KR102577867B1 - Resin composision - Google Patents

Abstract

[assignment]
Resin compositions that can produce cured products with low 10-point average roughness (Rz) and linear thermal expansion coefficient, high peel strength, and improved softness even when using inorganic fillers with a small average particle diameter or a large specific surface area. offer.
[Solution]
A resin composition containing (A) an epoxy resin, (B) an active ester-based curing agent, (C) a polyimide resin having a polycyclic aromatic hydrocarbon skeleton, and (D) an inorganic filler with an average particle diameter of 100 nm or less.

Description

Resin composition {RESIN COMPOSISION}

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

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

Japanese Patent Publication No. 2016-27097

The present inventors conducted a new study on the resin composition and obtained the following findings. When a large amount of an inorganic filler is contained in the resin composition, the surface area of the inorganic filler increases and the area of the interface between the inorganic filler also increases. As a result, it was discovered that the cured product of the resin composition became brittle and the roughened surface after roughening treatment became rough. In addition, from the viewpoint of thinning, etc., it was found that even when the resin composition contains an inorganic filler with a small average particle diameter or a large specific surface area, the cured product of the resin composition becomes softer because the surface area of the inorganic filler is large.

The object of the present invention is to provide a resin composition that can obtain a cured product with low 10-point average roughness (Rz) and linear thermal expansion coefficient and high peel strength even when using an inorganic filler with a small average particle diameter or a large specific surface area; A resin sheet containing the resin composition; The object is to provide a printed wiring board and a semiconductor device provided with an insulating layer formed using the resin composition.

In order to achieve the object of the present invention, the present inventors have carefully studied and found that thermoplastic resins containing phenoxy resins and aliphatic resins have excellent flexibility and are prone to desmear resistance because highly polar components such as alcohol are easily generated during curing. It was found that the 10-point average roughness (Rz) sometimes increases when roughening treatment is performed. Based on this knowledge, the present inventors further studied carefully and found that when component (C), which has a rigid and highly hydrophobic polycyclic aromatic hydrocarbon skeleton, is contained in the resin composition, an inorganic filler with a small average particle diameter or a large specific surface area can be created. The present invention was completed by finding that a resin composition capable of producing a cured product with low 10-point average roughness (Rz) and linear thermal expansion coefficient, high peel strength, and improved softness can be obtained even when using the resin composition.

That is, the present invention includes the following contents.

[1] (A) epoxy resin,

(B) activated ester-based curing agent,

(C) a polyimide resin having a polycyclic aromatic hydrocarbon skeleton, and

(D) contains inorganic fillers,

(D) A resin composition in which the average particle diameter of the component is 100 nm or less.

[2] (A) epoxy resin,

(B) activated ester-based curing agent,

(C) a polyimide resin having a polycyclic aromatic hydrocarbon skeleton, and

(D) contains inorganic fillers,

(D) A resin composition in which the specific surface area of the 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 weight average molecular weight of component (C) is 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] The mass ratio of the repeating unit having a polycyclic aromatic hydrocarbon backbone and the repeating unit having an imide structure (mass of repeating unit having a polycyclic aromatic hydrocarbon backbone/mass of repeating unit having an imide structure) is 0.5 or more and 2 or less. , the resin composition described in [6].

[8] The resin composition according to any one of [1] to [7], wherein the content of component (C) is 0.1% by mass or more and 3% by mass or less when the non-volatile component in the resin composition is 100% by mass.

[9] The resin composition according to any one of [1] to [8], wherein the content of component (B) is 1% by mass or more and 25% by mass or less when the non-volatile component in the resin composition is 100% by mass.

[10] The resin composition according to any one of [1] to [9], wherein the content of component (D) is 30% by mass or more and 80% by mass or less when the non-volatile component in the resin composition is 100% by mass.

[11] The resin composition according to any one of [1] to [10], further containing (E) a curing agent.

[12] (E) The resin composition according to [11], wherein the curing agent is a phenol-based curing agent.

[13] The resin composition according to any one of [1] to [12], which is used 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 used to form an interlayer insulating layer of a printed wiring board.

[16] A resin sheet comprising a support and a 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,

A printed wiring board, wherein the insulating layer is a cured product of the resin composition according to any one of [1] to [15].

[18] A semiconductor device including the printed wiring board described in [17].

According to the present invention, even when using an inorganic filler with a small average particle diameter or a large specific surface area, a cured product with low 10-point average roughness (Rz) and linear thermal expansion coefficient, high peel strength, and improved softness can be obtained. a resin composition; A resin sheet containing the resin composition; A printed wiring board and a semiconductor device provided with an insulating layer formed using the resin composition can be provided.

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 contains (A) an epoxy resin, (B) an active ester-based curing agent, (C) a polyimide resin having a polycyclic aromatic hydrocarbon skeleton, and (D) an inorganic filler, (D) The average particle diameter of the component is 100 nm or less. In addition, the resin composition of the second embodiment of the present invention contains (A) an epoxy resin, (B) an active ester-based curing agent, (C) a polyimide resin having a polycyclic aromatic hydrocarbon skeleton, and (D) an inorganic filler. And, the specific surface area of component (D) is 15 m ² /g or more. The resin composition of the first embodiment contains (C) a polyimide resin having a polycyclic aromatic hydrocarbon skeleton, and (D) even if it contains an inorganic filler with an average particle diameter of 100 nm or less, the 10-point average roughness (Rz) and linear thermal expansion are improved. A resin composition capable of obtaining a cured product with a low modulus, high peel strength, and improved softness can be obtained. Similarly, the resin composition of the second embodiment has a 10-point average roughness (Rz) even if it contains (C) a polyimide resin having a polycyclic aromatic hydrocarbon skeleton and (D) an inorganic filler with a specific surface area of 15 m ² /g or more. ) and a resin composition capable of obtaining a cured product with a low linear thermal expansion coefficient, high peel strength, and improved softness.

If necessary, the resin composition may further contain components such as (E) a curing agent (excluding the active ester-based curing agent), (F) a curing accelerator, (G) a thermoplastic resin, and (H) other additives. . Hereinafter, each component contained in the resin composition of the first and second embodiments of the present invention will be described in detail. Here, the resin composition of the first embodiment and the resin composition of the second embodiment may be collectively referred to as a “resin composition.”

<(A) Epoxy resin>

The resin composition includes (A) an epoxy resin. As epoxy resins, for example, bixylenol type epoxy resin, bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, bisphenol AF type epoxy resin, dicyclopentadiene type epoxy resin, trisphenol type epoxy resin. Resin, naphthol novolac type epoxy resin, phenol novolak type epoxy resin, tert-butyl-catechol type epoxy resin, naphthalene type epoxy resin, naphthol type epoxy resin, anthracene type epoxy resin, glycidylamine type epoxy resin, glycidyl Di-ester type epoxy resin, cresol novolac type epoxy resin, biphenyl type epoxy resin, linear aliphatic epoxy resin, epoxy resin with butadiene structure, alicyclic epoxy resin, heterocyclic epoxy resin, spiro ring-containing epoxy resin, cyclohexane type. An epoxy resin, a cyclohexanedimethanol type epoxy resin, a naphthylene ether type epoxy resin, a trimethylol type epoxy resin, and a tetraphenyl ethane type epoxy resin can be mentioned. Epoxy resins may be used individually, or two or more types may be used in combination.

It is preferable that the epoxy resin contains an epoxy resin having two or more epoxy groups in one molecule. When the non-volatile component of the epoxy resin is 100% by mass, it is preferable that at least 50% by mass or more is an epoxy resin having two or more epoxy groups in one molecule. Among them, the resin composition includes a combination of an epoxy resin that is liquid at a temperature of 20°C (hereinafter referred to as “liquid epoxy resin”) and an epoxy resin that is solid at a temperature of 20°C (hereinafter referred to as “solid epoxy resin”). It is desirable to do so. As the liquid epoxy resin, a liquid epoxy resin having two or more epoxy groups per molecule is preferable, and an aromatic liquid epoxy resin having two or more epoxy groups per molecule is more preferable. As the solid epoxy resin, a solid epoxy resin having 3 or more epoxy groups per molecule is preferable, and an aromatic solid epoxy resin having 3 or more epoxy groups per molecule is more preferable. In the present invention, aromatic epoxy resin means an epoxy resin having an aromatic ring in its molecule.

Liquid epoxy resins include bisphenol A-type epoxy resin, bisphenol F-type epoxy resin, bisphenol AF-type epoxy resin, naphthalene-type epoxy resin, glycidyl ester-type epoxy resin, glycidylamine-type epoxy resin, and phenol novolak-type epoxy resin. , alicyclic epoxy resins having an ester skeleton, cyclohexane-type epoxy resins, cyclohexanedimethanol-type epoxy resins, glycidylamine-type epoxy resins, and epoxy resins having a butadiene structure are preferable, and bisphenol A-type epoxy resins and bisphenol F-type epoxy resin and cyclohexane-type epoxy resin are more preferable, and bisphenol A-type epoxy resin is more preferable. Specific examples of liquid epoxy resins include "HP4032", "HP4032D", and "HP4032SS" (naphthalene-type epoxy resin) manufactured by DIC, and "828US", "jER828EL", "825", and "Epicoat 828EL" manufactured by Mitsubishi Chemical Corporation. 」(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” manufactured by Shin-Niptetsu Sumikink (mixture of bisphenol A-type epoxy resin and bisphenol F-type epoxy resin), “EX-721” manufactured by Nagase Chemtex Corporation (glycidyl ester type epoxy resin) ), “Celoxide 2021P” (alicyclic epoxy resin having an ester skeleton), “PB-3600” (epoxy resin having a butadiene structure) manufactured by Daicel Corporation, “ZX1658”, and “ZX1658GS” manufactured by Nippon-Steel Sumitkin Chemical Co., Ltd. "(liquid 1,4-glycidylcyclohexane type epoxy resin), "630LSD" (glycidylamine type epoxy resin) manufactured by Mitsubishi Chemical Corporation, etc. These may be used individually, or two or more types may be used in combination.

