or less, more preferably 2% by mass or less, and still more preferably 1.5% by mass or less.

<(D) Inorganic filler>
The resin composition of the first embodiment includes (D) an inorganic filler having an average particle diameter of 100 nm or less. Moreover, the resin composition of 2nd Embodiment contains the inorganic filler whose (D) specific surface area is 15 m < ² > / g or more. The material of the component (D) is not particularly limited. For example, 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, oxidation Examples thereof include titanium, zirconium oxide, barium titanate, barium zirconate titanate, barium zirconate, calcium zirconate, zirconium phosphate, and zirconium tungstate phosphate. Of these, silica is particularly preferred. Examples of the silica include amorphous silica, fused silica, crystalline silica, synthetic silica, and hollow silica. Moreover, spherical silica is preferable as the silica. An inorganic filler may be used individually by 1 type, and may be used in combination of 2 or more type.

The average particle diameter of the inorganic filler in the first embodiment is 100 nm or less, preferably 90 nm or less, more preferably 80 nm or less, from the viewpoints of thinning and reducing the ten-point average roughness (Rz). is there. The lower limit of the average particle diameter is not particularly limited, but can be preferably 1 nm or more, more preferably 5 nm or more, and further preferably 10 nm or more.
In addition, the average particle diameter of the inorganic filler in the second embodiment is preferably 100 nm or less, more preferably 90 nm or less, and more preferably 90 nm or less, from the viewpoint of reducing the thickness and reducing the ten-point average roughness (Rz). Preferably it is 80 nm or less. The lower limit of the average particle diameter is not particularly limited, but can be preferably 1 nm or more, more preferably 5 nm or more, and further preferably 10 nm or more.
Examples of commercially available inorganic fillers having such an average particle diameter include “UFP-30” manufactured by Denki Kagaku Kogyo Co., Ltd.

  The average particle diameter of the inorganic filler can be measured by a laser diffraction / scattering method based on Mie scattering theory. Specifically, the particle size distribution of the inorganic filler can be prepared on a volume basis by a laser diffraction / scattering particle size distribution measuring apparatus, and the median diameter can be measured as the average particle diameter. As the measurement sample, an inorganic filler dispersed in methyl ethyl ketone by ultrasonic waves can be preferably used. As a laser diffraction scattering type particle size distribution measuring device, “LA-500” manufactured by Horiba, Ltd., “SALD-2200” manufactured by Shimadzu Corporation, etc. can be used.

The specific surface area of the inorganic filler in the second embodiment is 15 m ² / g or more, more preferably 20 m ² / g or more, from the viewpoint of reducing the thickness and reducing the ten-point average roughness (Rz). Preferably it is 30 m ² / g or more. Although there is no special restriction | limiting in an upper limit, Preferably it is 60 m < ² > / g or less, More preferably, it is 50 m < ² > / g or less, More preferably, it is 40 m < ² > / g or less.
In addition, the specific surface area of the inorganic filler in the first embodiment is preferably 15 m ² / g or more, more preferably 20 m ² / g or more, from the viewpoint of reducing the thickness and reducing the ten-point average roughness (Rz). More preferably, it is 30 m ² / g or more. Although there is no special restriction | limiting in an upper limit, Preferably it is 60 m < ² > / g or less, More preferably, it is 50 m < ² > / g or less, More preferably, it is 40 m < ² > / g or less.
The specific surface area can be obtained by adsorbing nitrogen gas on the sample surface using a specific surface area measuring device (Macsorb HM-1210 manufactured by Mountec Co., Ltd.) according to the BET method, and calculating the specific surface area using the BET multipoint method.

  Inorganic fillers are fluorine-containing silane coupling agents, aminosilane coupling agents, epoxysilane coupling agents, mercaptosilane coupling agents, silane coupling agents, alkoxysilanes from the viewpoint of improving moisture resistance and dispersibility. It is preferably treated with one or more surface treatment agents such as an organosilazane compound and a titanate coupling agent, and more preferably treated with an aminosilane silane coupling agent. Examples of commercially available surface treatment agents include “KBM403” (3-glycidoxypropyltrimethoxysilane) manufactured by Shin-Etsu Chemical Co., Ltd., “KBM803” (3-mercaptopropyltrimethoxysilane) manufactured by Shin-Etsu Chemical Co., Ltd., Shin-Etsu. “KBE903” (3-aminopropyltriethoxysilane) manufactured by Chemical Industry Co., Ltd. “KBM573” (N-phenyl-3-aminopropyltrimethoxysilane) manufactured by Shin-Etsu Chemical Co., Ltd., “SZ-31” manufactured by Shin-Etsu Chemical Co., Ltd. ( Hexamethyldisilazane), “KBM103” (phenyltrimethoxysilane) manufactured by Shin-Etsu Chemical Co., Ltd., “KBM-4803” (long-chain epoxy type silane coupling agent) manufactured by Shin-Etsu Chemical Co., Ltd., “KBM-” manufactured by Shin-Etsu Chemical Co., Ltd. 7103 "(3,3,3-trifluoropropyltrimethoxysilane) and the like.

The degree of the surface treatment with the surface treatment agent is that the surface treatment is performed with 0.2 to 5 parts by mass of the surface treatment agent with respect to 100 parts by mass of the component (D) from the viewpoint of improving the dispersibility of the inorganic filler. It is preferable that the surface treatment is performed at 0.2 to 4 parts by mass, and the surface treatment is preferably performed at 0.3 to 3 parts by mass.
The degree of surface treatment with the surface treatment agent can be evaluated by the amount of carbon per unit surface area of the inorganic filler. Carbon content per unit surface area of the inorganic filler, from the viewpoint of improving dispersibility of the inorganic filler is preferably 0.02 mg / ^{m 2} or more, 0.1 mg / ^{m 2} or more preferably, 0.2 mg / ^{m 2} The above is more preferable. On the other hand, 1 mg / m ² or less is preferable, 0.8 mg / m ² or less is more preferable, and 0.5 mg / m ² or less is more preferable from the viewpoint of suppressing an increase in the melt viscosity of the resin varnish and the sheet form. preferable.

  The amount of carbon per unit surface area of the inorganic filler can be measured after the surface-treated inorganic filler is washed with a solvent (for example, methyl ethyl ketone (MEK)). Specifically, a sufficient amount of MEK as a solvent is added to the inorganic filler surface-treated with the surface treatment agent and ultrasonically cleaned at 25 ° C. for 5 minutes. After removing the supernatant and drying the solid, the carbon amount per unit surface area of the inorganic filler can be measured using a carbon analyzer. As the carbon analyzer, “EMIA-320V” manufactured by HORIBA, Ltd. can be used.

  The content of the component (D) is preferably 30% by mass or more, more preferably 35% by mass or more, and more preferably 35% by mass or more, when the nonvolatile component in the resin composition is 100% by mass from the viewpoint of reducing the linear thermal expansion coefficient. Preferably it is 40 mass% or more. From the viewpoint of improving the insulation performance, the upper limit is preferably 80% by mass or less, more preferably 70% by mass or less, and still more preferably 65% by mass or less.

<(E) Curing agent>
In one embodiment, the resin composition may contain (E) a curing agent. However, (E) curing agent here does not include (B) active ester curing agent. The component (E) is not particularly limited as long as it has a function of curing the component (A). For example, a phenol-based curing agent, a naphthol-based curing agent, a benzoxazine-based curing agent, a cyanate ester-based curing agent. And carbodiimide-based curing agents. Especially, as a (E) component, a phenol type hardening | curing agent is preferable. A hardening | curing agent may be used individually by 1 type, and may use 2 or more types together.

