TWI773745B - resin composition - Google Patents

Abstract

The object of the present invention is to provide a resin composition with a low minimum melt viscosity and excellent lamination properties that can be obtained as a cured product with excellent fine circuit formation ability and low dielectric tangent even when an inorganic filler with a small average particle size or a large specific surface area is used. Wait. The solution is a resin composition containing (A) an epoxy resin, (B) an active ester-based hardener, (C) a polyimide resin, and (D) an inorganic filler with an average particle size of 100 nm or less. In the resin composition of the material, when the resin component is 100% by mass, the content of the component (C) is 0.1% by mass or more and 6% by mass or less.

Description

resin composition

The present invention relates to resin compositions. Furthermore, it relates to the printed wiring board containing the resin sheet containing this resin composition, the insulating layer formed with the hardened|cured material of the resin composition, and a semiconductor device.

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

[Patent Document 1] Japanese Patent Application Laid-Open No. 2016-27097

[The problem to be solved by the invention]

The inventors of the present invention have obtained the following findings after further examination of the resin composition. When a large amount of an inorganic filler is contained in the resin composition, the minimum melt viscosity of the resin composition increases, and the embedding property of the film decreases. As a result, it was found that it was difficult to control the lamination property. In particular, from the viewpoint of thin film formation, when an inorganic filler with a small average particle size or a large specific surface area is contained in the resin composition, the minimum melt viscosity of the resin composition is further increased, and the embeddability is significantly reduced.

The object of the present invention is to provide a resin composition with a low minimum melt viscosity and excellent lamination properties, even when an inorganic filler with a small average particle size or a large specific surface area is used, and a cured product with excellent fine circuit formation ability and low dielectric tangent can be obtained. A resin sheet comprising the resin composition; a printed wiring board provided with an insulating layer formed using the resin composition, and a semiconductor device. [means to solve the problem]

As a result of diligent investigations in order to achieve the subject of the present invention, the inventors of the present invention found that when a specific amount of (C) component is contained in the resin composition, an inorganic filler with a small average particle size or a large specific surface area can be obtained even if it is used. , it is also possible to obtain a resin composition with excellent microcircuit forming ability, low dielectric tangent, low minimum melt viscosity, and excellent lamination properties of the cured product, thereby completing the present invention.

That is, the present invention includes the following. [1] A resin composition comprising (A) an epoxy resin, (B) an active ester-based hardener, (C) a polyimide resin, and (D) a resin composition of an inorganic filler, wherein ( The average particle diameter of the component D) is 100 nm or less, and the content of the component (C) is 0.1 mass % or more and 6 mass % or less when the resin component is 100 mass %. [2] A resin composition comprising (A) an epoxy resin, (B) an active ester-based hardener, (C) a polyimide resin, and (D) a resin composition of an inorganic filler, wherein ( When the specific surface area of the component D) is 15 m ² /g or more and the resin component is 100 mass %, the content of the (C) component is 0.1 mass % or more and 6 mass % or less. [3] The resin composition according to [1] or [2], wherein the component (C) is a polyimide resin having a polycyclic aromatic hydrocarbon skeleton. [4] The resin composition according to [3], wherein the polycyclic aromatic hydrocarbon skeleton is an aromatic hydrocarbon skeleton obtained by condensation of a 5-membered ring compound and an aromatic ring. [5] The resin composition according to [3] or [4], wherein the polycyclic aromatic hydrocarbon skeleton is at least any one of an indenane skeleton and a perylene skeleton. [6] The resin composition according to any one of [1] to [5], wherein the weight average molecular weight of the component (C) is 5,000 or more. [7] The resin composition according to any one of [1] to [6], wherein the component (C) has a repeating unit having a polycyclic aromatic hydrocarbon skeleton and a repeating unit having an imide structure. [8] The resin composition according to [7], wherein the mass ratio of the repeating unit having a polycyclic aromatic hydrocarbon skeleton to the repeating unit having an imide structure (mass of the repeating unit having a polycyclic aromatic hydrocarbon skeleton) /the mass of the repeating unit having an imide structure) is 0.5 or more and 2 or less. [9] The resin composition according to any one of [1] to [8], wherein the content of the component (C) is 0.1 mass % or more and 3 mass % when the non-volatile matter in the resin composition is 100 mass % %the following. [10] The resin composition according to any one of [1] to [9], wherein the content of component (B) is 1 mass % or more and 25 mass % when the non-volatile content in the resin composition is 100 mass % %the following. [11] The resin composition according to any one of [1] to [10], wherein the content of component (D) is 30% by mass or more and 80% by mass when the nonvolatile content in the resin composition is 100% by mass %the following. [12] The resin composition according to any one of [1] to [11], which further contains (E) a hardener. [13] The resin composition according to [12], wherein (E) the hardener is a phenol-based hardener. [14] The resin composition according to any one of [1] to [13], which is for forming an insulating layer of a printed wiring board. [15] The resin composition according to any one of [1] to [14], which is for forming an interlayer insulating layer of a printed wiring board. [16] A resin sheet, comprising a support, and a resin composition layer such as any one of [1] to [15] arranged on the support. [17] 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, wherein the insulating layer is such as [ The cured product of the resin composition of any one of 1] to [15]. [18] A semiconductor device comprising the printed wiring board according to [17]. [Effect of invention]

According to the present invention, even if an inorganic filler with a small average particle size or a large specific surface area is used, a resin composition with a low minimum melt viscosity and excellent lamination properties can be obtained as a cured product with excellent fine circuit forming ability and low dielectric tangent. ; A resin sheet comprising the resin composition; a printed wiring board provided with an insulating layer formed using the resin composition, and a semiconductor device.

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) epoxy resin, (B) active ester-based hardener, (C) polyimide resin, and (D) inorganic filler The average particle diameter of (D) component is 100 nm or less, and content of (C) component is 0.1 mass % or more and 6 mass % or less when resin component is 100 mass %. Even if the resin composition of the first embodiment contains (C) component, even if it contains (D) an inorganic filler having an average particle diameter of 100 nm or less, it is possible to obtain curing with excellent microcircuit formation ability and low dielectric tangent. Resin composition with low minimum melt viscosity and excellent lamination properties. Furthermore, the resin composition of the second embodiment is a resin composition containing (A) an epoxy resin, (B) an active ester-based hardener, (C) a polyimide resin, and (D) an inorganic filler, The specific surface area of the component (D) is 15 m ² /g or more, and the content of the component (C) is 0.1 mass % or more and 6 mass % or less when the resin component is 100 mass %. When the resin composition of the second embodiment contains the component (C), even if it contains an inorganic filler having a specific surface area of 15 m ² /g or more (D), it is possible to obtain an excellent microcircuit forming ability and a low dielectric tangent. The hardened product has a low minimum melt viscosity and a resin composition with excellent lamination properties.