Examples of the solid epoxy resin 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, Phenyl 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 preferred, 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 preferable, and bixylenol type epoxy resin, naphthol type epoxy resin, and biphenyl type epoxy resin are more preferable. Specific examples of solid epoxy resins include "HP4032H" (naphthalene-type epoxy resin), "HP-4700", "HP-4710" (naphthalene-type tetrafunctional epoxy resin), and "N-690" (cresol novolac) manufactured by DIC. 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” (Tris) manufactured by Nihon Kayaku Co., Ltd. Phenol type epoxy resin), “NC7000L” (naphthol novolak type epoxy resin), “NC3000H”, “NC3000”, “NC3000L”, “NC3100” (biphenyl type epoxy resin), “ ESN475V" (naphthalene type epoxy resin), "ESN485" (naphthol novolac type epoxy resin), "YX4000H", "YX4000", and "YL6121" (biphenyl type epoxy resin) manufactured by Mitsubishi Chemical Corporation, and "YX4000HK" (Vic silenol type epoxy resin), “YX8800” (anthracene type epoxy resin), “PG-100” and “CG-500” manufactured by Osaka Gas Chemicals, “YL7760” (bisphenol AF type epoxy resin) manufactured by Mitsubishi Chemical Corporation, “YL7800” (fluorene type epoxy resin), “jER1010” (solid bisphenol A type epoxy resin) manufactured by Mitsubishi Chemical Corporation, and “jER1031S” (tetraphenylethane type epoxy resin). These may be used individually, or two or more types may be used in combination.

When using a liquid epoxy resin and a solid epoxy resin together as component (A), the mass ratio (liquid epoxy resin:solid epoxy resin) is preferably in the range of 1:0.1 to 1:20. By keeping the ratio of the liquid epoxy resin and the solid epoxy resin within this range, i) appropriate adhesion is achieved when used in the form of a resin sheet, and ii) sufficient flexibility can be obtained when used in the form of a resin sheet, making it easy to handle. properties are improved, and iii) a cured product having sufficient breaking strength can be obtained. From the viewpoint of the effects of i) to iii) above, the amount ratio of the liquid epoxy resin and the solid epoxy resin (liquid epoxy resin:solid epoxy resin) is more preferably in the range of 1:0.3 to 1:10 as a mass ratio, and 1: A range of 0.5 to 1:1.5 is more preferred.

The content of component (A) in the resin composition is preferably 15% by mass or more, more preferably 15% by mass or more, when the non-volatile component in the resin composition is 100% by mass, from the viewpoint of obtaining an insulating layer showing good mechanical strength and insulation reliability. It is preferably 20% by mass or more, more 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 achieved, 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.

The epoxy equivalent of component (A) is preferably 50 to 5000, more preferably 50 to 3000, further preferably 80 to 2000, and still more preferably 110 to 1000. By reaching this range, the crosslinking density of the cured product becomes sufficient and an insulating layer with small surface roughness can be produced. In addition, epoxy equivalent can be measured according to JIS K7236, and is the mass of resin containing 1 equivalent of epoxy group.

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

<(B) Active ester-based hardener>

The resin composition includes (B) an active ester-based curing agent. An active ester-based curing agent is an active ester compound having one or more active ester groups in one molecule. As the active ester-based curing agent, an active ester-based curing agent having two or more active ester groups per molecule is preferable, for example, phenol esters, thiophenol esters, N-hydroxyamine esters, and heterocyclic hydroxy compounds. An active ester-based curing agent having two or more ester groups per molecule with high reaction activity, such as esters, is preferably used. The active ester-based curing agent may be used individually, or two or more types may be used in combination.

From the viewpoint of improving heat resistance, an active ester-based curing agent obtained by condensation reaction of a carboxylic acid compound and/or a thiocarboxylic acid compound with a hydroxy compound and/or a thiol compound is preferred. Among them, an active ester-based 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 active ester-based curing agent obtained by reacting a carboxylic acid compound with an aromatic compound having a phenolic hydroxyl group is more preferable. An aromatic compound having two or more active ester groups in one molecule is more preferable, and is an aromatic compound obtained by reacting a carboxylic acid compound having at least two or more carboxyl groups in one molecule with an aromatic compound having a phenolic hydroxyl group, Aromatic compounds having two or more active ester groups in the molecule are even more preferable. The active ester-based curing agent may be linear or branched. In addition, if the carboxylic acid compound having at least two or more carboxyl groups in one molecule is a compound containing an aliphatic chain, compatibility with the resin composition can be improved, and if it is a compound having an aromatic ring, heat resistance can be improved.

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, and even more preferably 2 to 8 carbon atoms, and specifically includes acetic acid, malonic acid, succinic acid, maleic acid, Itaconic acid, etc. can be 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 them, from the viewpoint of heat resistance, succinic acid, maleic acid, itaconic acid, phthalic acid, isophthalic acid, and terephthalic acid are preferable, and isophthalic acid and terephthalic acid are more preferable.

There is no particular limitation on the thiocarboxylic acid compound, and examples include thioacetic acid and thiobenzoic acid.

As a phenolic compound, for example, a phenol compound preferably has 6 to 40 carbon atoms, more preferably 6 to 30 carbon atoms, more preferably 6 to 23 carbon atoms, and even more preferably 6 to 22 carbon atoms. do. Suitable specific examples of phenol compounds include hydroquinone, resorcin, bisphenol A, bisphenol F, bisphenol S, phenolphthaline, methylated bisphenol A, methylated bisphenol F, methylated bisphenol S, phenol, o-cresol, m-cresol, p- Cresol, catechol, dihydroxybenzophenone, trihydroxybenzophenone, tetrahydroxybenzophenone, phloroglucine, benzenetriol, dicyclopentadiene type diphenol, etc. are mentioned. As the phenol compound, a phenol novolak or a phosphorus atom-containing oligomer having a phenolic hydroxyl group described in Japanese Patent Application Laid-Open No. 2013-40270 may be used.

The naphthol compound preferably has 10 to 40 carbon atoms, more preferably 10 to 30 carbon atoms, and even more preferably 10 to 20 carbon atoms. Suitable specific examples of naphthol compounds include α-naphthol, β-naphthol, 1,5-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, and 2,6-dihydroxynaphthalene. As the naphthol compound, naphthol novolak may also be used.

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-dihyde Roxynaphthalene, 2,6-dihydroxynaphthalene, dihydroxybenzophenone, trihydroxybenzophenone, tetrahydroxybenzophenone, phloroglucine, benzenetriol, dicyclopentadiene type diphenol, phenol novolak , phosphorus atom-containing oligomers having a phenolic hydroxyl group are preferred, and include catechol, 1,5-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, dihydroxybenzophenone, Trihydroxybenzophenone, tetrahydroxybenzophenone, phloroglucine, benzenetriol, dicyclopentadiene type diphenol, phenol novolak, and phosphorus atom-containing oligomers having phenolic hydroxyl groups are more preferred, 1,5 -Dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, dihydroxybenzophenone, trihydroxybenzophenone, tetrahydroxybenzophenone, dicyclopentadiene type diphenol, Phenol novolak, a phosphorus atom-containing oligomer having a phenolic hydroxyl group, is more preferable, and 1,5-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, and dicyclopentadiene type. Diphenol, phenol novolac, and phosphorus atom-containing oligomers having phenolic hydroxyl groups are more preferable, and 1,5-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, dihydroxynaphthalene, Cyclopentadiene type diphenol and a phosphorus atom-containing oligomer having a phenolic hydroxyl group are particularly preferred, and dicyclopentadiene type diphenol is particularly preferred.

There is no particular limitation on the thiol compound, but examples include benzenedithiol, triazinedithiol, and the like.

Suitable specific examples of the active ester curing agent include an active ester curing agent containing a dicyclopentadiene type diphenol structure, an active ester curing agent containing a naphthalene structure, an active ester curing agent containing an acetylated product of phenol novolac, and phenol. Active ester-based curing agents containing benzoylated novolacs, active ester-based curing agents obtained by reacting aromatic carboxylic acids with phosphorus atom-containing oligomers having phenolic hydroxyl groups, etc. are included, and among these, dicyclopentadiene type diphenol structure. More preferred are active ester-based curing agents containing, active ester-based curing agents containing a naphthalene structure, and active ester-based curing agents obtained by reacting an aromatic carboxylic acid with a phosphorus atom-containing oligomer having a phenolic hydroxyl group. In addition, in the present invention, “dicyclopentadiene type diphenol structure” refers to a divalent structural unit consisting of phenylene-dicyclopentylene-phenylene.

As the active ester-based curing agent, the active ester-based curing agent disclosed in Japanese Patent Application Laid-Open No. 2004-277460 and Japanese Patent Application Laid-Open No. 2013-40270 may be used, or a commercially available active ester curing agent may be used. . Commercially available active ester curing agents include, for example, "EXB9451", "EXB9460", "EXB9460S", "HPC-8000-65T", and "HPC-8000L-65M" manufactured by DIC (dicyclopentadiene type active ester-based curing agent containing a phenol structure), “EXB9416-70BK” manufactured by DIC (active ester-based curing agent containing a naphthalene structure), “DC808” manufactured by Mitsubishi Chemical Corporation (containing an acetylated product of phenol novolak) active ester-based curing agent), “YLH1026” manufactured by Mitsubishi Chemical Corporation (active ester-based curing agent containing a benzoylate of phenol novolak), and “EXB9050L-62M” manufactured by DIC Corporation (active ester-based curing agent containing a phosphorus atom). You can.

From the viewpoint of lowering the linear thermal expansion coefficient and increasing the peeling strength, the content of the active ester curing agent is preferably 1% by mass or more, and is more preferably 5% by mass or more when the non-volatile component in the resin composition is 100% by mass. It is preferable, and 10% by mass or more is more preferable. The upper limit of the content of the active ester-based curing agent is not particularly limited, but is preferably 25% by mass or less, more preferably 20% by mass or less, and even more preferably 15% by mass or less.