  As the phenol-based curing agent and the naphthol-based curing agent, a phenol-based curing agent having a novolak structure or a naphthol-based curing agent having a novolak structure is preferable from the viewpoint of heat resistance and water resistance. Moreover, from a viewpoint of adhesiveness with a conductor layer, a nitrogen-containing phenol type hardening | curing agent is preferable and a triazine frame | skeleton containing phenol type hardening | curing agent is more preferable.

  Specific examples of the phenol-based curing agent and the naphthol-based curing agent include, for example, “MEH-7700”, “MEH-7810”, “MEH-7785” manufactured by Meiwa Kasei Co., Ltd., “NHN” manufactured by Nippon Kayaku Co., Ltd. “CBN”, “GPH”, “SN170”, “SN180”, “SN190”, “SN475”, “SN485”, “SN495”, “SN-495V”, “SN375”, “SN395” manufactured by Nippon Steel & Sumikin Chemical Co., Ltd. ”,“ TD-2090 ”,“ LA-7052 ”,“ LA-7054 ”,“ LA-1356 ”,“ LA-3018-50P ”,“ EXB-9500 ”manufactured by DIC.

  Specific examples of the benzoxazine-based curing agent include “HFB2006M” manufactured by Showa Polymer Co., Ltd. and “Pd” and “Fa” manufactured by Shikoku Kasei Kogyo Co., Ltd.

  Examples of the cyanate ester curing agent include bisphenol A dicyanate, polyphenol cyanate, oligo (3-methylene-1,5-phenylene cyanate), 4,4′-methylenebis (2,6-dimethylphenyl cyanate), 4,4. '-Ethylidene diphenyl dicyanate, hexafluorobisphenol A dicyanate, 2,2-bis (4-cyanate) phenylpropane, 1,1-bis (4-cyanatephenylmethane), bis (4-cyanate-3,5-dimethyl) Bifunctional cyanate resins such as phenyl) methane, 1,3-bis (4-cyanatephenyl-1- (methylethylidene)) benzene, bis (4-cyanatephenyl) thioether, and bis (4-cyanatephenyl) ether, phenol Novolac and K Polyfunctional cyanate resin derived from tetrazole novolac, these cyanate resins and partially triazine of prepolymer. Specific examples of the cyanate ester curing agent include “PT30” and “PT60” (phenol novolac type polyfunctional cyanate ester resin), “ULL-950S” (polyfunctional cyanate ester resin), and “BA230” manufactured by Lonza Japan. , “BA230S75” (a prepolymer in which part or all of bisphenol A dicyanate is triazine-modified into a trimer), and the like.

  Specific examples of the carbodiimide curing agent include “V-03” and “V-07” manufactured by Nisshinbo Chemical Co., Ltd.

  When the resin composition contains the component (E), the amount ratio of the component (A) to the component (E) is [total number of epoxy groups in the component (A)]: [reactive group of the component (E) The ratio of the total number] is preferably in the range of 1: 0.01 to 1: 2, more preferably 1: 0.05 to 1: 1.5, and even more preferably 1: 0.08 to 1: 1. Here, the reactive group of (E) component is an active hydroxyl group etc., and changes with kinds of (E) component. The total number of epoxy groups in component (A) is a value obtained by totaling the values obtained by dividing the solid content mass of each component (A) by the epoxy equivalent for all components (A). The total number of reactive groups is a value obtained by adding the values obtained by dividing the solid content mass of each (E) component by the reactive group equivalent for all (E) components. By setting the amount ratio of the component (A) to the component (E) within such a range, the linear thermal expansion coefficient of the cured product of the resin composition can be further reduced, and the peel strength can be further improved. .

  Moreover, when a resin composition contains (E) component, the quantitative ratio of (A) epoxy resin, (B) component, and (E) component is [total number of epoxy groups of (A) component]: The ratio of [the total number of reactive groups of component (B) and reactive groups of component (E)] is preferably in the range of 1: 0.01 to 1: 3, more preferably 1: 0.005 to 1: 2. 1: 0.1 to 1: 1.5 is more preferable.

  When the resin composition contains the component (E), from the viewpoint of lowering the linear thermal expansion coefficient of the cured product of the resin composition and increasing the peel strength, the content of the component (E) When the non-volatile component is 100% by mass, it is preferably 15% by mass or less, more preferably 10% by mass or less, and further preferably 5% by mass or less. The lower limit is not particularly limited, but is preferably 1% by mass or more, more preferably 2% by mass or more, and further preferably 3% by mass or more.

<(F) Curing accelerator>
In one embodiment, the resin composition may contain (F) a curing accelerator. Examples of the curing accelerator include a phosphorus-based curing accelerator, an amine-based curing accelerator, an imidazole-based curing accelerator, a guanidine-based curing accelerator, a metal-based curing accelerator, and the like. A curing accelerator, an imidazole curing accelerator, and a metal curing accelerator are preferable, and an amine curing accelerator is more preferable. A hardening accelerator may be used individually by 1 type, and may be used in combination of 2 or more type.

  Examples of phosphorus curing accelerators include triphenylphosphine, phosphonium borate compounds, tetraphenylphosphonium tetraphenylborate, n-butylphosphonium tetraphenylborate, tetrabutylphosphonium decanoate, (4-methylphenyl) triphenylphosphonium thiocyanate. , Tetraphenylphosphonium thiocyanate, butyltriphenylphosphonium thiocyanate and the like, and triphenylphosphine and tetrabutylphosphonium decanoate are preferable.

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

  Examples of the imidazole curing accelerator include 2-methylimidazole, 2-undecylimidazole, 2-heptadecylimidazole, 1,2-dimethylimidazole, 2-ethyl-4-methylimidazole, 1,2-dimethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 1-benzyl-2-methylimidazole, 1-benzyl-2-phenylimidazole, 1-cyanoethyl-2-methylimidazole, 1-cyanoethyl-2-undecylimidazole, 1-cyanoethyl-2-ethyl-4-methylimidazole, 1-cyanoethyl-2-phenylimidazole, 1-cyanoethyl-2-undecylimidazolium trimellitate, 1-cyanoethyl- 2 Phenylimidazolium trimellitate, 2,4-diamino-6- [2'-methylimidazolyl- (1 ')]-ethyl-s-triazine, 2,4-diamino-6- [2'-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, 2,3-dihydro-1H-pyrrolo [1,2-a] benzimidazole, 1-dodecyl-2-me Examples thereof include imidazole compounds such as ru-3-benzylimidazolium chloride, 2-methylimidazoline, 2-phenylimidazoline, and adducts of imidazole compounds and epoxy resins, such as 2-ethyl-4-methylimidazole and 1-benzyl-2. -Phenylimidazole is preferred.

  Commercially available products may be used as the imidazole curing accelerator, and examples thereof include “P200-H50” manufactured by Mitsubishi Chemical Corporation.