The resin composition may further contain components such as (E) hardener (excluding active ester type hardener), (F) hardening accelerator, (G) thermoplastic resin, and (H) other additives as required. Hereinafter, each component contained in the resin composition of the 1st and 2nd embodiment of this invention is demonstrated in detail. Here, the resin composition of the first embodiment and the resin composition of the second embodiment are collectively referred to as "resin composition".

<(A) Epoxy resin>

The resin composition contains (A) an epoxy resin. Examples of epoxy resins include bixylenol type epoxy resins, bisphenol A type epoxy resins, bisphenol F type epoxy resins, bisphenol S type epoxy resins, bisphenol AF type epoxy resins, and dicyclopentane epoxy resins. Diene epoxy resin, trisphenol epoxy resin, naphthol novolak epoxy resin, phenol novolak epoxy resin, tert-butyl-catechol epoxy resin, naphthalene epoxy resin, Naphthol type epoxy resin, Anthracene type epoxy resin, Glycidylamine type epoxy resin, Glycidyl ester type epoxy resin, Cresol novolac type epoxy resin, Biphenyl type epoxy resin, Linear aliphatic ring Oxygen resin, epoxy resin with butadiene structure, alicyclic epoxy resin, heterocyclic epoxy resin, epoxy resin containing spiro ring, cyclohexane type epoxy resin, cyclohexane dimethanol type ring Oxygen resin, naphthylene ether type epoxy resin, trimethylol type epoxy resin, tetraphenylethane type epoxy resin, etc. An epoxy resin may be used individually by 1 type, and may be used in combination of 2 or more types.

The epoxy resin preferably contains an epoxy resin having two or more epoxy groups in one molecule. It is preferable that it is an epoxy resin which has 2 or more epoxy groups in 1 molecule at least 50 mass % or more when the nonvolatile content of an epoxy resin is 100 mass %. The resin composition is a combination of epoxy resins that are liquid at a temperature of 20°C (hereinafter referred to as "liquid epoxy resins") and epoxy resins that are solid at a temperature of 20°C (also called "solid epoxy resins"). Oxygen resin") is preferred. The liquid epoxy resin is preferably a liquid epoxy resin having two or more epoxy groups in one molecule, and more preferably an aromatic liquid epoxy resin having two or more epoxy groups in one molecule. The solid epoxy resin is preferably a solid epoxy resin having three or more epoxy groups in one molecule, and more preferably an aromatic solid epoxy resin having three or more epoxy groups in one molecule. this invention Among them, an aromatic epoxy resin means an epoxy resin having an aromatic ring in its molecule.

The liquid epoxy resin is preferably 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 Epoxy resin, phenol novolac type epoxy resin, alicyclic epoxy resin with ester skeleton, cyclohexane type epoxy resin, cyclohexane dimethanol type epoxy resin, and epoxy resin with butadiene structure Resin; more preferably bisphenol A type epoxy resin, bisphenol F type epoxy resin and cyclohexane type epoxy resin; more preferably bisphenol A type epoxy resin. Specific examples of liquid epoxy resins include "HP4032", "HP4032D", "HP4032SS" (naphthalene type epoxy resin) manufactured by DIC Corporation, "828US", "jER828EL", and "825" manufactured by Mitsubishi Chemical Corporation , "Epikote 828EL" (bisphenol A epoxy resin), "jER807", "1750" (bisphenol F epoxy resin), "jER152" (phenol novolak epoxy resin), "630", " 630LSD" (glycidylamine type epoxy resin), "ZX1059" (mixture of bisphenol A type epoxy resin and bisphenol F type epoxy resin) manufactured by Nippon Steel & Sumitomo Metal Chemical Co., Ltd., "Nagase ChemteX Co., Ltd." EX-721" (glycidyl ester epoxy resin), "Celloxide 2021P" (alicyclic epoxy resin with ester skeleton) manufactured by Daicel, "PB-3600" (epoxy resin with butadiene structure) ), "ZX1658", "ZX1658GS" (liquid 1,4-glycidyl cyclohexane-type epoxy resin) manufactured by Nippon Steel & Sumitomo Metal Chemical Co., Ltd., "630LSD" (glycidylamine-type epoxy resin manufactured by Mitsubishi Chemical Corporation) Oxygen resin) etc. These may be used individually by 1 type, and may be used in combination of 2 or more types.

Solid epoxy resin, preferably bixylenol type epoxy resin, naphthalene type epoxy resin, naphthalene type 4-functional epoxy resin, cresol novolac type epoxy resin, dicyclopentadiene type epoxy resin , trisphenol type epoxy resin, naphthol type epoxy resin, biphenyl type epoxy resin, naphthyl ether type epoxy resin, anthracene type epoxy resin, bisphenol A type epoxy resin, bisphenol AF type ring Oxygen resin, tetraphenylethane type epoxy resin; more preferably bixylenol type epoxy resin, naphthalene type epoxy resin, bisphenol AF type epoxy resin, naphthol type epoxy resin, biphenyl type epoxy resin Oxygen resin and naphthylene ether type epoxy resin; more preferably bixylenol type epoxy resin, naphthol type epoxy resin, biphenyl type epoxy resin. Specific examples of solid epoxy resins include "HP4032H" (naphthalene-type epoxy resin), "HP-4700", "HP-4710" (naphthalene-type tetrafunctional epoxy resin), "N- 690" (cresol novolac epoxy resin), "N-695" (cresol novolac epoxy resin), "HP-7200" (dicyclopentadiene epoxy resin), "HP-7200HH ", "HP-7200H", "EXA-7311", "EXA-7311-G3", "EXA-7311-G4", "EXA-7311-G4S", "HP6000" (naphthyl ether type epoxy resin ), "EPPN-502H" (trisphenol epoxy resin), "NC7000L" (naphthol novolac epoxy resin), "NC3000H", "NC3000", "NC3000L", "NC3100" manufactured by Nippon Kayaku Co., Ltd. "(biphenyl type epoxy resin), "ESN475V" (naphthalene type epoxy resin) manufactured by Nippon Steel & Sumitomo Metal Chemical Co., Ltd., "ESN485" (naphthol novolac type epoxy resin), "YX4000H" manufactured by Mitsubishi Chemical Corporation ", "YX4000", "YL6121" (biphenyl type epoxy resin), "YX4000HK" (bixylenol type epoxy resin), "YX8800" (anthracene type epoxy resin), "Osaka Gas Chemicals Co., Ltd." PG-100", "CG-500", "YL7760" (bisphenol AF type epoxy resin), "YL7800" (Fine type epoxy resin) manufactured by Mitsubishi Chemical Corporation, "jER1010" manufactured by Mitsubishi Chemical Corporation (solid bisphenol A type epoxy resin), "jER1031S" (tetraphenylethane type epoxy resin), etc. These may be used individually by 1 type, and may be used in combination of 2 or more types.