In addition, when the number of epoxy groups in the (A) epoxy resin is 1, the number of reactive groups in the active ester curing agent (B) is preferably 0.1 to 10, from the viewpoint of obtaining an insulating layer with good mechanical strength, and 0.1 to 5. It is more preferable, and 0.1 to 1 is still more preferable. Here, the “number of epoxy groups in the epoxy resin” is the solid mass of each epoxy resin present in the resin composition divided by the epoxy equivalent, which is the sum of the values for all epoxy resins. In addition, “reactive group” refers to a functional group that can react with an epoxy group, and “the number of reactive groups of the active ester curing agent” refers to the sum of the solid mass of the active ester curing agent present in the resin composition divided by the reactor equivalent. It is a value.

<(C) Polyimide resin having a polycyclic aromatic hydrocarbon skeleton>

The resin composition contains (C) a polyimide resin having a polycyclic aromatic hydrocarbon skeleton. By having a rigid polycyclic aromatic hydrocarbon skeleton, a cured product with low 10-point average roughness (Rz) and linear thermal expansion coefficient and high peel strength can be obtained even when using inorganic fillers with a small average particle diameter or a large specific surface area. can do. As mentioned above, thermoplastic resins containing phenoxy resins, aliphatic resins, etc. have high polarity, so desmear resistance is low, and as a result, the 10-point average roughness (Rz) may increase. In addition to the rigid imide resin, component (C) has a polycyclic aromatic hydrocarbon skeleton that is rigid and has excellent hydrophobicity. The cured product of the resin composition containing such component (C) has lower polarity than the case containing a thermoplastic resin such as phenoxy resin, and as a result, the roughness after roughening treatment can be lowered, so the 10-point average roughness (Rz) You can do it low. In addition, since component (C) has a rigid skeleton, destruction of the resin is unlikely to occur, and therefore, the peeling strength is increased. In addition, since component (C) has a rigid skeleton and is difficult to expand, it is thought that the coefficient of linear thermal expansion is lowered.

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

The polycyclic aromatic hydrocarbon skeleton does not need to have a substituent, and may have a substituent. There is no particular limitation as a substituent, and examples include a halogen atom, -OH, -OC _1-6 alkyl group, -N(C _1-6 alkyl group) ₂ , C _1-6 alkyl group, C _6-10 aryl group, -NH. ₂ , -CN, -C(O)OC _1-6 alkyl group, -COOH, -C(O)H, -NO ₂ , etc., a C _1-6 alkyl group is preferable, and a methyl group is more preferable. You may have only one type of substituent, or you may have multiple substituents.

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

Examples of the polycyclic aromatic hydrocarbon skeleton include an indane skeleton containing a 1,1,3-trimethylindane skeleton, and an aromatic hydrocarbon skeleton in which an aromatic ring is condensed with a 5-membered ring compound such as a fluorene skeleton; aromatic hydrocarbon skeletons in which aromatics are condensed, such as naphthalene skeleton and anthracene skeleton; Examples include an aromatic hydrocarbon skeleton (non-condensed aromatic hydrocarbon skeleton) having two or more aromatics without condensation, such as a biphenyl skeleton, and from the viewpoint of lowering the 10-point average roughness (Rz), a 5-membered ring compound and an aromatic ring are condensed. An aromatic hydrocarbon backbone is preferred. Among them, 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 peeling strength, it is preferable that the polycyclic aromatic hydrocarbon skeleton is at least one of an indane skeleton and a fluorene skeleton.

The component (C) is not particularly limited as long as it is an imide resin having a polycyclic aromatic hydrocarbon skeleton, but has a cyclic 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 that it is a polyimide resin having.

As the cyclic imide structure, for example, phthalimide, succinimide, glutalimide, 3-methylglutalimide, maleimide, dimethylmaleimide, trimellitimide, and pyromellitimide are preferred. Examples include phthalimide and succinimide, and among these, a polyimide resin having an aromatic imide structure is preferable, and phthalimide is more preferable.

Component (C) has a repeating unit having a polycyclic aromatic hydrocarbon skeleton and a repeating unit having 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 peeling strength. desirable.

As a repeating unit having a polycyclic aromatic hydrocarbon skeleton, for example, a repeating unit represented by the following formula (1) is preferable.

[Formula 1]

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

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

D in the formula (1) represents a single bond or a divalent linking group, and a divalent linking group is preferable. 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 of these. You can.

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

As an arylene group, an arylene group with 6 to 14 carbon atoms is preferable, and an arylene group with 6 to 10 carbon atoms is more preferable. Examples of the arylene group include phenylene group, naphthylene group, anthracenylene group, etc., and phenylene group is preferable.

The alkylene group and arylene group do not need to 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 groups include, for example, a group in which one or more arylene groups and one or more alkylene groups are bonded (a group consisting of a combination of an arylene group and an alkylene group), a group in which one or more oxygen atoms and one or more arylene groups are bonded ( A group consisting of a combination of an oxygen atom and an arylene group), etc. can be mentioned. Examples of groups in which one or more arylene groups and one or more alkylene groups are bonded include a divalent group consisting of phenylene-methylene, a divalent group consisting of phenylene-dimethylmethylene, etc. Examples of groups in which one or more oxygen atoms and one or more arylene groups are bonded include a divalent group consisting of phenylene-oxygen atom-phenylene, a divalent group consisting of an oxygen atom-phenylene, and an oxygen atom-naphthalene. A bivalent group consisting of such groups can be mentioned.

Suitable examples of repeating units 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 lowering the linear thermal expansion coefficient of the cured resin composition and increasing the glass transition temperature and peeling strength, the repeating unit having a cyclic imide structure is not particularly limited. It is preferable that it is a unit.

As the cyclic imide structure, for example, phthalimide, succinimide, glutalimide, 3-methylglutalimide, maleimide, dimethylmaleimide, trimellitimide, and pyromellitimide are preferred. Examples include phthalimide and succinimide, and among these, an aromatic imide structure is preferable and phthalimide is more preferable. The repeating unit having an imide structure may be a form in which the above-described 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 Chemical Formula 1.

Suitable examples of repeating units having an imide structure include the following.

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 preferably 0.5 or more. , more preferably 0.6 or more, further preferably 0.8 or more, preferably 2 or less, more preferably 1.8 or less, even more preferably 1.5 or less. By keeping the mass ratio within this range, it becomes possible to lower the coefficient of linear thermal expansion of the cured product of the resin composition and to increase the glass transition temperature and peel strength.

The manufacturing method of component (C) is not particularly limited, and it can be manufactured according to various methods. In a preferred embodiment, it can be obtained by polymerizing a monomer that serves as a repeating unit with an imide structure and a monomer that serves as a repeating unit with a polycyclic aromatic hydrocarbon skeleton. When performing polymerization, a polymerization initiator or the like may be used as needed.

The weight average molecular weight of component (C) is preferably 5000 or more, more preferably 10000 or more, from the viewpoint of obtaining a cured product with a low 10-point average roughness (Rz) and linear thermal expansion coefficient and high peel strength. Preferably it is 11,000 or more, preferably 100,000 or less, more preferably 50,000 or less, and even more preferably 30,000 or less. Here, the weight average molecular weight of component (C) is the weight average molecular weight in terms of polystyrene measured by gel permeation chromatography (GPC) method.

The content of component (C) is preferably 100% by mass of the non-volatile component in the resin composition from the viewpoint of obtaining a cured product with a low 10-point average roughness (Rz) and a low linear thermal expansion coefficient and a high peeling strength. It is 0.1 mass% or more, more preferably 0.3 mass% or more, and even more preferably 0.5 mass% or more. The upper limit is preferably 3% by mass or less, more preferably 2% by mass or less, and even more preferably 1.5% by mass or less.

<(D) Inorganic filler>

The resin composition of the first embodiment contains (D) an inorganic filler with an average particle diameter of 100 nm or less. Additionally, the resin composition of the second embodiment contains (D) an inorganic filler with a specific surface area of 15 m ² /g or more. The material of component (D) is not particularly limited, but includes, for example, silica, alumina, glass, cordierite, silicon oxide, barium sulfate, barium carbonate, talc, clay, mica powder, zinc oxide, hydrotalcite, and beryl. Mite, aluminum hydroxide, magnesium hydroxide, calcium carbonate, magnesium carbonate, magnesium oxide, boron nitride, aluminum nitride, manganese nitride, aluminum borate, strontium carbonate, strontium titanate, calcium titanate, magnesium titanate, bismuth titanate, titanium oxide, zirconium oxide, Examples include barium titanate, barium titanate-zirconate, barium zirconate, calcium zirconate, zirconium phosphate, and zirconium phosphate-tungstate. Among these, silica is particularly suitable. Examples of silica include amorphous silica, fused silica, crystalline silica, synthetic silica, and hollow silica. Moreover, as silica, spherical silica is preferable. Inorganic fillers may be used individually, or two or more types may be used in combination.

The average particle diameter of the inorganic filler in the first embodiment is 100 nm or less, preferably 90 nm or less, and more preferably 80 nm or less from the viewpoint of thinning and reducing the 10-point average roughness (Rz). The lower limit of the average particle diameter is not particularly limited, but is preferably 1 nm or more, more preferably 5 nm or more, and even more 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 still more preferably from the viewpoint of thinning and reducing the 10-point average roughness (Rz). It is 80nm or less. The lower limit of the average particle diameter is not particularly limited, but is preferably 1 nm or more, more preferably 5 nm or more, and even more preferably 10 nm or more.