  Examples of the guanidine curing accelerator include dicyandiamide, 1-methylguanidine, 1-ethylguanidine, 1-cyclohexylguanidine, 1-phenylguanidine, 1- (o-tolyl) guanidine, dimethylguanidine, diphenylguanidine, trimethylguanidine, Tetramethylguanidine, pentamethylguanidine, 1,5,7-triazabicyclo [4.4.0] dec-5-ene, 7-methyl-1,5,7-triazabicyclo [4.4.0] Deca-5-ene, 1-methyl biguanide, 1-ethyl biguanide, 1-n-butyl biguanide, 1-n-octadecyl biguanide, 1,1-dimethyl biguanide, 1,1-diethyl biguanide, 1-cyclohexyl biguanide, 1 -Allyl biguanide, 1-phenyl biguanide, 1- ( - tolyl) biguanide, and the like, dicyandiamide, 1,5,7-triazabicyclo [4.4.0] dec-5-ene are preferred.

  As a metal type hardening accelerator, the organometallic complex or organometallic salt of metals, such as cobalt, copper, zinc, iron, nickel, manganese, tin, is mentioned, for example. Specific examples of the organometallic complex include organic cobalt complexes such as cobalt (II) acetylacetonate and cobalt (III) acetylacetonate, organic copper complexes such as copper (II) acetylacetonate, and zinc (II) acetylacetonate. Organic zinc complexes such as iron (III) acetylacetonate, organic nickel complexes such as nickel (II) acetylacetonate, and organic manganese complexes such as manganese (II) acetylacetonate. Examples of the organic metal salt include zinc octylate, tin octylate, zinc naphthenate, cobalt naphthenate, tin stearate, and zinc stearate.

  When the resin composition contains a curing accelerator, the content of the curing accelerator is preferably 0.01% by mass or more, more preferably 0.05%, when the nonvolatile component in the resin composition is 100% by mass. It is at least mass%, more preferably at least 0.1 mass%. An upper limit becomes like this. Preferably it is 3 mass% or less, More preferably, it is 2 mass% or less, More preferably, it is 1 mass% or less. By setting the content of the curing accelerator within such a range, a cured product of the resin composition having a low linear thermal expansion coefficient and a high peel strength can be obtained.

<(G) Thermoplastic resin>
In one embodiment, the resin composition may contain (G) a thermoplastic resin. However, the (G) thermoplastic resin here does not include (C) a polyimide resin having a polycyclic aromatic hydrocarbon.

  Examples of the thermoplastic resin include a phenoxy resin, a polyvinyl acetal resin, a polyolefin resin, a polybutadiene resin, a polyimide resin (excluding a polyimide resin corresponding to the component (C)), a polyamideimide resin, a polyetherimide resin, a polysulfone resin, Examples include polyethersulfone resins, polyphenylene ether resins, polycarbonate resins, polyetheretherketone resins, polyester resins, and the like, and phenoxy resins are preferred. A thermoplastic resin may be used individually by 1 type, or may be used in combination of 2 or more type.

  The polystyrene-converted weight average molecular weight of the thermoplastic resin is preferably 8,000 or more, more preferably 10,000 or more, still more preferably 20,000 or more, and particularly preferably 40,000 or more. Although an upper limit is not specifically limited, Preferably it is 70,000 or less, More preferably, it is 60,000 or less. The weight average molecular weight in terms of polystyrene of the thermoplastic resin is measured by a gel permeation chromatography (GPC) method. Specifically, the polystyrene-converted weight average molecular weight of the thermoplastic resin is LC-9A / RID-6A manufactured by Shimadzu Corporation as a measuring device, and Shodex K-800P / K-804L / K- manufactured by Showa Denko KK as a column. 804L can be calculated using a standard polystyrene calibration curve by measuring the column temperature at 40 ° C. using chloroform or the like as the mobile phase.

  Examples of the phenoxy resin include bisphenol A skeleton, bisphenol F skeleton, bisphenol S skeleton, bisphenolacetophenone skeleton, novolac skeleton, biphenyl skeleton, fluorene skeleton, dicyclopentadiene skeleton, norbornene skeleton, naphthalene skeleton, anthracene skeleton, adamantane skeleton, terpene Examples thereof include phenoxy resins having a skeleton and one or more skeletons selected from the group consisting of a trimethylcyclohexane skeleton. The terminal of the phenoxy resin may be any functional group such as a phenolic hydroxyl group or an epoxy group. A phenoxy resin may be used individually by 1 type, and may be used in combination of 2 or more type. Specific examples of the phenoxy resin include “1256” and “4250” (both bisphenol A skeleton-containing phenoxy resin), “YX8100” (bisphenol S skeleton-containing phenoxy resin), and “YX6954” (bisphenolacetophenone) manufactured by Mitsubishi Chemical Corporation. In addition, “FX280” and “FX293” manufactured by NS ”,“ YL6794 ”,“ YL7213 ”,“ YL7290 ”,“ YL7482 ”, and the like.

  Examples of the polyvinyl acetal resin include a polyvinyl formal resin and a polyvinyl butyral resin, and a polyvinyl butyral resin is preferable. Specific examples of the polyvinyl acetal resin include, for example, “Electrical butyral 4000-2”, “Electrical butyral 5000-A”, “Electrical butyral 6000-C”, “Electrical butyral 6000-EP”, and Sekisui. Examples include ESREC BH series, BX series (for example, BX-5Z), KS series (for example, KS-1), BL series, and BM series manufactured by Chemical Industries.

  Specific examples of the polyimide resin include “Rika Coat SN20” and “Rika Coat PN20” manufactured by Shin Nippon Rika Co., Ltd. Specific examples of the polyimide resin include linear polyimide obtained by reacting a bifunctional hydroxyl group-terminated polybutadiene, a diisocyanate compound and a tetrabasic acid anhydride (polyimide described in JP-A-2006-37083), a polysiloxane skeleton. Examples thereof include modified polyimides such as containing polyimide (polyimides described in JP-A Nos. 2002-12667 and 2000-319386).

  Specific examples of the polyethersulfone resin include “PES5003P” manufactured by Sumitomo Chemical Co., Ltd. Specific examples of the polyphenylene ether resin include an oligophenylene ether / styrene resin “OPE-2St 1200” having a vinyl group manufactured by Mitsubishi Gas Chemical Company.

  Specific examples of the polysulfone resin include polysulfone “P1700” and “P3500” manufactured by Solvay Advanced Polymers.

  When the resin composition contains a thermoplastic resin, the content of the thermoplastic resin is preferably 0.1% by mass or more, more preferably 0.3% when the nonvolatile component in the resin composition is 100% by mass. It is at least 0.5% by mass, more preferably at least 0.5% by mass. The upper limit is preferably 10% by mass or less, more preferably 5% by mass or less, and further preferably 3% by mass.

<(H) Other additives>
In one embodiment, the resin composition may further contain other additives as necessary. Examples of such other additives include organic phosphorus compounds, organic nitrogen-containing phosphorus compounds, Flame retardants such as nitrogen compounds, silicone compounds and metal hydroxides; organic fillers such as rubber particles; organometallic compounds such as organic copper compounds, organic zinc compounds and organic cobalt compounds; thickeners, antifoaming agents, leveling And resin additives such as a colorant, an adhesion-imparting agent, and a colorant.

<Physical properties and uses of resin composition>
The resin composition of the present invention provides an insulating layer (cured product of the resin composition layer) having a low ten-point average roughness (Rz) and a linear thermal expansion coefficient after the roughening treatment and a high peel strength. Therefore, the resin composition of the present invention can be suitably used as a resin composition layer for insulating applications. Specifically, the resin composition of the present invention can be suitably used as a resin composition (resin composition for an insulating layer of a printed wiring board) for forming an insulating layer of a printed wiring board. It can be more suitably used as a resin composition (resin composition for an interlayer insulating layer of a printed wiring board) for forming an interlayer insulating layer of a board. Moreover, since the resin composition of this invention brings about an insulating layer favorable for component embedding property, it can be used conveniently also when a printed wiring board is a component built-in circuit board. Moreover, the resin composition of the present invention is a resin composition for forming a conductive layer (including a rewiring layer) on the insulating layer (an insulating layer for forming a conductive layer). It can be suitably used as a forming resin composition).