When a liquid epoxy resin and a solid epoxy resin are used in combination as the component (A), the ratio of these (liquid epoxy resin: solid epoxy resin) is preferably 1:0.1~1 in terms of mass ratio : the range of 20. The ratio of the liquid epoxy resin to the solid epoxy resin is within this range, i) when it is used in the form of a resin sheet, it will bring moderate adhesion, and ii) when it is used in the form of a resin sheet, it can be obtained. Flexibility and handleability are improved, and iii) a cured product having sufficient breaking strength can be obtained. From the viewpoint of the effects of the above i) to iii), the ratio by mass of the liquid epoxy resin to the solid epoxy resin (liquid epoxy resin: solid epoxy resin) is more preferably The range of 1:0.2~1:5, and more preferably the range of 1:0.3~1:1.

From the viewpoint of obtaining an insulating layer exhibiting good mechanical strength and insulation reliability, when the nonvolatile content in the resin composition is 100% by mass, the content of component (A) in the resin composition is preferably 15%. % by mass or more, more preferably 20% by mass or more, still 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 exhibited, but is preferably 60 mass % or less, more preferably 45 mass % or less, 40 mass % or less, or 35 mass % or less.

The epoxy equivalent of the component (A) is preferably 50 to 5000, more preferably 50 to 3000, still more preferably 80 to 2000, and still more preferably 110 to 1000. By making it into this range, the crosslinking density of hardened|cured material becomes sufficient, and an insulating layer with small surface roughness can be provided. In addition, the epoxy equivalent can be measured according to JIS K7236, and it is the mass of the resin containing 1 equivalent of epoxy groups.

The weight average molecular weight of the 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 type hardener>

The resin composition contains (B) an active ester-based curing agent. The active ester-based curing agent is an active ester compound having one or more active ester groups in one molecule. Active ester-based hardeners, preferably active ester-based hardeners having two or more active ester groups in one molecule, for example, phenolic esters, thiophenolic esters, N-hydroxylamine esters, heterocyclic hydroxyl groups are preferably used An active ester-based hardener having two or more highly reactive ester groups in one molecule of esters of a compound. The active ester-based hardener may be used alone or in combination of two or more.

From the viewpoint of improving heat resistance, an active ester-based curing agent obtained by a 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 hardener 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; An aromatic compound having two or more active ester groups in one molecule obtained by reacting a carboxylic acid compound with an aromatic compound having a phenolic hydroxyl group; and more preferably having at least two or more carboxyl groups in one molecule The carboxylic acid compound is an aromatic compound obtained by reacting with an aromatic compound having a phenolic hydroxyl group, and is an aromatic compound having two or more active ester groups in one molecule. The active ester-based hardener may be linear or branched. In addition, if the carboxylic acid compound having at least two carboxyl groups in one molecule is a compound containing an aliphatic chain, the compatibility with the resin composition can be improved, and if it is a compound having an aromatic ring, heat resistance can be improved. Sex becomes higher.

Examples of the carboxylic acid compound include aliphatic carboxylic acids having 1 to 20 carbon atoms and aromatic carboxylic acids having 1 to 20 carbon atoms. Aliphatic carboxylic acid, preferably 1 to 20 carbon atoms, more preferably 2 to 10 carbon atoms, and more preferably 2 to 8 carbon atoms, and specifically, acetic acid, malonic acid, and succinic acid are exemplified , maleic acid, itaconic acid, etc. The aromatic carboxylic acid preferably has 1 to 20 carbon atoms, more preferably 7 to 10 carbon atoms, and specifically, benzoic acid, phthalic acid, isophthalic acid, terephthalic acid, benzene Pyretic acid, etc. From the viewpoint of heat resistance, among them, succinic acid, maleic acid, itaconic acid, phthalic acid, isophthalic acid, and terephthalic acid are preferred; more preferred are isophthalic acid, terephthalic acid formic acid.

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

The phenolic compound, for example, preferably has 6 to 40 carbon atoms, more preferably 6 to 30 carbon atoms, still more preferably 6 to 23 carbon atoms, and still more preferably 6 to 22 carbon atoms. Suitable specific examples of the phenolic compound include hydroquinone, resorcinol, bisphenol A, bisphenol F, bisphenol S, phenolphthalein, methylated bisphenol A, methylated bisphenol F, and methylated bisphenol. Phenol S, phenol, o-cresol, m-cresol, p-cresol, catechol, dihydroxybenzophenone, trihydroxybenzophenone, tetrahydroxybenzophenone, phloroglucinol, benzenetriol, dicyclopentadiene diphenol, etc. Moreover, as a phenolic compound, a phenol novolak and the phosphorus atom-containing oligomer which has a phenolic hydroxyl group and is described in Unexamined-Japanese-Patent No. 2013-40270 can also be used.

The naphthol compound, for example, preferably has 10 to 40 carbon atoms, more preferably 10 to 30 carbon atoms, and more preferably 10 to 20 carbon atoms. Suitable specific examples of the naphthol compound include α-naphthol, β-naphthol, 1,5-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, and the like. Moreover, a naphthol novolak can also be used as a naphthol compound.

Among them, bisphenol A, bisphenol F, bisphenol S, methylated bisphenol A, methylated bisphenol F, methylated bisphenol S, catechol, α-naphthol, β-naphthol, 1,5-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, dihydroxybenzophenone, trihydroxybenzophenone, tetrahydroxybenzophenone, phloroglucinol, Triol, dicyclopentadiene-type diphenol, phenol novolak, oligomers containing phosphorus atoms with phenolic hydroxyl groups are preferred; more preferred are catechol, 1,5-dihydroxynaphthalene, 1,6 -Dihydroxynaphthalene, 2,6-dihydroxynaphthalene, dihydroxybenzophenone, trihydroxybenzophenone, tetrahydroxybenzophenone, phloroglucinol, benzenetriol, dicyclopentadiene Phenol, novolac, oligomer containing phosphorus atom with phenolic hydroxyl group; more preferably 1,5-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, dihydroxydihydroxynaphthalene Benzophenone, trihydroxybenzophenone, tetrahydroxybenzophenone, dicyclopentadiene-type diphenols, novolacs, oligomers with phenolic hydroxyl groups containing phosphorus atoms; still more preferably 1 ,5-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, dicyclopentadiene-type diphenols, phenolic novolacs, oligomers containing phosphorus atoms with phenolic hydroxyl groups; and More preferably, 1,5-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, dicyclopentadiene-type diphenols, and oligomers containing phosphorus atoms with phenolic hydroxyl groups; Particularly preferred is a dicyclopentadiene-type diphenol.