Examples of commercially available inorganic fillers having such an average particle diameter include “UFP-30” manufactured by Denki Chemical 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 using a laser diffraction scattering type particle size distribution measuring device, and the median diameter can be measured as the average particle diameter. The measurement sample can preferably be one in which an inorganic filler is dispersed in methyl ethyl ketone by ultrasonic waves. As a laser diffraction scattering type particle size distribution measuring device, “LA-500” manufactured by Horiba Chemical Industries, Ltd., “SALD-2200” manufactured by Shimadzu Chemical Company, 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 thinning and reducing the 10-point average roughness (Rz). It is more than 30m ² /g. There is no particular limitation on the upper limit, but it is preferably 60 m ² /g or less, more preferably 50 m ² /g or less, and even more preferably 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 thinning and reducing the 10-point average roughness (Rz). More preferably, it is 30 m ² /g or more. There is no particular limitation on the upper limit, but it is preferably 60 m ² /g or less, more preferably 50 m ² /g or less, and even more preferably 40 m ² /g or less.

The specific surface area can be obtained by adsorbing nitrogen gas to the surface of the sample using a specific surface area measuring device (Macsorb HM-1210, manufactured by Mountec) according to the BET method, and calculating the specific surface area using the BET multipoint method.

Inorganic fillers include fluorine-containing silane coupling agents, aminosilane coupling agents, epoxysilane coupling agents, mercaptosilane coupling agents, silane coupling agents, alkoxysilanes, and organosilazane compounds from the viewpoint of increasing moisture resistance and dispersibility. , it is preferable that it is treated with one or more surface treatment agents such as a titanate-based coupling agent, and it is more preferable that it is treated with an aminosilane-based silane coupling agent. Commercially available surface treatment agents include, for example, "KBM403" (3-glycidoxypropyltrimethoxysilane) manufactured by Shin-Etsu Chemical, and "KBM803" (3-mercaptopropyltrimethoxysilane) manufactured by Shin-Etsu Chemical. silane), “KBE903” (3-aminopropyltriethoxysilane) manufactured by Shin-Etsu Chemical Co., Ltd., “KBM573” (N-phenyl-3-aminopropyltrimethoxysilane) manufactured by Shin-Etsu Chemical Co., Ltd., Shin-Etsu Chemical Co., Ltd. “SZ-31” (hexamethyldisilazane) manufactured by Kogyo Co., Ltd., “KBM103” (phenyltrimethoxysilane) manufactured by Shin-Etsu Chemical Co., Ltd., “KBM-4803” (long chain epoxy type silane couple) manufactured by Shin-Etsu Chemical Co., Ltd. ring agent), "KBM-7103" (3,3,3-trifluoropropyltrimethoxysilane) manufactured by Shin-Etsu Chemical Co., Ltd., etc.

From the viewpoint of improving the dispersibility of the inorganic filler, the degree of surface treatment with the surface treatment agent is preferably 0.2 to 5 parts by mass of the surface treatment agent, based on 100 parts by mass of component (D), preferably 0.2 parts by mass. It is preferable that the surface is treated in an amount of 0.3 to 4 parts by mass, and it is preferable that the surface is treated in an amount of 0.3 to 3 parts by mass.

The degree of surface treatment by a surface treatment agent can be evaluated by the amount of carbon per unit surface area of the inorganic filler. From the viewpoint of improving the dispersibility of the inorganic filler, the amount of carbon per unit surface area of the inorganic filler is preferably 0.02 mg/m ² or more, more preferably 0.1 mg/m ² or more, and even more preferably 0.2 mg/m ² or more. . On the other hand, from the viewpoint of suppressing an increase in the melt viscosity of the resin varnish and the melt viscosity in sheet form, 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 even more preferable. desirable.

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 a surface treatment agent, and ultrasonic cleaning is performed at 25°C for 5 minutes. After removing the supernatant and drying the solid content, the amount of carbon per unit surface area of the inorganic filler can be measured using a carbon analyzer. As a carbon analyzer, "EMIA-320V" manufactured by Horiba Chemical Co., Ltd., etc. can be used.

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

<(E) Hardener>

In one embodiment, the resin composition may contain (E) a curing agent. However, the (E) curing agent referred to here does not include the (B) active ester-based curing agent. The component (E) is not particularly limited as long as it has the function of curing the component (A), and examples include phenol-based curing agents, naphthol-based curing agents, benzoxazine-based curing agents, cyanate ester-based curing agents, and carbodiimide-based curing agents. etc. can be mentioned. Among them, a phenol-based curing agent is preferable as the (E) component. One type of hardening agent may be used individually, or two or more types may be used 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. Furthermore, from the viewpoint of adhesion to the conductor layer, a nitrogen-containing phenol-based curing agent is preferable, and a triazine skeleton-containing phenol-based curing agent is more preferable.

Specific examples of phenol-based curing agents and naphthol-based curing agents include, for example, “MEH-7700”, “MEH-7810”, and “MEH-7851” manufactured by Meiwa Kasei Co., Ltd., “NHN” and “CBN” manufactured by Nihon Kayaku Co., Ltd. ”, “GPH”, “SN170”, “SN180”, “SN190”, “SN475”, “SN485”, “SN495”, “SN-495V”, “SN375”, “SN395” manufactured by Shin-Niptetsu Sumikink Kagaku Co., Ltd. ", "TD-2090", "LA-7052", "LA-7054", "LA-1356", "LA-3018-50P", and "EXB-9500" manufactured by DIC Corporation.

Specific examples of the benzoxazine-based curing agent include “HFB2006M” manufactured by Showa Kobunshi Corporation and “P-d” and “F-a” manufactured by Shikoku Chemical Seiko Co., Ltd.

Examples of cyanate ester-based curing agents include bisphenol A dicyanate, polyphenol cyanate, oligo(3-methylene-1,5-phenylenecyanate), and 4,4'-methylenebis(2,6- dimethylphenylcyanate), 4,4'-ethylidenediphenyldicyanate, hexafluorobisphenol A dicyanate, 2,2-bis(4-cyanate)phenylpropane, 1,1-bis(4- Cyanatephenylmethane), bis(4-cyanate-3,5-dimethylphenyl)methane, 1,3-bis(4-cyanatephenyl-1-(methylethylidene))benzene, bis(4-cyanate) Bifunctional cyanate resins such as natephenyl)thioether and bis(4-cyanatephenyl)ether, polyfunctional cyanate resins derived from phenol novolak and cresol novolac, etc., some of these cyanate resins are triazinated. Prepolymers, etc. can be mentioned. Specific examples of cyanate ester-based curing agents include "PT30" and "PT60" (phenol novolak-type polyfunctional cyanate ester resin), "ULL-950S" (polyfunctional cyanate ester resin), and "BA230" manufactured by Lonza Japan Co., Ltd. ", "BA230S75" (a prepolymer in which part or all of bisphenol A dicyanate is triazylated to form a trimer), etc.

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

When the resin composition contains component (E), the amount ratio of component (A) and component (E) is the ratio of [total number of epoxy groups in component (A)]:[total number of reactive groups in component (E)]. , the range of 1:0.01 to 1:2 is preferable, 1:0.05 to 1:1.5 is more preferable, and 1:0.08 to 1:1 is still more preferable. Here, the reactive group of component (E) is an active hydroxyl group, etc., and varies depending on the type of component (E). In addition, the total number of epoxy groups of component (A) means the solid mass of each (A) component divided by the epoxy equivalent, and the sum of all (A) components, and the total number of reactive groups of component (E) means , the solid mass of each (E) component divided by the reactor equivalent is the sum of all (E) components. By setting the amount ratio of component (A) and component (E) within this range, the coefficient of linear thermal expansion of the cured product of the resin composition can be lowered, and the peeling strength can be further improved.

In addition, when the resin composition contains component (E), the amount ratio of (A) epoxy resin, component (B), and component (E) is [total number of epoxy groups in component (A)]:[component (B) The ratio of the total number of reactors and reactors of component (E) is preferably in the range of 1:0.01 to 1:3, more preferably in the range of 1:0.005 to 1:2, and more preferably in the range of 1:0.1 to 1:1.5. It is more desirable.

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

<(F) Curing accelerator>

In one embodiment, the resin composition may contain (F) a curing accelerator. Examples of the curing accelerator include phosphorus-based curing accelerators, amine-based curing accelerators, imidazole-based curing accelerators, guanidine-based curing accelerators, and metal-based curing accelerators. Accelerators and metal-based curing accelerators are preferable, and amine-based curing accelerators are more preferable. The curing accelerator may be used individually, or two or more types may be used in combination.

Examples of phosphorus-based curing accelerators include triphenylphosphine, phosphonium borate compound, tetraphenylphosphonium tetraphenyl borate, n-butylphosphonium tetraphenyl borate, tetrabutylphosphonium decanoate, and (4-methylphenyl)triphenyl. Examples include phosphonium thiocyanate, tetraphenylphosphonium thiocyanate, butyltriphenylphosphonium thiocyanate, and triphenylphosphine and tetrabutylphosphonium decanoate are preferred.

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

Examples of imidazole-based curing accelerators include 2-methylimidazole, 2-undecylimidazole, 2-heptadecylimidazole, 1,2-dimethylimidazole, and 2-ethyl-4-methyl. Imidazole, 1,2-dimethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 1-benzyl-2-methyl Midazole, 1-benzyl-2-phenylimidazole, 1-cyanoethyl-2-methylimidazole, 1-cyanoethyl-2-undecylimidazole, 1-cyanoethyl-2-ethyl -4-methylimidazole, 1-cyanoethyl-2-phenylimidazole, 1-cyanoethyl-2-undecylimidazolium trimellitate, 1-cyanoethyl-2-phenylimidazolium Trimellitate, 2,4-diamino-6-[2'-methylimidazolyl-(1')]-ethyl-s-triazine, 2,4-diamino-6-[2'-undecyl imidazolyl-(1')]-ethyl-s-triazine, 2,4-diamino-6-[2'-ethyl-4'-methylimidazolyl-(1')]-ethyl-s- Triazine, 2,4-diamino-6-[2'-methylimidazolyl-(1')]-ethyl-s-triazine 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 ]Imidazole compounds such as benzimidazole, 1-dodecyl-2-methyl-3-benzylimidazolium chloride, 2-methylimidazoline, and 2-phenylimidazoline, and the relationship between imidazole compounds and epoxy resins Examples include duct bodies, and 2-ethyl-4-methylimidazole and 1-benzyl-2-phenylimidazole are preferred.