  A cured product obtained by thermally curing the resin composition at 100 ° C. for 30 minutes and then at 180 ° C. for 30 minutes exhibits a characteristic that the ten-point average roughness (Rz) after the roughening treatment is low. That is, an insulating layer having a low ten-point average roughness is provided. The ten-point average roughness (Rz) is preferably 1500 nm or less, more preferably 1000 nm or less, and still more preferably 600 nm or less. The lower limit is not particularly limited, but may be 1 nm or more. The ten-point average roughness (Rz) can be measured according to the method described in <Measurement of peel strength and ten-point average roughness (Rz value)> described later.

  A cured product obtained by thermosetting the resin composition at 100 ° C. for 30 minutes and then at 180 ° C. for 30 minutes exhibits a characteristic of high peel strength (plating peel strength). That is, an insulating layer with high peel strength is provided. The peel strength is preferably 145 kgf / cm or more, more preferably 148 kgf / cm or more, and further preferably 150 kgf / cm or more. The upper limit is not particularly limited, but may be 300 kgf / cm or less. The peel strength can be measured according to the method described in <Measurement of peel strength and ten-point average roughness (Rz value)> described later.

  A cured product obtained by thermally curing the resin composition at 200 ° C. for 90 minutes exhibits a characteristic that the glass transition temperature is high. Thus, an insulating layer with improved brittleness is provided. The glass transition temperature is preferably 145 ° C. or higher, more preferably 148 ° C. or higher, and further preferably 150 ° C. or higher. Although an upper limit is not specifically limited, It can be set as 300 degrees C or less. The glass transition temperature can be measured according to the method described in <Measurement of glass transition temperature and linear thermal expansion coefficient> described later.

  A cured product obtained by thermosetting the resin composition at 200 ° C. for 90 minutes exhibits a characteristic that the coefficient of linear thermal expansion is low. That is, an insulating layer having a low linear thermal expansion coefficient is provided. The linear thermal expansion coefficient is preferably 45 ppm or less, more preferably 44 ppm or less, and still more preferably 43 ppm or less. The lower limit is not particularly limited, but may be 1 ppm or more. The linear thermal expansion coefficient can be measured according to the method described later in <Measurement of glass transition temperature and linear thermal expansion coefficient>.

[Resin sheet]
The resin sheet of the present invention includes a support and a resin composition layer formed on the support and formed of the resin composition of the present invention.

  The thickness of the resin composition layer is preferably 200 μm or less, more preferably 100 μm or less, still more preferably 50 μm or less, even more preferably 20 μm or less, 15 μm or less, or 10 μm or less, from the viewpoint of thinning the printed wiring board. is there. Although the minimum of the thickness of a resin composition layer is not specifically limited, Usually, it may be 1 micrometer or more, 3 micrometers or more, etc.

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

  When a film made of a plastic material is used as the support, examples of the plastic material include polyethylene terephthalate (hereinafter sometimes abbreviated as “PET”) and polyethylene naphthalate (hereinafter abbreviated as “PEN”). .) Polyester, polycarbonate (hereinafter sometimes abbreviated as “PC”), polymethyl methacrylate (PMMA) and other acrylics, cyclic polyolefin, triacetyl cellulose (TAC), polyether sulfide (PES), polyether Examples include ketones and polyimides. Among these, polyethylene terephthalate and polyethylene naphthalate are preferable, and inexpensive polyethylene terephthalate is particularly preferable.

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

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

  Moreover, as a support body, you may use the support body with a release layer which has a release layer in the surface joined to a resin composition layer. Examples of the release agent used for the release layer of the support with a release layer include one or more release agents selected from the group consisting of alkyd resins, polyolefin resins, urethane resins, and silicone resins. . As the support with a release layer, a commercially available product may be used. For example, “SK-1”, “SK-1” manufactured by Lintec Corporation, which is a PET film having a release layer mainly composed of an alkyd resin release agent. AL-5 ”,“ AL-7 ”,“ Lumirror T60 ”manufactured by Toray Industries, Inc.,“ Purex ”manufactured by Teijin Limited,“ Unipeel ”manufactured by Unitika Ltd., and the like.

  Although it does not specifically limit as thickness of a support body, The range of 5 micrometers-75 micrometers is preferable, and the range of 10 micrometers-60 micrometers is more preferable. In addition, when using a support body with a release layer, it is preferable that the thickness of the whole support body with a release layer is the said range.

  In one embodiment, the resin sheet may further include other layers as necessary. Examples of such other layers include a protective film according to the support provided on the surface of the resin composition layer that is not joined to the support (that is, the surface opposite to the support). It is done. Although the thickness of a protective film is not specifically limited, For example, they are 1 micrometer-40 micrometers. By laminating the protective film, it is possible to suppress adhesion and scratches of dust and the like on the surface of the resin composition layer.

  The resin sheet is prepared by, for example, preparing a resin varnish in which a resin composition is dissolved in an organic solvent, applying the resin varnish on a support using a die coater or the like, and further drying to form a resin composition layer. Can be manufactured.

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

  Drying may be performed by a known method such as heating or hot air blowing. The drying conditions are not particularly limited, but the drying is performed so that the content of the organic solvent in the resin composition layer is 10% by mass or less, preferably 5% by mass or less. Depending on the boiling point of the organic solvent in the resin varnish, for example, when using a resin varnish containing 30% by mass to 60% by mass of the organic solvent, the resin composition is dried at 50 ° C. to 150 ° C. for 3 minutes to 10 minutes. A physical layer can be formed.

  The resin sheet can be stored in a roll. When the resin sheet has a protective film, it can be used by peeling off the protective film.

[Printed wiring board]
The printed wiring board of the present invention includes an insulating layer, a first conductor layer, and a second conductor layer formed of a cured product of the resin composition of the present invention. The insulating layer is provided between the first conductor layer and the second conductor layer, and insulates the first conductor layer from the second conductor layer (the conductor layer is referred to as a wiring layer). is there).

  The thickness of the insulating layer between the first and second conductor layers is preferably 6 μm or less, more preferably 5.5 μm or less, and even more preferably 5 μm or less. The lower limit is not particularly limited, but may be 0.1 μm or more. The distance between the first conductor layer and the second conductor layer (the thickness of the insulating layer between the first and second conductor layers) is the main surface of the first conductor layer 1 as shown in FIG. 11 and the thickness t 1 of the insulating layer 3 between the main surface 21 of the second conductor layer 2. The first and second conductor layers are conductor layers adjacent to each other via an insulating layer, and the main surface 11 and the main surface 21 face each other.

  The total thickness t2 of the insulating layer is preferably 15 μm or less, more preferably 13 μm or less, and even more preferably 10 μm or less. Although it does not specifically limit about a minimum, Usually, it can be set as 1 micrometer or more, 1.5 micrometers or more, 2 micrometers or more, etc.