The thiol compound is not particularly limited, and examples thereof include benzenedithiol, triazinedithiol, and the like.

Suitable specific examples of active ester-based hardeners include active ester-based hardeners containing dicyclopentadiene-type diphenol structures, active ester-based hardeners containing naphthalene structures, and active ester-based hardeners containing phenol novolac. Ester-based hardeners, active ester-based hardeners containing benzyl compounds of phenolic novolacs, active ester-based hardeners obtained by reacting aromatic carboxylic acids with oligomers containing phosphorus atoms having phenolic hydroxyl groups, etc., Among them, active ester-based hardeners containing dicyclopentadiene-type diphenol structures, active ester-based hardeners containing naphthalene structures, and aromatic carboxylic acids and phenolic hydroxyl-containing oligomers containing phosphorus atoms are particularly used. The resulting active ester-based hardener is more preferable. In addition, in the present invention, "dicyclopentadiene-type diphenol structure" means a divalent structural unit composed of phenylene-dicyclopentene-phenylene.

As the active ester-based hardener, the active-ester-based hardener disclosed in JP-A-2004-277460 and JP-A-2013-40270 can be used, and a commercially available active-ester-based hardener can also be used. Examples of commercially available active ester-based curing agents include "EXB9451", "EXB9460", "EXB9460S", "HPC-8000-65T", and "HPC-8000L-65M" (containing dicyclopentadiene) manufactured by DIC Corporation. Type diphenol structure active ester hardener), "EXB9416-70BK" made by DIC Corporation (active ester hardener containing naphthalene structure), "DC808" made by Mitsubishi Chemical Corporation (acetate containing phenol novolak) active ester hardener), "YLH1026" manufactured by Mitsubishi Chemical Corporation (active ester hardener containing benzyl compound of phenolic novolac), "EXB9050L-62M" manufactured by DIC Corporation (active ester containing phosphorus atom) hardener).

From the viewpoint of obtaining a cured product with excellent fine circuit forming ability and low dielectric tangent, the content of the active ester-based curing agent is preferably 1 mass % or more when the nonvolatile content in the resin composition is 100 mass %. More preferably, it is 5 mass % or more, and still more preferably 10 mass % or more. 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 still more preferably 15% by mass or less.

In addition, from the viewpoint of obtaining an insulating layer with good mechanical strength, when the number of epoxy groups of the (A) epoxy resin is 1, the number of reactive groups of the (B) active ester-based hardener is preferably 0.1 to 10, or more It is preferably 0.1 to 5, and more preferably 0.1 to 1. Here, "the number of epoxy groups of epoxy resins" refers to a value obtained by dividing the solid content mass of each epoxy resin present in the resin composition by the epoxy equivalent for all epoxy resins. In addition, "reactive group" means a functional group that can react with an epoxy group, and "the number of reactive groups of the active ester-based hardener" means the solid content mass of the active-ester-based hardener existing in the resin composition divided by The value of the reactive group equivalent is given as the total value of all.

<(C) Polyimide resin> The resin composition of the present invention contains (C) polyimide resin. When an inorganic filler with a small average particle size or a large specific surface area is contained in the resin composition, the melt viscosity of the resin composition generally increases. On the other hand, the resin composition of this invention containing (C)component can suppress the rise of the melt viscosity of a resin composition. The suppression of the melt viscosity increase is considered to be obtained by the low polarity of the polyimide resin and the high compatibility between the epoxy resin and the polyimide resin. In addition, thermoplastic resins containing phenoxy resins and aliphatic resins generally tend to generate highly polar components such as alcohols during curing, and as a result, the dielectric tangent of the cured resin composition may become high. On the other hand, the hardened|cured material of the resin composition of this invention containing (C)component is considered to have lower polarity than the case of the thermoplastic resin containing a phenoxy resin or the like. As a result, the dielectric tangent of the cured product decreases. In addition, since the resin composition of the present invention can form a rough surface including fine irregularities by roughening treatment, a sufficient anchor effect can be obtained even when a fine circuit is formed. As a result, The ability to form a fine circuit becomes excellent.

The content of the component (C) is 0.1 mass % or more, preferably 0.3 mass % or more, more preferably 0.5 mass %, from the viewpoint of reducing the dielectric tangent when the resin component of the resin composition is 100 mass %. More than, more preferably, 0.8 mass % or more. The upper limit is 6 mass % or less, preferably 5.8 mass % or less, more preferably 5.5 mass % or less, and still more preferably 5.2 mass % or less, from the viewpoint of obtaining a cured product excellent in fine circuit forming ability.

"Resin component" refers to the component that excludes inorganic fillers among the non-volatile components constituting the resin composition.

The component (C) is not particularly limited as long as it is a polyimide resin. As the component (C), for example, polyimide resins such as "Rikacoat SN20" and "Rikacoat PN20" manufactured by Nippon Chemical Co., Ltd; The obtained linear polyimide (polyimide described in Japanese Patent Laid-Open No. 2006-37083) and polyimide containing a polysiloxane skeleton (Japanese Patent Laid-Open No. 2002-12667 and Japanese Patent Laid-Open No. 2000) - Modified polyimide such as polyimide described in Gazette No. 319386, etc.; "dimer diamine polyimide resin"); polyimide resin with polycyclic aromatic hydrocarbon skeleton. Among them, as the component (C), from the viewpoints of further improving the ability to form fine circuits and lowering the minimum melt viscosity, particularly preferred are dimer diamine polyimide resins and polymers having a polycyclic aromatic hydrocarbon skeleton. The imide resin is more preferably a polyimide resin having a polycyclic aromatic hydrocarbon skeleton.

(dimer diamine polyimide resin) Dimer diamine polyimide resin, in its molecular structure, contains a structural unit having a structure formed by polymerizing dimer diamine, and has a polyvalent carboxyl The structural unit of the structure formed by the polymerization of acid compounds. In the following description, a structural unit having a structure formed by polymerizing a dimer diamine may be referred to as a "dimer diamine unit". Moreover, the structural unit which has the structure formed by superposing|polymerizing a polyhydric carboxylic acid compound is called "polyhydric carboxylic acid unit". Usually, in the molecule of the dimer diamine polyimide resin, the dimer diamine unit and the polycarboxylic acid unit are bonded by a cyclic imide bond.