As an imidazole-based curing accelerator, a commercial product may be used, for example, “P200-H50” manufactured by Mitsubishi Chemical Corporation.

Examples of guanidine-based curing accelerators include dicyandiamide, 1-methylguanidine, 1-ethylguanidine, 1-cyclohexylguanidine, 1-phenylguanidine, 1-(o-tolyl)guanidine, dimethylguanidine, and diphenylguanidine. , trimethylguanidine, tetramethylguanidine, pentamethylguanidine, 1,5,7-triazabicyclo[4.4.0]deca-5-ene, 7-methyl-1,5,7-triazabicyclo[4.4.0] Deca-5-ene, 1-methylbiguanide, 1-ethylbiguanide, 1-n-butylbiguanide, 1-n-octadecylbiguanide, 1,1-dimethylbiguanide, 1, 1-diethyl biguanide, 1-cyclohexyl biguanide, 1-allyl biguanide, 1-phenyl biguanide, 1-(o-tolyl) biguanide, etc., dicyandiamide, 1,5,7-triazabicyclo[4.4.0]deca-5-ene is preferred.

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

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% by mass or more, when the non-volatile component in the resin composition is 100% by mass. It is 0.1% by mass or more. The upper limit is preferably 3% by mass or less, more preferably 2% by mass or less, and even more preferably 1% by mass or less. By keeping the content of the curing accelerator within this range, a cured product of the resin composition with a low linear thermal expansion coefficient and high peeling strength can be obtained.

<(G) Thermoplastic resin>

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

Thermoplastic resins include, for example, phenoxy resin, polyvinyl acetal resin, polyolefin resin, polybutadiene resin, polyimide resin (however, excluding the polyimide resin corresponding to component (C)), polyamideimide resin, Examples include polyetherimide resin, polysulfone resin, polyethersulfone resin, polyphenylene ether resin, polycarbonate resin, polyetheretherketone resin, and polyester resin, with phenoxy resin being preferred. Thermoplastic resins may be used individually, or may be used in combination of two or more types.

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

Examples of the phenoxy resin include bisphenol A skeleton, bisphenol F skeleton, bisphenol S skeleton, bisphenol acetophenone skeleton, novolac skeleton, biphenyl skeleton, fluorene skeleton, dicyclopentadiene skeleton, norbornene skeleton, and naphthalene. and a phenoxy resin having at least one skeleton selected from the group consisting of an anthracene skeleton, an adamantane skeleton, a terpene skeleton, and a trimethylcyclohexane skeleton. The terminal of the phenoxy resin may be any functional group such as a phenolic hydroxyl group or an epoxy group. Phenoxy resins may be used individually, or two or more types may be used in combination. Specific examples of phenoxy resins include "1256" and "4250" (both phenoxy resins containing a bisphenol A skeleton), "YX8100" (phenoxy resins containing a bisphenol S skeleton), and "YX6954" (bisphenol aceto) manufactured by Mitsubishi Chemical Corporation. phenoxy resin containing a phenone skeleton), and in addition, "FX280" and "FX293" manufactured by Nippon-Steel Chemicals, and "YL7500BH30", "YX6954BH30", "YX7553", and "YX7553BH30" manufactured by Mitsubishi Chemical Corporation. ", "YL7769BH30", "YL6794", "YL7213", "YL7290", and "YL7482".

Examples of the polyvinyl acetal resin include polyvinyl formal resin and polyvinyl butyral resin, with polyvinyl butyral resin being preferred. Specific examples of polyvinyl acetal resins include, for example, Denki Butyral 4000-2, Denki Butyral 5000-A, Denki Butyral 6000-C, and Denki Butyral 6000-C manufactured by Denki Chemical Co., Ltd. Denki Butyral 6000-EP", Sekisui Chemicals' S-Lec BH series, BX series (e.g. BX-5Z), KS series (e.g. KS-1), BL series, BM series, etc. You can.

Specific examples of the polyimide resin include “Licacote SN20” and “Licacote PN20” manufactured by New Nippon Chemical Co., Ltd. Specific examples of polyimide resins include linear polyimides obtained by reacting bifunctional hydroxyl group-terminated polybutadiene, diisocyanate compounds, and tetrabasic acid anhydrides (polyimides described in Japanese Patent Application Laid-Open No. 2006-37083); and modified polyimides such as polysiloxane skeleton-containing polyimides (polyimides described in Japanese Patent Application Laid-Open No. 2002-12667 and Japanese Patent Application Laid-Open No. 2000-319386, etc.).

Specific examples of the polyether sulfone resin include "PES5003P" manufactured by Tsumitomo Chemical Co., Ltd. Specific examples of the polyphenylene ether resin include the oligophenylene ether-styrene resin "OPE-2St 1200" having a vinyl group manufactured by Mitsubishi Chemical Corporation.

Specific examples of polysulfone resins 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% by mass or more, when the non-volatile component in the resin composition is 100% by mass. It is 0.5% by mass or more. The upper limit is preferably 10 mass% or less, more preferably 5 mass% or less, and even more preferably 3 mass%.

<(H) Other additives>

In one embodiment, the resin composition may further contain other additives as needed. Examples of such other additives include organophosphorus compounds, organic nitrogen-containing phosphorus compounds, nitrogen compounds, silicon compounds, and metal hydroxides. flame retardants; Organic fillers such as rubber particles; organometallic compounds such as organic copper compounds, organic zinc compounds, and organic cobalt compounds; Resin additives such as thickeners, antifoaming agents, leveling agents, adhesion imparting agents, and colorants can be mentioned.

<Physical properties and uses of resin composition>

The resin composition of the present invention produces an insulating layer (cured product of the resin composition layer) with low 10-point average roughness (Rz) and linear thermal expansion coefficient after roughening treatment and high peeling strength. Therefore, the resin composition of the present invention can be suitably used as a resin composition layer for insulation purposes. Specifically, the resin composition of the present invention can be suitably used as a resin composition for forming an insulating layer of a printed wiring board (resin composition for an insulating layer of a printed wiring board), and a resin composition for forming an interlayer insulating layer of a printed wiring board. It can be more suitably used as (resin composition for interlayer insulating layer of printed wiring board). Additionally, since the resin composition of the present invention produces an insulating layer with good component embedding properties, it can be suitably used even when the printed wiring board is a component-embedded circuit board. Additionally, the resin composition of the present invention is suitable as a resin composition for forming an insulating layer (resin composition for forming an insulating layer for forming a conductor layer) for forming a conductor layer (including a rewiring layer) on an insulating layer. It can be used easily.

The cured product obtained by heat-curing the resin composition at 100°C for 30 minutes and then at 180°C for 30 minutes exhibits the characteristic of low 10-point average roughness (Rz) after roughening treatment. That is, it results in an insulating layer with a low 10-point average roughness. The 10-point average roughness (Rz) is preferably 1500 nm or less, more preferably 1000 nm or less, and even more preferably 600 nm or less. The lower limit is not particularly limited, but may be 1 nm or more. The 10-point average roughness (Rz) can be measured according to the method described in <Measurement of peel strength and 10-point average roughness (Rz value)> described later.

The cured product obtained by heat-curing the resin composition at 100°C for 30 minutes and then at 180°C for 30 minutes exhibits the characteristic of high peel strength (plating peel strength). That is, it results in an insulating layer with high peel strength. The peeling strength is preferably 145 kgf/cm or more, more preferably 148 kgf/cm or more, and even more preferably 150 kgf/cm or more. The upper limit is not particularly limited, but may be 300 kgf/cm or less. Peel strength can be measured according to the method described in <Measurement of peel strength and 10-point average roughness (Rz value)> described later.

The cured product obtained by heat-curing the resin composition at 200°C for 90 minutes exhibits the characteristic of high glass transition temperature. This results in an insulating layer with improved brittleness. The glass transition temperature is preferably 145°C or higher, more preferably 148°C or higher, and even more preferably 150°C or higher. The upper limit is not particularly limited, but may be 300°C or lower. 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.

The cured product obtained by heat-curing the resin composition at 200°C for 90 minutes exhibits the characteristic of low linear thermal expansion coefficient. In other words, it results in an insulating layer with a low coefficient of linear thermal expansion. The linear thermal expansion coefficient is preferably 45 ppm or less, more preferably 44 ppm or less, and even more preferably 43 ppm or less. The lower limit is not particularly limited, but may be 1ppm or more. The linear thermal expansion coefficient can be measured according to the method described in <Measurement of glass transition temperature and linear thermal expansion coefficient> described later.

[Resin sheet]

The resin sheet of the present invention includes a support and a resin composition layer formed from the resin composition of the present invention provided on the support.

From the viewpoint of reducing the thickness of the printed wiring board, the thickness of the resin composition layer is preferably 200 μm or less, more preferably 100 μm or less, further preferably 50 μm or less, even more preferably 20 μm or less, 15 μm or less, Or it is 10㎛ or less. The lower limit of the thickness of the resin composition layer is not particularly limited, but can usually be 1 μm or more, 3 μm or more, etc.

Examples of the support include films made of plastic materials, metal foils, and release papers, and films and metal foils made of plastic materials are preferred.

When using a film made of a plastic material as a support, examples of the plastic material include polyethylene terephthalate (hereinafter sometimes abbreviated as “PET”) and polyethylene naphthalate (hereinafter sometimes abbreviated as “PEN”). polyester such as polyester (hereinafter sometimes abbreviated as “PC”), polycarbonate (hereinafter sometimes abbreviated as “PC”), acrylic such as polymethyl methacrylate (PMMA), cyclic polyolefin, triacetylcellulose (TAC), and polyether sulfide (PES) ), polyether ketone, polyimide, etc. Among them, polyethylene terephthalate and polyethylene naphthalate are preferable, and inexpensive polyethylene terephthalate is especially preferable.