A printed wiring board can be manufactured by the method including the process of following (I) and (II) using the above-mentioned resin sheet.
(I) The process of laminating | stacking so that the resin composition layer of a resin sheet may join to an inner layer board | substrate on an inner layer board | substrate (II) The process of thermosetting a resin composition layer and forming an insulating layer

  The “inner layer substrate” used in the step (I) is a member that becomes a printed wiring board substrate, for example, a glass epoxy substrate, a metal substrate, a polyester substrate, a polyimide substrate, a BT resin substrate, a thermosetting polyphenylene ether substrate. Etc. Moreover, this board | substrate may have a conductor layer in the single side | surface or both surfaces, and this conductor layer may be patterned. An inner layer substrate having a conductor layer (circuit) formed on one or both sides of the substrate may be referred to as an “inner layer circuit board”. Further, when the printed wiring board is manufactured, an intermediate product in which an insulating layer and / or a conductor layer is to be formed is also included in the “inner layer substrate” in the present invention. When the printed wiring board is a circuit board with a built-in component, an inner layer board with a built-in component can be used.

  Lamination | stacking of an inner layer board | substrate and a resin sheet can be performed by heat-pressing a resin sheet to an inner layer board | substrate from the support body side, for example. Examples of the member that heat-presses the resin sheet to the inner layer substrate (hereinafter, also referred to as “heat-pressing member”) include a heated metal plate (SUS end plate) or a metal roll (SUS roll). It is preferable that the thermocompression-bonding member is not pressed directly on the resin sheet, but is pressed through an elastic material such as heat-resistant rubber so that the resin sheet sufficiently follows the surface irregularities of the inner layer substrate.

  Lamination of the inner layer substrate and the resin sheet may be performed by a vacuum laminating method. In the vacuum laminating method, the thermocompression bonding temperature is preferably in the range of 60 ° C to 160 ° C, more preferably 80 ° C to 140 ° C, and the thermocompression bonding pressure is preferably 0.098 MPa to 1.77 MPa, more preferably 0. The thermocompression bonding time is preferably in the range of 20 seconds to 400 seconds, more preferably in the range of 30 seconds to 300 seconds. Lamination is preferably performed under reduced pressure conditions with a pressure of 26.7 hPa or less.

  Lamination can be performed with a commercially available vacuum laminator. Examples of the commercially available vacuum laminator include a vacuum pressurizing laminator manufactured by Meiki Seisakusho, a vacuum applicator manufactured by Nikko Materials, and a batch vacuum pressurizing laminator.

  After lamination, the laminated resin sheets may be smoothed under normal pressure (atmospheric pressure), for example, by pressing a thermocompression bonding member from the support side. The pressing conditions for the smoothing treatment can be the same conditions as the thermocompression bonding conditions for the laminate. The smoothing treatment can be performed with a commercially available laminator. In addition, you may perform lamination | stacking and a smoothing process continuously using said commercially available vacuum laminator.

  The support may be removed between step (I) and step (II), or may be removed after step (II).

  In step (II), the resin composition layer is thermally cured to form an insulating layer.

  The thermosetting conditions for the resin composition layer are not particularly limited, and the conditions normally employed when forming the insulating layer of the printed wiring board may be used.

  For example, although the thermosetting conditions of the resin composition layer vary depending on the type of the resin composition, the curing temperature is in the range of 120 ° C to 240 ° C (preferably in the range of 150 ° C to 220 ° C, more preferably in the range of 170 ° C to 200 ° C.) and the curing time can be in the range of 5 minutes to 120 minutes (preferably 10 minutes to 100 minutes, more preferably 15 minutes to 90 minutes).

  Before the resin composition layer is thermally cured, the resin composition layer may be preheated at a temperature lower than the curing temperature. For example, prior to thermosetting the resin composition layer, the resin composition layer is formed at a temperature of 50 ° C. or higher and lower than 120 ° C. (preferably 60 ° C. or higher and 115 ° C. or lower, more preferably 70 ° C. or higher and 110 ° C. or lower). Preheating may be performed for 5 minutes or more (preferably 5 minutes to 150 minutes, more preferably 15 minutes to 120 minutes, and further preferably 15 minutes to 100 minutes).

  When manufacturing a printed wiring board, you may further implement (III) the process of drilling in an insulating layer, (IV) the process of roughening an insulating layer, and (V) the process of forming a conductor layer. These steps (III) to (V) may be carried out according to various methods known to those skilled in the art, which are used for manufacturing printed wiring boards. In addition, when removing a support body after process (II), removal of this support body is performed between process (II) and process (III), between process (III) and process (IV), or process ( It may be carried out between IV) and step (V). Moreover, if necessary, the formation of the insulating layer and the conductor layer in steps (II) to (V) may be repeated to form a multilayer wiring board. In this case, the thickness of the insulating layer between the respective conductor layers (t1 in FIG. 1) is preferably within the above range.

  Step (III) is a step of making a hole in the insulating layer, whereby holes such as via holes and through holes can be formed in the insulating layer. Step (III) may be performed using, for example, a drill, laser, plasma, or the like, depending on the composition of the resin composition used for forming the insulating layer. The dimensions and shape of the holes may be appropriately determined according to the design of the printed wiring board.

  Step (IV) is a step of roughening the insulating layer. The procedure and conditions for the roughening treatment are not particularly limited, and known procedures and conditions that are usually used when forming an insulating layer of a printed wiring board can be employed. For example, the insulating layer can be roughened by performing a swelling treatment with a swelling liquid, a roughening treatment with an oxidizing agent, and a neutralization treatment with a neutralizing liquid in this order. The swelling liquid used for the roughening treatment is not particularly limited, and examples thereof include an alkaline solution and a surfactant solution, and an alkaline solution is preferable. Examples of the alkaline solution include a sodium hydroxide solution and a potassium hydroxide solution. preferable. Examples of commercially available swelling liquids include “Swelling Dip Securigans P” and “Swelling Dip Securigans SBU” manufactured by Atotech Japan. Although the swelling process by a swelling liquid is not specifically limited, For example, it can perform by immersing an insulating layer for 1 minute-20 minutes in 30 degreeC-90 degreeC swelling liquid. From the viewpoint of suppressing the swelling of the resin in the insulating layer to an appropriate level, it is preferable to immerse the insulating layer in a swelling liquid at 40 ° C. to 80 ° C. for 5 minutes to 15 minutes. Although it does not specifically limit as an oxidizing agent used for a roughening process, For example, the alkaline permanganate solution which melt | dissolved potassium permanganate and sodium permanganate in the aqueous solution of sodium hydroxide is mentioned. The roughening treatment with an oxidizing agent such as an alkaline permanganic acid solution is preferably performed by immersing the insulating layer in an oxidizing agent solution heated to 60 to 80 ° C. for 10 to 30 minutes. The concentration of permanganate in the alkaline permanganate solution is preferably 5% by mass to 10% by mass. Examples of commercially available oxidizers include alkaline permanganate solutions such as “Concentrate Compact CP” and “Dosing Solution Securigans P” manufactured by Atotech Japan. Moreover, as a neutralization liquid used for a roughening process, acidic aqueous solution is preferable, As a commercial item, "Reduction Solution Securigant P" by Atotech Japan is mentioned, for example. The treatment with the neutralizing solution can be performed by immersing the treated surface subjected to the roughening treatment with the oxidizing agent in the neutralizing solution at 30 to 80 ° C. for 5 to 30 minutes. From the viewpoint of workability and the like, a method of immersing an object subjected to roughening treatment with an oxidizing agent in a neutralizing solution at 40 ° C. to 70 ° C. for 5 minutes to 20 minutes is preferable.