Dimer Diamine is a dimer of aliphatic amine, and contains two amine groups in one molecule. These amine groups are usually primary amine groups represented by -NH ₂ .

The number of carbon atoms per molecule of the dimer diamine is preferably 19 or more, more preferably 27 or more; preferably 49 or less, more preferably 41 or less. In addition, the aliphatic group contained in the dimer diamine may be a saturated aliphatic group or an unsaturated aliphatic group. In addition, the dimer diamine unit may have a carbon-carbon unsaturated bond. The number of carbon-carbon unsaturated bonds per dimer diamine unit is preferably 0 to 3, more preferably 0 to 1, and particularly preferably 0.

The dimer diamine usually includes an aliphatic main chain composed of aliphatic hydrocarbon groups linked to two amine groups, and aliphatic side chains composed of two aliphatic hydrocarbon groups bonded to the main chain. Therefore, the dimer diamine unit usually contains 2 side chains composed of aliphatic hydrocarbon groups per dimer diamine unit, and the aliphatic hydrocarbon group as the side chain is preferably an unbranched straight-chain aliphatic group. family of hydrocarbons. Furthermore, from the viewpoint of remarkably obtaining the desired effects of the present invention, the number of carbon atoms per aliphatic hydrocarbon group as a side chain is preferably 2 or more, preferably 19 or less, more preferably 18 or less. Further, from the viewpoint of remarkably obtaining the desired effect of the present invention, among the two side chains per one dimer diamine unit, preferably one or more side chains are saturated aliphatic hydrocarbon groups, particularly preferred. All side chains are saturated aliphatic hydrocarbon groups.

The dimer diamine may be an alicyclic diamine containing a ring in the molecule, or a chain aliphatic diamine not containing a ring in the molecule. Therefore, the aliphatic group contained in the dimer diamine unit may also contain a ring in its molecular structure.

For specific dimer diamine, refer to the dimer diamine described in Japanese Patent No. 5534378 .

The dimer diamine can be produced, for example, by reductive amination of unsaturated fatty acids such as dimer acids, or esters thereof, higher unsaturated nitriles, or higher unsaturated alcohols, followed by dimerization. In addition, dimer diamine, for example, can be obtained by dimerizing the aforementioned unsaturated fatty acid, or its ester, higher unsaturated nitrile or higher unsaturated alcohol to obtain polyvalent fatty acid, polyvalent nitrile or polyhydric alcohol, and then reducing Aminated to manufacture. Furthermore, the production method of dimer diamine may also include carrying out hydrogenation reaction. For the production method of the dimer diamine, the method described in Japanese Patent Application Laid-Open No. 9-12712 can be referred to.

The polyvalent carboxylic acid compound refers to a carboxylic acid compound having a valence of divalent or higher, and examples thereof include carboxylic acids having 2 or more carboxyl groups per molecule and anhydrides thereof. Among them, the polyvalent carboxylic acid is particularly preferably a tetracarboxylic acid compound, and particularly preferably an aromatic tetracarboxylic acid compound, from the viewpoint of remarkably obtaining the desired effect of the present invention.

Aromatic tetracarboxylic acid compound, for example, pyromellitic acid, pyromellitic dianhydride, 4,4'-oxydiphthalic dianhydride, 3,3',4,4'-diphenylmethane Ketonetetracarboxylic dianhydride, 3,3',4,4'-diphenyl ether tetracarboxylic dianhydride, 3,3',4,4'-diphenyltetracarboxylic dianhydride, 1,2 ,3,4-benzenetetracarboxylic anhydride, 1,4,5,8-naphthalenetetracarboxylic anhydride, 2,3,6,7-naphthalenetetracarboxylic anhydride, 3,3',4,4'-biphenyltetracarboxylic Acid dianhydride, 2,2',3,3'-biphenyltetracarboxylic dianhydride, 2,3,3',4'-biphenyltetracarboxylic dianhydride, 2,3,3',4'- Benzophenone tetracarboxylic dianhydride, 2,3,3',4'-diphenyl ether tetracarboxylic dianhydride, 2,3,3',4'-diphenyltetracarboxylic dianhydride, 2,2-bis(3,3',4,4'-tetracarboxyphenyl)tetrafluoropropane dianhydride, 2,2'-bis(3,4-dicarboxyphenoxyphenyl)stilbene dianhydride, 2,2-bis(2,3-dicarboxyphenyl)propane dianhydride, 2,2-bis(3,4-dicarboxyphenyl)propane dianhydride, cyclopentanetetracarboxylic anhydride, butane-1, 2,3,4-tetracarboxylic acid, 2,3,5-tricarboxycyclopentylacetic anhydride, 4,4'-[propane-2,2-diylbis(1,4-phenoxy)] Diphthalic dianhydride, etc.

For the particularly preferred structural unit contained in the dimer diamine polyimide resin, reference can be made to Japanese Patent No. 5534378 .

In the dimer diamine polyimide resin, the amount ratio of the dimer diamine unit and the polyvalent carboxylic acid unit is arbitrary as long as the effect of the present invention is not significantly impaired. Usually, the amount ratio of the dimer diamine unit to the polycarboxylic acid unit in the dimer diamine polyimide resin is the ratio of the dimeric diamine unit used as the raw material for producing the dimer diamine polyimide resin The feed ratio of the polymer diamine and the polycarboxylic acid compound is the same. The amount ratio represented by "the number of moles of polyvalent carboxylic acid unit/the number of moles of dimer diamine unit" is specifically, preferably 0.6 or more, particularly preferably 0.8 or more, more preferably 1.4 or less, especially Preferably it is 1.2 or less. The desired effect of the present invention can be remarkably obtained by making the aforementioned quantitative ratio within the aforementioned range.

The dimer diamine polyimide resin may contain arbitrary structural units other than the dimer diamine unit and the polyvalent carboxylic acid unit as required. The dimer diamine polyimide resin may be used alone or in combination of two or more at any ratio.

The dimer diamine polyimide resin can be produced by polymerizing, for example, a dimer diamine and a polyvalent carboxylic acid compound. In addition, the dimer diamine polyimide resin, for example, can be obtained by polymerizing a dimer diamine and a polycarboxylic acid compound to obtain a polyamide acid, and then the polyamide acid can be dehydrated and cyclized to obtain a polyamide acid. Manufactured by imidization. Further, in the production method of the dimer diamine polyimide resin, the polyimide resin can also be obtained by polymerizing the dimer diamine and a polycarboxylic acid compound, and then the chain extension agent is used to carry out chain extension. reaction. For the production method of the dimer diamine polyimide resin, for example, Japanese Patent No. 5534378 can be referred to.