When using a metal foil as a support, examples of the metal foil include copper foil, aluminum foil, etc., and copper foil is preferable. As the copper foil, a foil made of a simple metal of copper may be used, or a foil made of an alloy of copper and another metal (for example, tin, chromium, silver, magnesium, nickel, zirconium, silicon, titanium, etc.) may be used.

The support may be subjected to mat treatment, corona treatment, or antistatic treatment on the surface that is joined to the resin composition layer.

Additionally, as the support, a support with a release layer having a release layer on the surface bonded to the resin composition layer may be used. Examples of the release agent used in the release layer of the support with a release layer include at least one type of release agent selected from the group consisting of alkyd resin, polyolefin resin, urethane resin, and silicone resin. The support with the release layer may be a commercially available product, for example, "SK-1", "AL-5", and "AL-" manufactured by Lintec, which are PET films with a release layer containing an alkyd resin-based release agent as a main component. 7”, “Lumiror T60” manufactured by Toray Corporation, “Purex” manufactured by Teijin Corporation, and “Unifill” manufactured by Unichika Corporation.

The thickness of the support is not particularly limited, but is preferably in the range of 5 μm to 75 μm, and more preferably in the range of 10 μm to 60 μm. In addition, when using a support body with a release layer, it is preferable that the entire thickness of the support body with a release layer is within the above range.

In one embodiment, the resin sheet may further include other layers as needed. Examples of these other layers include a protective film similar to the support provided on the side of the resin composition layer that is not bonded to the support (that is, the side opposite to the support). The thickness of the protective film is not particularly limited, but is, for example, 1 μm to 40 μm. By laminating a protective film, adhesion of dust or the like to the surface of the resin composition layer and scratches can be suppressed.

The resin sheet can be manufactured, for example, by preparing a resin varnish in which a resin composition is dissolved in an organic solvent, applying this resin varnish on a support using a die coater, etc., and then drying to form a resin composition layer. .

Organic solvents include, for example, ketones such as acetone, methyl ethyl ketone (MEK) and cyclohexanone, acetic acid esters such as ethyl acetate, butyl acetate, cellosolve acetate, propylene glycol monomethyl ether acetate and carbitol acetate, Carbitols such as cellosolve and butylcarbitol, aromatic hydrocarbons such as toluene and xylene, and amide solvents such as dimethylformamide, dimethylacetamide (DMAc), and N-methylpyrrolidone. Organic solvents may be used individually, or two or more types may be used in combination.

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

The resin sheet can be stored by rolling it into a roll shape. When the resin sheet has a protective film, it becomes usable 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 from 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 and the second conductor layer (the conductor layer is sometimes called a wiring layer).

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. There is no particular limitation on the lower limit, but it can be 0.1 μm or more. The gap between the first conductor layer and the second conductor layer (thickness of the insulating layer between the first and second conductor layers) is, as an example shown in FIG. 1, the main surface 11 of the first conductor layer 1 and It refers to the thickness (t1) of the insulating layer (3) between the main surfaces (21) of the second conductor layer (2). The first and second conductor layers are conductor layers adjacent to each other through an insulating layer, and the main surfaces 11 and 21 face each other.

In addition, the thickness (t2) of the entire insulating layer is preferably 15 μm or less, more preferably 13 μm or less, and even more preferably 10 μm or less. There is no particular limitation on the lower limit, but usually it can be 1 μm or more, 1.5 μm or more, 2 μm or more, etc.

A printed wiring board can be manufactured by a method including the following steps (I) and (II) using the above-described resin sheet.

(I) A process of laminating the resin composition layer of the resin sheet on the inner layer substrate so that it is bonded to the inner layer substrate.

(II) Process of forming an insulating layer by heat curing the resin composition layer

The “inner layer substrate” used in step (I) is a member that becomes the substrate of the printed wiring board, for example, glass epoxy substrate, metal substrate, polyester substrate, polyimide substrate, BT resin substrate, and thermosetting polyphenylene. Ether substrates, etc. can be mentioned. Additionally, the substrate may have a conductor layer on one or both sides, and this conductor layer may be pattern-processed. An inner layer substrate on which a conductor layer (circuit) is formed on one or both sides of the substrate is sometimes called an “inner layer circuit board.” Additionally, when manufacturing a printed wiring board, intermediate products on which an insulating layer and/or a conductor layer are to be formed are also included in the "inner layer substrate" referred to in the present invention. If the printed wiring board is a circuit board with embedded components, an inner layer board with embedded components can be used.

Lamination of the inner layer substrate and the resin sheet can be performed, for example, by heat-pressing the resin sheet to the inner layer substrate from the support side. Examples of members for heat-pressing the resin sheet to the inner layer substrate (hereinafter also referred to as “heat-pressing members”) include heated metal plates (SUS head plates, etc.) or metal rolls (SUS rolls). In addition, it is preferable not to press the heat-compression member directly onto the resin sheet, but to press it 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 lamination method. In the vacuum lamination method, the heat-pressing temperature is preferably in the range of 60°C to 160°C, more preferably in the range of 80°C to 140°C, and the heat-compression pressure is preferably in the range of 0.098MPa to 1.77MPa, more preferably It is in the range of 0.29 MPa to 1.47 MPa, and the heat compression 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 carried out under reduced pressure conditions of 26.7 hPa or less.

Lamination can be performed using a commercially available vacuum laminator. Examples of commercially available vacuum laminators include a vacuum pressurization laminator manufactured by Meiki Seisakusho, a vacuum applicator manufactured by Nikko Materials, and a batch vacuum pressurized laminator.

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

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 heat-cured to form an insulating layer.

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

For example, the heat curing conditions of the resin composition layer vary depending on the type of resin composition, etc., but 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 170°C). 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 thermally curing the resin composition layer, the resin composition layer may be preheated to a temperature lower than the curing temperature. For example, prior to heat curing the resin composition layer, the resin composition layer is cured at a temperature of 50°C or higher and less 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 even more preferably 15 minutes to 100 minutes).

When manufacturing a printed wiring board, (III) a step of perforating the insulating layer, (IV) a step of roughening the insulating layer, and (V) a step of forming a conductor layer may be additionally performed. These steps (III) to (V) may be carried out according to various methods known to those skilled in the art that are used in the production of printed wiring boards. Additionally, when the support is removed after step (II), the support may be removed between steps (II) and (III), between steps (III) and (IV), or between steps (IV) and (V). It may be carried out in between. Additionally, 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 each conductor layer (t1 in FIG. 1) is preferably within the above range.

Process (III) is a process of drilling into the insulating layer, thereby forming holes such as via holes and through holes in the insulating layer. Step (III) may be performed using, for example, a drill, laser, plasma, etc., depending on the composition of the resin composition used to form the insulating layer. The size and shape of the hole may be appropriately determined depending on the design of the printed wiring board.

Process (IV) is a process of roughening the insulating layer. The procedures and conditions of the roughening process are not particularly limited, and known procedures and conditions usually used in forming the insulating layer of a printed wiring board can be adopted. For example, the insulating layer can be roughened by performing swelling treatment with a swelling liquid, roughening treatment with an oxidizing agent, and neutralization treatment with a neutralizing liquid in this order. The swelling liquid used in the roughening treatment is not particularly limited, and includes an alkaline solution and a surfactant solution, and is preferably an alkaline solution. Sodium hydroxide solution and potassium hydroxide solution are more preferable as the alkaline solution. Examples of commercially available swelling liquids include “Swelling Deep Securiganth P” and “Swelling Deep Securiganth SBU” manufactured by Atotech Japan. The swelling treatment using the swelling liquid is not particularly limited, but can be performed, for example, by immersing the insulating layer in a swelling liquid of 30°C to 90°C for 1 minute to 20 minutes. From the viewpoint of suppressing swelling of the insulating layer resin to an appropriate level, it is preferable to immerse the insulating layer in a swelling liquid of 40°C to 80°C for 5 to 15 minutes. The oxidizing agent used in the roughening treatment is not particularly limited, but examples include an alkaline permanganate solution obtained by dissolving potassium permanganate or sodium permanganate in an aqueous solution of sodium hydroxide. 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°C to 80°C for 10 to 30 minutes. Additionally, the concentration of permanganate in the alkaline permanganate solution is preferably 5% by mass to 10% by mass. Examples of commercially available oxidizing agents include alkaline permanganate solutions such as “Concentrate Compact CP” and “Dosing Solution Securiganth P” manufactured by Atotech Japan. In addition, an acidic aqueous solution is preferable as a neutralizing liquid used in the roughening treatment, and examples of commercial products include "Reduction Solution Securiganth P" manufactured by Atotech Japan. Treatment with a neutralizing liquid can be performed by immersing the treated surface, which has undergone roughening treatment with an oxidizing agent, in a neutralizing liquid at 30°C to 80°C for 5 to 30 minutes. In terms of workability, etc., a method of immersing an object that has been roughened with an oxidizing agent in a neutralizing liquid at 40°C to 70°C for 5 to 20 minutes is preferable.

In one embodiment, the arithmetic mean roughness (Ra) of the surface of the insulating layer after roughening is preferably 400 nm or less, more preferably 350 nm or less, and still more preferably 300 nm or less. There is no particular limitation on the lower limit, but it is preferably 0.5 nm or more, and more preferably 1 nm or more. In addition, the root mean square roughness (Rq) of the surface of the insulating layer after the roughening treatment is preferably 400 nm or less, more preferably 350 nm or less, and even more preferably 300 nm or less. There is no particular limitation on the lower limit, but it is preferably 0.5 nm or more, and more preferably 1 nm or more. The arithmetic mean roughness (Ra) and root mean square roughness (Rq) of the surface of the insulating layer can be measured using a non-contact surface roughness meter.