  In one embodiment, the arithmetic average roughness (Ra) of the insulating layer surface after the roughening treatment is preferably 400 nm or less, more preferably 350 nm or less, and further preferably 300 nm or less. Although it does not specifically limit about a minimum, Preferably it is 0.5 nm or more, More preferably, it can be set to 1 nm or more. Further, the root mean square roughness (Rq) of the insulating layer surface after the roughening treatment is preferably 400 nm or less, more preferably 350 nm or less, and further preferably 300 nm or less. Although it does not specifically limit about a minimum, Preferably it is 0.5 nm or more, More preferably, it can be set to 1 nm or more. The arithmetic mean roughness (Ra) and root mean square roughness (Rq) of the insulating layer surface can be measured using a non-contact type surface roughness meter.

  Step (V) is a step of forming a conductor layer. When the conductor layer is not formed on the inner layer substrate, the step (V) is a step of forming the first conductor layer. When the conductor layer is formed on the inner layer substrate, the conductor layer is the first conductor layer. Step (V) is a step of forming the second conductor layer.

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

  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 laminated. When the conductor layer has a multilayer structure, the layer in contact with the insulating layer is preferably a single metal layer of chromium, zinc or titanium, or an alloy layer of nickel / chromium alloy.

  Although the thickness of a conductor layer is based on the design of a desired printed wiring board, generally it is 3 micrometers-35 micrometers, Preferably it is 5 micrometers-30 micrometers.

  In one embodiment, the conductor layer may be formed by plating. For example, a conductive layer having a desired wiring pattern can be formed by plating on the surface of the insulating layer by a conventionally known technique such as a semi-additive method or a full additive method. It is preferable to form by a method. Hereinafter, an example in which the conductor layer is formed by a semi-additive method will be described.

  First, a plating seed layer is formed on the surface of the insulating layer by electroless plating. Next, a mask pattern that exposes a part of the plating seed layer corresponding to a desired wiring pattern is formed on the formed plating seed layer. A metal layer is formed by electrolytic plating on the exposed plating seed layer, and then the mask pattern is removed. Thereafter, an unnecessary plating seed layer can be removed by etching or the like to form a conductor layer having a desired wiring pattern.

  Since the resin sheet of the present invention provides an insulating layer having a good component embedding property, it can be suitably used even when the printed wiring board is a component built-in circuit board. The component built-in circuit board can be manufactured by a known manufacturing method.

  A printed wiring board manufactured using the resin sheet of the present invention is an aspect including an insulating layer that is a cured product of the resin composition layer of the resin sheet, and an embedded wiring layer embedded in the insulating layer. Also good.

[Semiconductor device]
The semiconductor device of the present invention includes the printed wiring board of the present invention. The semiconductor device of the present invention can be manufactured using the printed wiring board of the present invention.

  Examples of the semiconductor device include various semiconductor devices used for electrical products (for example, computers, mobile phones, digital cameras, and televisions) and vehicles (for example, motorcycles, automobiles, trains, ships, and aircrafts).

  The semiconductor device of the present invention can be manufactured by mounting a component (semiconductor chip) on a conductive portion of a printed wiring board. The “conduction location” is a “location where an electrical signal is transmitted on a printed wiring board”, and the location may be a surface or an embedded location. The semiconductor chip is not particularly limited as long as it is an electric circuit element made of a semiconductor.

  The semiconductor chip mounting method for manufacturing the semiconductor device is not particularly limited as long as the semiconductor chip functions effectively. Specifically, the wire bonding mounting method, the flip chip mounting method, and the bumpless buildup layer are used. (BBUL) mounting method, anisotropic conductive film (ACF) mounting method, non-conductive film (NCF) mounting method, and the like. Here, “a mounting method using a build-up layer without a bump (BBUL)” means “a mounting method in which a semiconductor chip is directly embedded in a recess of a printed wiring board and the semiconductor chip and wiring on the printed wiring board are connected”. It is.

  Hereinafter, the present invention will be specifically described by way of examples. The present invention is not limited to these examples. In the following description, “parts” and “%” representing amounts mean “parts by mass” and “% by mass”, respectively, unless otherwise specified.

  First, various measurement methods and evaluation methods will be described.

<Measurement of peel strength and ten-point average roughness (Rz value)>
(Preparation of samples for peel strength and ten-point average roughness (Rz value) measurement)
(1) Underlayer treatment of inner layer circuit board Glass cloth base epoxy resin double-sided copper-clad laminate (copper foil thickness 18 μm, substrate thickness 0.8 mm, Panasonic Corporation “R1766”) on which an inner layer circuit is formed as an inner layer A circuit board was prepared, and both surfaces thereof were immersed in a micro-etching agent (“CZ8101” manufactured by MEC Co., Ltd.) to roughen the copper surface (copper etching amount: 1.0 μm).

(2) Lamination of resin sheet A resin sheet having a resin composition layer thickness of 10 μm prepared in Examples and Comparative Examples was batch-type vacuum pressure laminator (manufactured by Nikko Materials, 2-stage buildup laminator, CVP700) was used to laminate both surfaces of the inner circuit board so that the resin composition layer was bonded to the inner circuit board. The laminating process was carried out by reducing the pressure for 30 seconds to a pressure of 13 hPa or less, and then pressure bonding at 100 ° C. and a pressure of 0.74 MPa for 30 seconds. Next, hot pressing was performed at 100 ° C. and a pressure of 0.5 MPa for 60 seconds.

(3) Curing of resin composition After laminating a resin sheet having a resin composition layer thickness of 10 μm, the resin composition layer is thermally cured at 100 ° C. for 30 minutes and then at 180 ° C. for 30 minutes for insulation. A layer was formed. Thereafter, the support was peeled off to expose the insulating layer.

(4) Roughening treatment The substrate with the insulating layer exposed was immersed in a swelling solution (“Swelling Dip Securigant P” manufactured by Atotech Japan, sodium hydroxide aqueous solution containing diethylene glycol monobutyl ether) at 60 ° C. for 10 minutes, and then Immerse in an oxidizing agent (Atotech Japan "Concentrate Compact CP", aqueous solution with potassium permanganate concentration of about 6% by mass, sodium hydroxide concentration of about 4% by mass) for 20 minutes at 80 ° C, and finally neutralize (Atotech Japan "Reduction Solution Securiganto P", hydroxylamine sulfate aqueous solution) was immersed at 40 ° C for 5 minutes. Thereafter, it was dried at 80 ° C. for 15 minutes. The obtained substrate is referred to as “evaluation substrate a”.

(5) Formation of conductor layer According to a semi-additive method, a conductor layer was formed on the roughened surface of the insulating layer. That is, the conductor layer was formed by performing a plating process (copper plating process using a chemical solution manufactured by Atotech Japan) including the following processes 1 to 6.