(Polyimide resin with polycyclic aromatic hydrocarbon skeleton)

Polycyclic aromatic hydrocarbons refer to hydrocarbons containing two or more cyclic structures in one molecule, and at least one of the cyclic structures is an aromatic ring. The two or more cyclic structures may be condensed or not. condensation.

The polycyclic aromatic hydrocarbon skeleton may have no substituent or may have a substituent. The substituent is not particularly limited, for example, halogen atom, -OH, -OC _1-6 alkyl, -N(C _1-6 alkyl) ₂ , C _1-6 alkyl, C _6-10 aryl, -NH ₂ , -CN, -C(O)OC _1-6 alkyl, -COOH, -C(O)H, -NO ₂ etc., preferably C _1-6 alkyl, more preferably methyl. The substituent may have only one kind or a plurality of kinds.

Here, the term "C _pq " (p and q are positive integers and satisfy p<q) means that the number of carbon atoms of the organic group described after the term is p to q. For example, the expression "C _1-6 alkyl" means an alkyl group having 1 to 6 carbon atoms.

The polycyclic aromatic hydrocarbon skeleton includes, for example, an indenane skeleton including a 1,1,3-trimethylindenane skeleton and the like, and a 5-membered ring such as an indene skeleton. Aromatic hydrocarbon skeletons obtained by condensation of compounds and aromatic rings; naphthalene skeletons, aromatic hydrocarbon skeletons obtained by condensation of aromatic rings such as anthracene skeletons; biphenyl skeletons without condensation but with two or more aromatic rings Aromatic hydrocarbon skeleton (non-condensed aromatic hydrocarbon skeleton), etc., from the viewpoint of further improving the ability to form fine circuits and lowering the minimum melt viscosity, preferably an aromatic hydrocarbon obtained by condensing a 5-membered ring compound with an aromatic ring Hydrocarbon skeleton. Among them, from the viewpoint of reducing the linear thermal expansion coefficient of the cured product of the resin composition, and increasing the glass transition temperature and peel strength, the polycyclic aromatic hydrocarbon skeleton, especially at least one of an indenane skeleton and a perylene skeleton, is preferred. .

From the viewpoint of further improving the ability to form fine circuits and lowering the minimum melt viscosity, the imide resin having a polycyclic aromatic hydrocarbon skeleton preferably has a polycyclic aromatic hydrocarbon skeleton and a cyclic imide structure The polyimide resin.

The cyclic imide structure includes, for example, phthalimide, succinimide, glutarimide, 3-methylglutarimide, maleimide, and dimethylmaleimide. Imide, trimellitimide, pyromellitic imide, preferably phthalimide, succinimide, especially polyimide having an aromatic imide structure The amine resin is preferably, more preferably phthalimide.

From the viewpoint of reducing the coefficient of linear thermal expansion of the cured product of the resin composition, and increasing the glass transition temperature and peel strength, the component (C) preferably has a repeating unit having a polycyclic aromatic hydrocarbon skeleton, and an imide having a repeating unit. A repeating unit of structure.

Repeating units with a polycyclic aromatic hydrocarbon backbone, such as Preferably, it is a repeating unit represented by the following general formula (1).

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

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

D in formula (1) represents a single bond or a divalent linking group, preferably a divalent linking group. Divalent linking group, for example, oxygen atom, sulfur atom, alkylene group, arylidene group, -NH-, -C(=O)-, -SO-, or a combination of two or more of these. The basis of composition, etc.

The alkylene group is preferably an alkylene group having 1 to 10 carbon atoms, more preferably an alkylene group having 1 to 6 carbon atoms, and still more preferably an alkylene group having 1 to 3 carbon atoms. The alkylene group may be any of linear, branched and cyclic. Such an alkylene group includes, for example, a methylene group, an ethylidene group, a propylidene group, a butylene group, a pentylene group, a hexylene group, and the like, and a methylene group is preferred.

The aryl group is preferably an aryl group having 6 to 14 carbon atoms, and more preferably an aryl group having 6 to 10 carbon atoms. The arylidene group includes, for example, a phenylene group, a naphthylene group, an anthracene group, and the like, and a phenylene group is preferred.

The alkylene group and the arylidene group may have no substituent or may have a substituent. The substituents are the same as those which the polycyclic aromatic hydrocarbon skeleton may have.

The group constituted by a combination of two or more of these is preferably constituted by a combination of two or more of oxygen atoms, arylidene groups, and alkylene groups foundation. Such a group includes, for example, a group in which one or more arylidene groups are bonded to one or more alkylene groups (a group consisting of a combination of an arylidene group and an alkylene group), and one or more oxygen groups. A group in which an atom is bonded to at least one aryl group (a group consisting of a combination of an oxygen atom and an aryl group), and the like. A group in which one or more arylidene groups and one or more alkylene groups are bonded, for example, a divalent group consisting of a phenylene group-methylene group, a group consisting of a phenylene group-dimethylmethylene group, The basis of the two valences formed, etc. A group in which one or more oxygen atoms are bonded to one or more arylidene groups includes, for example, a divalent group consisting of a phenylene group-oxygen atom-phenylene group, and a group consisting of an oxygen atom-phenylene group. A divalent group constituted, a divalent group constituted by an oxygen atom-naphthylene group, and the like.

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

The repeating unit having an imide structure is not particularly limited as long as it has an imide structure. From the viewpoints of further improving the ability to form fine circuits and lowering the minimum melt viscosity, repeating units having a cyclic imide structure are preferred. unit.

The cyclic imide structure includes, for example, phthalimide, succinimide, glutarimide, 3-methylglutarimide, maleimide, and dimethylmaleimide. Imide, trimellitimide, pyromellitic imide, preferably phthalimide and succinimide, among which aromatic imide structure is preferred, more preferred For phthalimide. The repeating unit having an imide structure may be a form in which the above-mentioned imide structure and a divalent linking group are bonded. The divalent linking group is the same as the divalent linking group represented by D in the general formula (1).

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

Mass ratio of repeating units with polycyclic aromatic hydrocarbon skeleton to repeating units with imide structure (mass of repeating units with polycyclic aromatic hydrocarbon skeleton/mass of repeating units with imide structure) , preferably 0.5 or more, more preferably 0.6 or more, still more preferably 0.8 or more, preferably 2 or less, more preferably 1.8 or less, and still more preferably 1.5 or less. By making this mass ratio into such a range, the linear thermal expansion coefficient of the hardened|cured material of a resin composition can be reduced, and glass transition temperature and peeling strength can be raised.