Process (V) is a process of forming a conductor layer. When no conductor layer is formed on the inner layer substrate, step (V) is a step of forming a first conductor layer, and when a conductor layer is formed on the inner layer substrate, the conductor layer is the first conductor layer, and step ( V) is the process of forming the second conductor layer.

The conductor material used in the conductor layer is not particularly limited. In a suitable embodiment, the conductor layer comprises one or more metals selected from the group consisting of gold, platinum, palladium, silver, copper, aluminum, cobalt, chromium, zinc, nickel, titanium, tungsten, iron, tin and indium. . The conductor layer may be a single metal layer or an alloy layer, and the alloy layer may be, for example, an alloy of two or more metals selected from the above-described group (e.g., nickel-chromium alloy, copper-nickel alloy, and copper-titanium alloy) ) can include a layer formed of. Among them, from the viewpoint of versatility of forming the conductor layer, cost, ease of patterning, etc., a single metal layer of chromium, nickel, titanium, aluminum, zinc, gold, palladium, silver or copper, or a nickel-chromium alloy, copper-nickel alloy, An alloy layer of a copper-titanium alloy is preferable, a monometal layer of chromium, nickel, titanium, aluminum, zinc, gold, palladium, silver, or copper, or an alloy layer of a nickel-chromium alloy is more preferable, and a monometal layer of copper is still more preferable. do.

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

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

In one embodiment, the conductor layer may be formed by plating. For example, a conductor layer with a desired wiring pattern can be formed by plating on the surface of the insulating layer using a conventionally known technique such as a semi-additive method or a full additive method, and from the viewpoint of ease of manufacturing, the semi-additive method can be used. It is preferable to form it by the additive method. Hereinafter, an example of forming a conductor layer by a semi-additive method will be disclosed.

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

Since the resin sheet of the present invention forms an insulating layer with good component embedding properties, it can be suitably used even when the printed wiring board is a component-embedded circuit board. A circuit board with built-in components can be manufactured by a known manufacturing method.

The printed wiring board manufactured using the resin sheet of the present invention may be provided with 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.

[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 semiconductor devices include various semiconductor devices used in electrical appliances (e.g., computers, mobile phones, digital cameras, televisions, etc.) and vehicles (e.g., motorcycles, automobiles, trams, ships, aircraft, etc.). there is.

The semiconductor device of the present invention can be manufactured by mounting components (semiconductor chips) in conduction points of a printed wiring board. A “continuity location” is a “location that transmits an electric signal on a printed wiring board,” and the location may be on the surface or buried. Additionally, 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 when manufacturing a semiconductor device is not particularly limited as long as the semiconductor chip functions effectively, but specifically includes the wire bonding mounting method, flip chip mounting method, and bumpless build-up layer (BBUL). Examples include a mounting method, a mounting method using an anisotropic conductive film (ACF), and a mounting method using a non-conductive film (NCF). Here, the “mounting method using a bumpless build-up layer (BBUL)” refers to a “mounting method in which a semiconductor chip is directly embedded in a recessed portion of a printed wiring board and the semiconductor chip is connected to the wiring on the printed wiring board.”

Example

Hereinafter, the present invention will be described in more detail through examples. The present invention is not limited to these examples. In addition, “part” and “%” indicating quantities below mean “part by mass” and “% by mass”, respectively, unless otherwise specified.

First, various measurement and evaluation methods will be explained.

<Measurement of peel strength and 10-point average roughness (Rz value)>

(Preparation of samples for measuring peel strength and 10-point average roughness (Rz value))

(1) Base processing of inner layer circuit board

A glass cloth-based epoxy resin double-sided copper-clad laminate (copper foil thickness 18 μm, substrate thickness 0.8 mm, “R1766” manufactured by Panasonic Corporation) on which an inner layer circuit was formed was prepared as an inner layer circuit board, and both sides were treated with a micro-etchant (Mack Co., Ltd.). The copper surface was roughened by immersing it in (manufactured by “CＺ8101”) (copper etching amount: 1.0 μm).

(2) Lamination of resin sheets

The resin sheet having a thickness of 10 ㎛ of the resin composition layer produced in the examples and comparative examples was layered using a batch-type vacuum pressurization laminator (2-stage built-up laminator, CVP700, manufactured by Nikko Materials Co., Ltd.), and the resin composition layer was formed as an inner layer. To bond it to the circuit board, both sides of the inner layer circuit board were laminated. The lamination treatment was performed by reducing the pressure for 30 seconds to bring the atmospheric pressure to 13 hPa or less, and then compressing it at 100°C and a pressure of 0.74 MPa for 30 seconds. Next, heat pressing was performed at 100°C and a pressure of 0.5 MPa for 60 seconds.

(3) Curing of the resin composition

After laminating a resin sheet with a thickness of 10 μm, the resin composition layer was heat-cured at 100°C for 30 minutes and then at 180°C for 30 minutes to form an insulating layer. Afterwards, the support was peeled off to expose the insulating layer.

(4) Harmonization processing

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

(5) Formation of conductor layer

A conductor layer was formed on the roughened surface of the insulating layer according to the semi-additive method. That is, a plating process (copper plating process using a chemical solution manufactured by Atotech Japan) including the steps 1 to 6 below was performed to form a conductor layer.

1. Alkaline cleaning (cleaning and charge adjustment of the surface of the insulating layer where via holes are installed)

The surface of evaluation board a was cleaned at 60°C for 5 minutes using Cleaning Cleaner Securiganth 902 (brand name).

2. Soft etching (cleaning inside via hole)

The surface of the evaluation substrate a was treated at 30°C for 1 minute using an aqueous sulfuric acidic sodium peroxodisulfate solution.

3. Pre-dip (adjustment of charge on the surface of the insulating layer to impart Pd)

The surface of evaluation substrate a was treated for 1 minute at room temperature using Pre.Dip Neoganth B (brand name).

4. Provision of activator (provision of Pd to the surface of the insulating layer)

The surface of evaluation substrate a was treated at 35°C for 5 minutes using Activator Neoganth 834 (brand name).

5. Reduction (reduces Pd given to the insulating layer)

The surface of evaluation board a was treated at 30°C for 5 minutes using a mixture of Reducer Neoganth WA (brand name) and Reducer Acceralator 810 mod. (brand name).

6. Electroless copper plating process (Cu is deposited on the surface of the insulating layer (Pd surface))

The surface of evaluation board a was treated at 35°C using a mixture of Basic Solution Printganth MSK-DK (brand name), Copper solution Printganth MSK (brand name), Stabilizer Printganth MSK-DK (brand name), and Reducer Cu (brand name). Processed for 30 minutes. The thickness of the formed electroless copper plating layer was 1㎛.

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

(Measurement of 10-point average roughness (Rz))

For evaluation board a before forming the conductor layer, a non-contact surface roughness meter (“WYKO NT3300” manufactured by BCO Instruments) was used in VSI contact mode with a 50x lens, and the measurement range was 121 ㎛ × 92 ㎛. From the obtained values, the maximum height roughness (Rz) described in Japanese Industrial Standards (JIS B0601-2001) was determined.

(Measurement of peel strength of plated conductor layer)

The peeling strength of the plated conductor layer was measured for evaluation board b in accordance with Japanese Industrial Standards (JIS C6481). Specifically, a cut of 10 mm in width and 100 mm in length was made in the conductor layer of evaluation board b, one end of this was peeled off, picked up with a plier, and 35 mm was peeled off in the vertical direction at a speed of 50 mm/min at room temperature. The load (kgf/cm) was measured to determine the peel strength. A tensile tester (“AC-50C-SL” manufactured by TSE) was used for the measurement.

<Measurement of glass transition temperature and linear thermal expansion coefficient>

(Production of hardened product for evaluation)

The resin sheet having a thickness of 25 μm of the resin composition layer produced in the examples and comparative examples was heated at 200° C. for 90 minutes to heat-cure the resin composition layer, and then the support was peeled off. The obtained cured product is referred to as “cured product c for evaluation.”

(Measurement of glass transition temperature and linear thermal expansion coefficient)

The cured product c for evaluation was cut into test pieces with a width of 5 mm and a length of 15 mm. The above test piece was subjected to thermomechanical analysis by the tensile weighting method using a thermomechanical analysis device (“Thermo Plus TMA8310” manufactured by Rigac Co., Ltd.). In detail, the test piece was mounted on the thermomechanical analysis device, and then measured twice in succession under the measurement conditions of a load of 1 g and a temperature increase rate of 5°C/min. And in two measurements, the glass transition temperature (°C) and the linear thermal expansion coefficient (ppm/°C) in the planar 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 meter connected to a reflux condenser, a nitrogen introduction tube, and a stirrer was prepared. In 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-aminophenol 29.6 g of phenyl]-1,1,3-trimethylindane was added, and the mixture was stirred at 45°C for 2 hours under a nitrogen stream to perform a reaction to obtain a reaction solution.

Next, the temperature of this reaction solution was raised and maintained at about 160°C, and the condensation water was azeotropically removed with toluene under a nitrogen stream. It was confirmed that a predetermined amount of water was accumulated in the moisture measuring water tank and that the outflow of water was no longer visible. After confirmation, the reaction solution was further heated and stirred at 200°C for 1 hour. After that, it was cooled, and a varnish containing 20% by mass of a polyimide resin having a 1,1,3-trimethylindane skeleton (hereinafter sometimes referred to as “polyimide resin 1”) was obtained. The obtained polyimide resin 1 had a repeating unit represented by the following formula (X1) and a repeating unit represented by the formula (X2). Additionally, the weight average molecular weight of polyimide resin 1 was 12000.