1. Alkali cleaning (cleaning and charge adjustment of the surface of the insulating layer with via holes)
The surface of the evaluation substrate “a” was cleaned at 60 ° C. for 5 minutes using a Cleaning Cleaner Security 902 (trade name).
2. Soft etching (cleaning inside via holes)
The surface of the evaluation substrate a was treated at 30 ° C. for 1 minute using an aqueous solution of acidic sodium peroxodisulfate.
3. Pre-dip (adjustment of surface charge of insulating layer for Pd application)
The surface of the evaluation substrate “a” is set to Pre. Using Dip Neoganth B (trade name), it was treated at room temperature for 1 minute.
4). Activator application (Pd application to the surface of the insulating layer)
The surface of the evaluation substrate a was treated with Activator Neoganth 834 (trade name) at 35 ° C. for 5 minutes.
5. Reduction (reduction of Pd applied to the insulating layer)
The surface of the evaluation substrate a is set to Reducer Neoganth WA (trade name) and Reducer Accelerator 810 mod. Using a mixture with (trade name), it was treated at 30 ° C. for 5 minutes.
6). Electroless copper plating process (Cu is deposited on the surface of the insulating layer (Pd surface))
The surface of the evaluation substrate a is mixed with Basic Solution Printganth MSK-DK (trade name), Copper solution Printganth MSK (trade name), Stabilizer Printganth MSK-DK (trade name), and Reducer Cu (trade name). For 30 minutes at 35 ° C. The thickness of the formed electroless copper plating layer was 1 μm.

  Next, after annealing at 150 ° C. for 30 minutes, an etching resist was formed and a pattern was formed by etching. Then, copper sulfate electrolytic plating was performed using a chemical solution manufactured by Atotech Japan, a conductor layer having a thickness of 25 μm was formed, and annealing treatment was performed at 200 ° C. for 60 minutes. The obtained substrate is referred to as “evaluation substrate b”.

(Measurement of ten-point average roughness (Rz))
About the evaluation board | substrate a before forming a conductor layer, using a non-contact-type surface roughness meter ("WYKO NT3300" by Beeco Instruments Co., Ltd.), a measurement range can be obtained as 121 μm × 92 μm with a VSI contact mode and a 50 × lens. The maximum height roughness (Rz) described in Japanese Industrial Standard (JIS B0601-2001) was determined by numerical values.

(Measurement of peel strength of plated conductor layer)
The peel strength of the plated conductor layer was measured according to the Japanese Industrial Standard (JIS C6481) for the evaluation substrate b. Specifically, the conductor layer of the evaluation board b is cut into a portion having a width of 10 mm and a length of 100 mm, this one end is peeled off and grasped with a grasping tool, and at room temperature in the vertical direction at a speed of 50 mm / min. The load (kgf / cm) when 35 mm was peeled off was measured to determine the peel strength (peel strength). For the measurement, a tensile tester (“AC-50C-SL” manufactured by TSE) was used.

<Measurement of glass transition temperature and linear thermal expansion coefficient>
(Production of cured product for evaluation)
The resin sheet produced in Examples and Comparative Examples having a resin composition layer thickness of 25 μm was heated at 200 ° C. for 90 minutes to thermally cure the resin composition layer, and then the support was peeled off. The obtained cured product is referred to as “evaluated cured product c”.

(Measurement of glass transition temperature and linear thermal expansion coefficient)
The evaluation cured product c was cut into a test piece having a width of 5 mm and a length of 15 mm. The test piece was subjected to thermomechanical analysis by a tensile load method using a thermomechanical analyzer (“Thermo Plus TMA8310” manufactured by Rigaku Corporation). Specifically, after the test piece was mounted on the thermomechanical analyzer, the test piece was measured twice continuously under the measurement conditions of a load of 1 g and a heating rate of 5 ° C./min. In two measurements, the glass transition temperature (° C.) and the linear thermal expansion coefficient (ppm / ° C.) in the plane direction in the range from 25 ° C. to 150 ° C. were calculated, and the average value was obtained.

<Synthesis Example 1: Synthesis of polyimide resin 1 having a polycyclic aromatic hydrocarbon skeleton>
A 500 mL separable flask equipped with a moisture quantitative receiver connected with a reflux condenser, a nitrogen inlet tube, and a stirrer was prepared. To this flask, 20.3 g of 4,4′-oxydiphthalic anhydride (ODPA), 200 g of γ-butyrolactone, 20 g of toluene, and 5- (4-aminophenoxy) -3- [4- (4-aminophenoxy) Phenyl] -1,1,3-trimethylindane (29.6 g) was added, and the reaction was performed by stirring at 45 ° C. for 2 hours under a nitrogen stream to obtain a reaction solution.

  Next, the temperature of the reaction solution was raised and the condensed water was removed azeotropically with toluene under a nitrogen stream while maintaining the temperature at about 160 ° C. It was confirmed that a predetermined amount of water had accumulated in the moisture meter and that no outflow of water was observed. After confirmation, the reaction solution was further heated and stirred at 200 ° C. for 1 hour. Then, it cooled and obtained the varnish which contains 20 mass% of polyimide resins which have a 1,1,3-trimethylindan frame | skeleton (henceforth "polyimide resin 1"). The obtained polyimide resin 1 had a repeating unit represented by the following formula (X1) and a repeating unit represented by (X2). Moreover, the weight average molecular weight of the polyimide resin 1 was 12000.

<Synthesis Example 2: Synthesis of polyimide resin 2 having a polycyclic aromatic hydrocarbon skeleton>
In Synthesis Example 1, 29.6 g of 5- (4-aminophenoxy) -3- [4- (4-aminophenoxy) phenyl] -1,1,3-trimethylindane was converted into 9,9-bis (4-amino). Phenyl) fluorene was changed to 22.9 g. Except for the above, a varnish containing 20% by mass of a polyimide resin having a fluorene skeleton (hereinafter sometimes referred to as “polyimide resin 2”) was obtained in the same manner as in Synthesis Example 1. The obtained polyimide resin 2 had a repeating unit represented by the following formula (X3) and a repeating unit represented by the above formula (X2). Moreover, the weight average molecular weight of the polyimide resin 2 was 14000.

<Synthesis Example 3: Synthesis of polyimide resin 3 having no polycyclic aromatic hydrocarbon skeleton>
In a reaction vessel equipped with a stirrer, a water separator, a thermometer and a nitrogen gas inlet tube, 65.0 g of aromatic tetracarboxylic dianhydride (“BisDA-1000” manufactured by SABIC Japan), 266.5 g of cyclohexanone, and 44.4 g of methylcyclohexane was charged and the solution was heated to 60 ° C. Next, 43.7 g of dimer diamine (“PRIAMINE 1075” manufactured by Croda Japan Co., Ltd.) and 5.4 g of 1,3-bisaminomethylcyclohexane were dropped, and an imidization reaction was performed at 140 ° C. over 1 hour. As a result, a varnish containing a dimer diamine polyimide resin (non-volatile content: 30% by mass) was obtained (hereinafter sometimes referred to as “polyimide resin 3”). Moreover, the weight average molecular weight of the polyimide resin 3 was 25000.

<Example 1>
30 parts of bisphenol A type epoxy resin (Mitsubishi Chemical "828 US", epoxy equivalent of about 180), biphenyl type epoxy resin (Nippon Kayaku "NC3000H", epoxy equivalent of about 269), 40 parts of solvent naphtha and The mixture was dissolved in 15 parts of cyclohexanone with heating while stirring, and then cooled to room temperature. To this mixed solution, spherical silica (average particle size 0.078 μm, specific surface area 30.7 m ² / g, manufactured by Denki Kagaku Kogyo Co., Ltd.) surface-treated with an aminosilane coupling agent (“KBM573” manufactured by Shin-Etsu Chemical Co., Ltd.) UFP-30 ") 100 parts, triazine skeleton-containing phenolic curing agent (" LA-3018-50P "manufactured by DIC, hydroxyl equivalent of about 151, 2-methoxypropanol solution having a solid content of 50%), 14 parts, active ester curing 40 parts of an agent (“HPC-8000-65T” manufactured by DIC, toluene solution with an active group equivalent of about 223 and 65% by mass of nonvolatile components), varnish containing the polyimide resin 1 synthesized in Synthesis Example 1 (solid content of 20% by mass) 20 parts of γ-butyrolactone solution, curing accelerator (“DMAP”, 4-dimethylaminopyridine, methyl ethyl ketone having a solid content of 5% by mass (hereinafter referred to as “DMAP”) Abbreviated as "MEK") solution) 6 parts were mixed, and uniformly dispersed in a high-speed rotary mixer to prepare a resin varnish 1.