The manufacturing method of the polyimide resin which has a polycyclic aromatic hydrocarbon skeleton is not specifically limited, It can manufacture according to various methods. As a suitable embodiment, it can be obtained by polymerizing a monomer as a repeating unit having an imide structure with a monomer having a repeating unit having a polycyclic aromatic hydrocarbon skeleton. During the polymerization, a polymerization initiator or the like may be used as necessary.

The weight average molecular weight of the component (C) is preferably 5,000 or more, more preferably 10,000 or more, more preferably 11,000 or more, and more preferably 100,000 or less, from the viewpoint of further improving the ability to form fine circuits and reducing the minimum melt viscosity. , more preferably 50,000 or less, and still more preferably 30,000 or less. Here, the weight average molecular weight of the component (C) is the weight average molecular weight in terms of polystyrene measured by gel permeation chromatography (GPC).

<(D) Inorganic Filler> The resin composition of the first embodiment contains (D) an inorganic filler having an average particle diameter of 100 nm or less. Furthermore, the resin composition of the second embodiment contains (D) an inorganic filler having a specific surface area of 15 m ² /g or more. The material of the component (D) is not particularly limited, for example, silica, alumina, glass, lapis lazuli, silica, barium sulfate, barium carbonate, talc, clay, mica powder, zinc oxide, hydrotalcite, hydrated aluminum Stone, 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, titanium Bismuth acid, titanium oxide, zirconium oxide, barium titanate, barium titanate zirconate, barium zirconate, calcium zirconate, zirconium phosphate, and zirconium tungstate phosphate, etc. Among these, silica is particularly suitable. Silica includes, for example, amorphous silica, fused silica, crystalline silica, synthetic silica, hollow silica, and the like. In addition, the silica is preferably spherical silica. The inorganic filler may be used alone or in combination of two or more.

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 thin film formation and improvement of fine circuit forming ability. The lower limit of the average particle diameter is not particularly limited, but from the viewpoint of improving the layerability, it is preferably 1 nm or more, more preferably 5 nm or more, and still more preferably 10 nm or more. In addition, from the viewpoint of thin film reduction and improvement of the ability to form fine circuits, 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 80 nm or less . The lower limit of the average particle diameter is not particularly limited, and it is preferably 1 nm or more, more preferably 5 nm or more, and still more preferably 10 nm or more. Commercially available inorganic fillers having such an average particle size include "UFP-30" manufactured by Denki Chemical Industries, Ltd., and the like.

The average particle size of the inorganic filler can be measured by a laser diffraction/scattering method based on Mie scattering theory. Specifically, the particle size distribution of the inorganic filler can be made on a volume basis by a laser diffraction scattering particle size distribution measuring device, and the median diameter can be used as the average particle size to measure. For the measurement sample, it is preferable to use an inorganic filler dispersed in methyl ethyl ketone by ultrasonic waves. As the laser diffraction scattering particle size distribution analyzer, "LA-500" manufactured by Horiba Corporation, "SALD-2200" manufactured by Shimadzu Corporation, and the like 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, and still more preferably 30 m ² /g or more, from the viewpoint of improving the ability to form fine circuits. From the viewpoint of improving the layerability, the upper limit is preferably 60 m ² /g or less, more preferably 50 m ² /g or less, and still more preferably 40 m ² /g or less. In addition, from the viewpoint of improving the ability to form fine circuits, 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, and still more preferably 30 m ² /g or more. The upper limit is not particularly limited, but is preferably not more than 60 m ² /g, more preferably not more than 50 m ² /g, and still more preferably not more than 40 m ² /g. The specific surface area can be obtained by adsorbing nitrogen gas on the sample surface using a specific surface area measuring device (Macsorb HM-1210 manufactured by MOUNTECH) in accordance with the BET method, and calculating the specific surface area using the BET multipoint method.

From the viewpoint of improving moisture resistance and dispersibility, the inorganic filler is preferably a fluorine-containing silane coupling agent, an aminosilane-based coupling agent, an epoxysilane-based coupling agent, a mercaptosilane-based coupling agent, or a silane-based coupling agent. It is treated with one or more surface treatment agents such as mixtures, alkoxysilanes, organosilazane compounds, and titanate-based coupling agents; more preferably, it is treated with an aminosilane-based silane coupling agent. Commercially available surface treatment agents include, for example, "KBM403" (3-glycidyloxypropyltrimethoxysilane) manufactured by Shin-Etsu Chemical Co., Ltd., "KBM803" (3-mercaptopropyltrimethoxysilane) manufactured by Shin-Etsu Chemical Co., Ltd. silane), "KBE903" (3-aminopropyltriethoxysilane) manufactured by Shin-Etsu Chemical Co., Ltd., "KBM573" (N-phenyl-3-aminopropyltrimethoxysilane) manufactured by Shin-Etsu Chemical Co., Ltd. ), "SZ-31" (hexamethyldisilazane) manufactured by Shin-Etsu Chemical Co., Ltd., "KBM103" (phenyltrimethoxysilane) manufactured by Shin-Etsu Chemical Co., Ltd., "KBM-4803" manufactured by Shin-Etsu Chemical Co., Ltd. ( Long-chain epoxy type silane coupling 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 relative to 100 parts by mass of the component (D) The surface treatment is more preferably 0.2 parts by mass to 4 parts by mass, and still more preferably 0.3 parts by mass to 3 parts by mass. The degree of surface treatment with the surface treatment agent can be evaluated by the amount of carbon per unit surface area of the inorganic filler. From the viewpoint of improving the dispersibility of the inorganic filler, the carbon content 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 still more preferably 0.2 mg /m ² or more. On the other hand, from the viewpoint of suppressing the increase in the melt viscosity of the resin coating and the melt viscosity in the form of a sheet, it is preferably 1 mg/m ² or less, more preferably 0.8 mg/m ² or less, and still more preferably 0.5 mg/m m ² or less.

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

From the viewpoint of reducing the dielectric tangent, when the nonvolatile content in the resin composition is 100% by mass, the content of the component (D) is preferably 30% by mass or more, more preferably 35% by mass or more, and even more preferably It is 40 mass % or more. From the viewpoint of improving insulating performance, the upper limit is preferably 80% by mass or less, more preferably 70% by mass or less, and still more preferably 65% by mass or less.

<(E) Hardener> In one embodiment, the resin composition may contain (E) hardener. However, (E) hardener referred to here does not include (B) active ester type hardener. The component (E) is not particularly limited as long as it has a function of curing the component (A), and examples thereof include phenol-based curing agents, naphthol-based curing agents, benzoxazine-based curing agents, and cyanate-based curing agents. , and carbodiimide-based hardeners. Among them, as the component (E), a phenol-based hardener is particularly preferable. The hardener may be used alone or in combination of two or more.