[Formula X1]

[Formula X2]

<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 mixed with 9,9-bis(4). -Aminophenyl)fluorene was changed to 22.9g. 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 except for the above. The obtained polyimide resin 2 had a repeating unit represented by the following formula (X3) and a repeating unit represented by the formula (X2). Additionally, the weight average molecular weight of polyimide resin 2 was 14000.

[Formula X3]

<Synthesis Example 3: Synthesis of polyimide resin 3 without polycyclic aromatic hydrocarbon skeleton>

In a reaction vessel equipped with a stirrer, fountain, thermometer, and nitrogen gas introduction 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 were added. Injection and the solution was heated to 60°C. Next, 43.7 g of dimer diamine (“PRIAMINE 1075” manufactured by Croda Japan) and 5.4 g of 1,3-bisaminomethylcyclohexane were added dropwise, and then an imidization reaction was performed at 140°C for 1 hour. As a result, a varnish (non-volatile matter 30% by mass) containing dimerdiamine polyimide resin was obtained (hereinafter sometimes referred to as “polyimide resin 3”). Additionally, the weight average molecular weight of polyimide resin 3 was 25000.

<Example 1>

30 parts of bisphenol A type epoxy resin (“828US” manufactured by Mitsubishi Chemical Corporation, epoxy equivalent approximately 180), 30 parts of biphenyl type epoxy resin (“NC3000H” manufactured by Nippon Kayaku, epoxy equivalent approximately 269), 40 parts of solvent naphtha and cyclo It was heated and dissolved with stirring in 15 parts of hexanone mixed solvent, and then cooled to room temperature. To this mixed solution, spherical silica (average particle diameter 0.078 ㎛, specific surface area 30.7 m ² /g, “UFP” manufactured by Denki Chemical) surface-treated with an aminosilane-based coupling agent (“KBM573” manufactured by Shin-Etsu Chemical Co., Ltd.) -30") 100 parts, a phenol-based curing agent containing a triazine skeleton (“LA-3018-50P” manufactured by DIC, hydroxyl equivalent weight of about 151, 2-methoxypropanol solution with a solid content of 50%), 14 parts, an active ester-based curing agent ( 40 parts of “HPC-8000-65T” manufactured by DIC, a toluene solution with an active group equivalent of about 223 and a non-volatile component of 65% by mass), a varnish containing the polyimide resin 1 synthesized in Synthesis Example 1 (γ with a solid content of 20% by mass) - Mix 20 parts of butyrolactone solution and 6 parts of curing accelerator (“DMAP”, 4-dimethylaminopyridine, methyl ethyl ketone (hereinafter abbreviated as “MEK”) solution with a solid content of 5% by mass) and mix with a high-speed rotating mixer. Resin varnish 1 was prepared by uniformly dispersing it.

As a support, two PET films with an alkyd resin-based release layer (“AL5” manufactured by Lintec, thickness 38 μm) were prepared. On the release layer of each support, resin varnish 1 was uniformly applied so that the thickness of the dried resin composition layer was 10 μm and 25 μm, and dried at 70 to 95 ° C. for 2 minutes to produce resin sheet 1.

<Example 2>

In Example 1, 30 parts of a biphenyl type epoxy resin (“NC3000H” manufactured by Nihon Kayaku Co., Ltd., epoxy equivalent weight approximately 269) and 30 parts of a naphthol-type epoxy resin (“ESN475V” manufactured by Nihon-Nippon Chemical Industries, Ltd., epoxy equivalent weight 332) were used. Changed. Resin varnish 2 and resin sheet 2 were produced in the same manner as in Example 1 except for the above.

<Example 3>

In Example 1, 30 parts of biphenyl-type epoxy resin (“NC3000H” manufactured by Nippon Kayaku, epoxy equivalent of about 269) was changed to 30 parts of bixylenol-type epoxy resin (“YX4000HK” manufactured by Mitsubishi Chemical Corporation, epoxy equivalent of about 185). did. Resin varnish 3 and resin sheet 3 were produced in the same manner as in Example 1 except for the above.

<Example 4>

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

<Example 5>

In Example 1, 20 parts of the varnish containing polyimide resin 1 synthesized in Synthesis Example 1 (γ-butyrolactone solution with a solid content of 20% by mass) was mixed with the varnish containing polyimide resin 2 synthesized in Synthesis Example 2. (γ-Butyrolactone solution with a solid content of 20% by mass) was changed to 20 parts. Resin varnish 5 and resin sheet 5 were produced in the same manner as in Example 1 except for the above.

<Comparative Example 1>

In Example 1, 20 parts of the varnish containing the polyimide resin synthesized in Synthesis Example 1 (γ-butyrolactone solution with a solid content of 20% by mass) was mixed with a phenoxy resin (“YX6954BH30” manufactured by Mitsubishi Chemical Corporation, solid content of 30% by mass). % of a 1:1 solution of MEK and cyclohexanone) was changed to 13 parts. Resin varnish 6 and resin sheet 6 were produced in the same manner as in Example 1 except for the above.

<Comparative Example 2>

In Example 1, 20 parts of the varnish containing the polyimide resin synthesized in Synthesis Example 1 (γ-butyrolactone solution with a solid content of 20% by mass) was mixed with the varnish containing the polyimide resin 3 synthesized in Synthesis Example 3 ( A mixed solution of cyclohexanone and methylcyclohexane with a solid content of 30% by mass) was changed to 13 parts. Resin varnish 7 and resin sheet 7 were produced in the same manner as in Example 1 except for the above.

The components used to prepare resin compositions 1 to 7 and their mixing amounts (converted to non-volatile components) are listed in the table below. In addition, "content (mass %) of component (D)" in the table below represents the content of component (D) when the non-volatile component in the resin composition is 100 mass %.

In Examples 1 to 5, it was confirmed that even when components (E) to (G) were not contained, the same results as in the above examples were obtained, although there was a difference in degree.

1: first conductor layer
11: Main surface of first conductor layer
2: second conductor layer
21: Main surface of second conductor layer
3: Insulating layer
t1: Spacing between the first conductor layer and the second conductor layer (thickness of the insulating layer between the first and second conductor layers)
t2: Thickness of the entire insulating layer

Claims (20)

(A) epoxy resin,
(B) activated ester-based curing agent,
(C) polyimide resin having a polycyclic aromatic hydrocarbon skeleton,
(D) inorganic fillers, and
(B) Contains (E) a curing agent other than an active ester-based curing agent,
(D) A resin composition in which the average particle diameter of component is 100 nm or less,
(C) A resin composition in which the content of component 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. (A) epoxy resin,
(B) activated ester-based curing agent,
(C) polyimide resin having a polycyclic aromatic hydrocarbon skeleton,
(D) inorganic fillers, and
(B) Contains (E) a curing agent other than an active ester-based curing agent,
(D) A resin composition wherein the specific surface area of the component is 15 m ² /g or more,
(C) A resin composition in which the content of component 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. (A) epoxy resin,
(B) activated ester-based curing agent,
(C) polyimide resin having a polycyclic aromatic hydrocarbon skeleton,
(D) inorganic fillers, and
(B) Contains (E) a curing agent other than an active ester-based curing agent,
(D) A resin composition in which the average particle diameter of component is 100 nm or less,
(C) A resin composition in which the component is selected from the group consisting of a polyimide resin having a fluorene skeleton and a polyimide resin having a repeating unit represented by the following formula (1).
[Formula 1]

(In Formula 1, A represents a polycyclic aromatic hydrocarbon skeleton, and D represents a divalent linking group) (A) epoxy resin,
(B) activated ester-based curing agent,
(C) polyimide resin having a polycyclic aromatic hydrocarbon skeleton,
(D) inorganic fillers, and
(B) Contains (E) a curing agent other than an active ester-based curing agent,
(D) A resin composition wherein the specific surface area of the component is 15 m ² /g or more,
(C) A resin composition in which the component is selected from the group consisting of a polyimide resin having a fluorene skeleton and a polyimide resin having a repeating unit represented by the following formula (1).
[Formula 1]

(In Formula 1, A represents a polycyclic aromatic hydrocarbon skeleton, and D represents a divalent linking group) The resin composition according to any one of claims 1 to 4, 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 4, wherein the polycyclic aromatic hydrocarbon skeleton is at least one of an indane skeleton and a fluorene skeleton. The resin composition according to any one of claims 1 to 4, wherein the weight average molecular weight of component (C) is 5000 or more. The resin composition according to any one of claims 1 to 4, wherein component (C) has a repeating unit having a polycyclic aromatic hydrocarbon skeleton and a repeating unit having an imide structure. The method of claim 8, wherein the mass ratio of the repeating unit having a polycyclic aromatic hydrocarbon backbone and the repeating unit having an imide structure (mass of repeating unit having a polycyclic aromatic hydrocarbon backbone/mass of repeating unit having an imide structure) is 0.5. A resin composition that is 2 or less. The resin composition according to claim 3 or 4, wherein the content of 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 according to any one of claims 1 to 4, wherein the content of component (B) is 1% by mass or more and 25% by mass or less when the nonvolatile component in the resin composition is 100% by mass. The resin composition according to any one of claims 1 to 4, wherein the content of component (D) is 30% by mass or more and 80% by mass or less when the nonvolatile component in the resin composition is 100% by mass. delete The resin composition according to claim 1, wherein (E) the curing agent is a phenol-based curing agent. The resin composition according to any one of claims 1 to 4, which is used for forming an insulating layer for forming a conductor layer. The resin composition according to any one of claims 1 to 4, which is used for forming an insulating layer of a printed wiring board. The resin composition according to any one of claims 1 to 4, which is used for forming an interlayer insulating layer of a printed wiring board. A resin sheet comprising a support and the resin composition layer according to any one of claims 1 to 4 provided on the support. A printed wiring board comprising a first conductor layer, a second conductor layer, and an insulating layer formed between the first conductor layer and the second conductor layer,
A printed wiring board, wherein the insulating layer is a cured product of the resin composition according to any one of claims 1 to 4. A semiconductor device comprising the printed wiring board according to claim 19.

Images