  Two PET films with an alkyd resin release layer (“AL5” manufactured by Lintec Corporation, thickness 38 μm) were prepared as supports. The resin varnish 1 is uniformly applied on the release layer of each support so that the thickness of the resin composition layer after drying is 10 μm and 25 μm, and dried at 70 to 95 ° C. for 2 minutes, Sheet 1 was produced.

<Example 2>
In Example 1, 30 parts of biphenyl type epoxy resin (“NC3000H” manufactured by Nippon Kayaku Co., Ltd., epoxy equivalent of about 269) is changed to 30 parts of naphthol type epoxy resin (“ESN475V” manufactured by Nippon Steel & Sumikin Chemical Co., Ltd., 332). did. Except for the above, a resin varnish 2 and a resin sheet 2 were produced in the same manner as in Example 1.

<Example 3>
In Example 1, 30 parts of biphenyl type epoxy resin (Nippon Kayaku Co., Ltd. “NC3000H”, epoxy equivalent of about 269) was replaced with 30 parts of bixylenol type epoxy resin (Mitsubishi Chemical Corporation “YX4000HK”, epoxy equivalent of about 185). changed. Except for the above, a resin varnish 3 and a resin sheet 3 were produced in the same manner as in Example 1.

<Example 4>
In Example 1, 20 parts of the varnish containing the polyimide resin 1 synthesized in Synthesis Example 1 (γ-butyrolactone solution having a solid content of 20% by mass) was changed to 10 parts, and further, phenoxy resin (“YX6954BH30” manufactured by Mitsubishi Chemical Corporation). 7 parts of a 30% by mass solid solution of MEK and cyclohexanone (1: 1). Except for the above, a resin varnish 4 and a resin sheet 4 were produced in the same manner as in Example 1.

<Example 5>
In Example 1, 20 parts of a varnish containing the polyimide resin 1 synthesized in Synthesis Example 1 (γ-butyrolactone solution having a solid content of 20% by mass) and a varnish containing 20% by mass of the polyimide resin 2 synthesized in Synthesis Example 2 were obtained. % Γ-butyrolactone solution). Except for the above, a resin varnish 5 and a resin sheet 5 were produced in the same manner as in Example 1.

<Comparative Example 1>
In Example 1, 20 parts of varnish containing the polyimide resin synthesized in Synthesis Example 1 (γ-butyrolactone solution having a solid content of 20% by mass) was added to phenoxy resin (“YX6954BH30” manufactured by Mitsubishi Chemical Corporation), MEK having a solid content of 30% by mass. And a 1: 1 solution of cyclohexanone). Except for the above, a resin varnish 6 and a resin sheet 6 were produced in the same manner as in Example 1.

<Comparative Example 2>
In Example 1, 20 parts of a varnish containing the polyimide resin synthesized in Synthesis Example 1 (γ-butyrolactone solution having a solid content of 20% by mass) and a varnish containing 30% by mass of the polyimide resin 3 synthesized in Synthesis Example 3 were prepared. The mixed solution of cyclohexanone and methylcyclohexane was changed to 13 parts. Except for the above, a resin varnish 7 and a resin sheet 7 were produced in the same manner as in Example 1.

  The components used for the preparation of the resin compositions 1 to 7 and their blending amounts (in terms of non-volatile content) are shown in the following table. In addition, “content (%) of component (D)” in the following table represents the content of component (D) when the nonvolatile component in the resin composition is 100% by mass.

  In Examples 1-5, even if it is a case where it does not contain (E) component-(G) component, although it has a difference in a grade, it has confirmed that it results in the same result as the said Example.

DESCRIPTION OF SYMBOLS 1 1st conductor layer 11 Main surface 2 of 1st conductor layer 2nd conductor layer 21 Main surface of 2nd conductor layer 3 Insulating layer t1 Space | interval (1st conductor layer and 1st conductor layer) And the thickness of the insulating layer between the second conductor layers)
t2 Total thickness of insulating layer

Claims (18)

(A) epoxy resin,
(B) an active ester curing agent,
(C) a polyimide resin having a polycyclic aromatic hydrocarbon skeleton, and (D) an inorganic filler,
(D) The resin composition whose average particle diameter of a component is 100 nm or less. (A) epoxy resin,
(B) an active ester curing agent,
(C) a polyimide resin having a polycyclic aromatic hydrocarbon skeleton, and (D) an inorganic filler,
(D) The resin composition whose specific surface area of a component is 15 m < ² > / g or more.   The resin composition according to claim 1 or 2, wherein the polycyclic aromatic hydrocarbon skeleton is an aromatic hydrocarbon skeleton in which a 5-membered ring compound and an aromatic ring are condensed.   The resin composition according to any one of claims 1 to 3, wherein the polycyclic aromatic hydrocarbon skeleton is at least one of an indane skeleton and a fluorene skeleton.   (C) The resin composition of any one of Claims 1-4 whose weight average molecular weights of component are 5000 or more.   The resin composition according to any one of claims 1 to 5, wherein the component (C) has a repeating unit having a polycyclic aromatic hydrocarbon skeleton and a repeating unit having an imide structure.   The mass ratio of the repeating unit having a polycyclic aromatic hydrocarbon skeleton and the repeating unit having an imide structure (mass of repeating unit having a polycyclic aromatic hydrocarbon skeleton / mass of repeating unit having an imide structure) is: The resin composition according to claim 6, which is 0.5 or more and 2 or less.   (C) Content of a component is 0.1 to 3 mass% of any one of Claims 1-7 when the non-volatile component in a resin composition is 100 mass%. Resin composition.   (B) Resin composition of any one of Claims 1-8 whose content of a component is 1 mass% or more and 25 mass% or less when the non-volatile component in a resin composition is 100 mass%. object.   (D) Resin composition of any one of Claims 1-9 whose content of a component is 30 to 80 mass% when the non-volatile component in a resin composition is 100 mass%. object.   Furthermore (E) The resin composition of any one of Claims 1-10 containing a hardening | curing agent.   (E) The resin composition of Claim 11 whose hardening agent is a phenol type hardening | curing agent.   The resin composition according to any one of claims 1 to 12, which is used for forming an insulating layer for forming a conductor layer.   The resin composition according to any one of claims 1 to 13, which is used for forming an insulating layer of a printed wiring board.   The resin composition according to any one of claims 1 to 14, which is used for forming an interlayer insulating layer of a printed wiring board.   The resin sheet containing a support body and the resin composition layer of any one of Claims 1-15 provided on this support body. A printed wiring board including a first conductor layer, a second conductor layer, and an insulating layer formed between the first conductor layer and the second conductor layer,
The printed wiring board, wherein the insulating layer is a cured product of the resin composition according to any one of claims 1 to 15.   A semiconductor device comprising the printed wiring board according to claim 17.

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