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

Specific examples of phenol-based hardeners and naphthol-based hardeners include "MEH-7700", "MEH-7810", and "MEH-7851" manufactured by Meiwa Chemical Co., Ltd., "NHN" manufactured by Nippon Kayaku Co., Ltd., "CBN", "GPH", "SN170", "SN180", "SN190", "SN475", "SN485", "SN495", "SN-495V", "SN375", "SN-495V" manufactured by Nippon Steel & Sumitomo Metal Chemical Co., Ltd. SN395, "TD-2090", "LA-7052", "LA-7054", "LA-1356", "LA-3018-50P", "EXB-9500" manufactured by DIC Corporation, etc.

Specific examples of the benzoxazine-based curing agent include "HFB2006M" manufactured by Showa Polymer Co., Ltd., and "P-d" and "F-a" manufactured by Shikoku Chemical Industry Co., Ltd.

Examples of cyanate-based curing agents include bisphenol A dicyanate, polyphenol cyanate, oligo(3-methylene-1,5-phenylene cyanate), 4,4'-phenylene cyanate Methyl bis(2,6-dimethylphenylcyanate), 4,4'-ethylene diphenyl dicyanate, hexafluorobisphenol A dicyanate, 2,2-bis( 4-cyanate)phenylpropane, 1,1-bis(4-cyanatephenylmethane), bis(4-cyanate-3,5-dimethylphenyl)methane, 1,3- 2 Functional cyanate resins; polyfunctional cyanate resins derived from phenol novolacs and cresol novolacs, etc., and prepolymers obtained by triazinizing a part of these cyanate resins. Specific examples of cyanate-based hardeners include "PT30" and "PT60" (novolak type polyfunctional cyanate resin) and "ULL-950S" (polyfunctional cyanate resin) manufactured by Lonza Japan. , "BA230", "BA230S75" (part or all of bisphenol A dicyanate is triazinated to become a trimer prepolymer) and the like.

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

When the resin composition contains the component (E), the ratio of the amount of the component (A) to the component (E) is calculated as [the total number of epoxy groups of the component (A)]: [the total number of reactive groups of the component (E)] The ratio meter is preferably in the range of 1:0.01~1:2, more preferably 1:0.05~1:1.5, and still more preferably 1:0.08~1:1. Here, the reactive group of the (E) component refers to an active hydroxyl group and the like, and varies depending on the type of the (E) component. In addition, the total number of epoxy groups of (A) component refers to the total value obtained by dividing the solid content mass of each (A) component by the epoxy equivalent for all (A) components, and (E) component The total number of reactive groups refers to the total value obtained by dividing the solid content mass of each component (E) by the equivalent weight of reactive groups for all (E) components. Within this range, the amount ratio of the component (A) to the component (E) can further reduce the linear thermal expansion coefficient of the cured product of the resin composition and further improve the peel strength.

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

When the resin composition contains the component (E), from the viewpoint of further improving the ability to form fine circuits and reducing the minimum melt viscosity, the content of the component (E) when the non-volatile content in the resin composition is 100% by mass, Preferably it is 15 mass % or less, More preferably, it is 10 mass % or less, More preferably, it is 5 mass % or less. In addition, the lower limit is not particularly limited, but is preferably 1 mass % or more, more preferably 2 mass % or more, and still more preferably 3 mass % or more.

<(F) Hardening accelerator> In one embodiment, the resin composition may contain (F) hardening accelerator. Examples of the curing accelerator include phosphorus-based curing accelerators, amine-based curing accelerators, imidazole-based curing accelerators, guanidine-based curing accelerators, metal-based curing accelerators, and the like, and preferably phosphorus-based curing accelerators and amine-based curing accelerators agent, imidazole-based curing accelerator, metal-based curing accelerator, more preferably amine-based curing accelerator. A hardening accelerator may be used individually by 1 type, and may be used in combination of 2 or more types.

Phosphorus-based curing accelerators include, for example, triphenylphosphine, phosphonium borate compounds, tetraphenylphosphonium tetraphenylborate, n-butylphosphonium tetraphenylborate, tetrabutylphosphonium decanoate, (4 -methylphenyl) triphenylphosphonium thiocyanate, tetraphenylphosphonium thiocyanate, butyltriphenylphosphonium thiocyanate, etc., preferably triphenylphosphine, tetrabutylphosphonium decanoic acid Salt.

Amine-based hardening accelerators include, for example, trialkylamines such as triethylamine and tributylamine; aminomethyl)phenol, 1,8-diazabicyclo(5,4,0)-undecene, etc., preferably 4-dimethylaminopyridine, 1,8-diazabicyclo( 5,4,0)-undecene.

Examples of imidazole-based curing accelerators include 2-methylimidazole, 2-undecylimidazole, 2-heptadecylimidazole, 1,2-dimethylimidazole, and 2-ethyl-4-methylimidazole , 1,2-dimethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 1-benzyl-2-methylimidazole, 1-Benzyl-2-phenylimidazole, 1-cyanoethyl-2-methylimidazole, 1-cyanoethyl-2-undecylimidazole, 1-cyanoethyl-2-ethyl yl-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-diamine yl-6-[2'-undecylimidazolyl-(1')]-ethyl-s-triazine, 2,4-diamino-6-[2'-ethyl-4'-methyl Imidazolyl-(1')]-ethyl-s-triazine, 2,4-diamino-6-[2'-methylimidazolyl-(1')]-ethyl-s-triazine Isocyanuric acid adduct, 2-phenylimidazole isocyanuric acid adduct, 2-phenyl-4,5-dihydroxymethylimidazole, 2-phenyl-4-methyl-5- Hydroxymethylimidazole, 2,3-Dihydro-1H-pyrrolo[1,2-a]benzimidazole, 1-dodecyl-2-methyl-3-benzylimidazolium chloride, 2 - imidazole compounds such as methylimidazoline, 2-phenylimidazoline, and adducts of imidazole compounds and epoxy resins, preferably 2-ethyl-4-methylimidazole, 1-benzyl-2- Phenylimidazole.

As an imidazole type hardening accelerator, a commercial item can also be used, for example, "P200-H50" by Mitsubishi Chemical Corporation, etc. are mentioned.

Examples of guanidine-based curing accelerators include dicyandiamine, 1-methylguanidine, 1-ethylguanidine, 1-cyclohexylguanidine, 1-phenylguanidine, 1-(o-tolyl)guanidine, and dimethylguanidine. guanidine, diphenylguanidine, trimethylguanidine, tetramethylguanidine, pentamethylguanidine, 1,5,7-triazabicyclo[4.4.0]dec-5-ene, 7-methyl-1 ,5,7-triazabicyclo[4.4.0]dec-5-ene, 1-methyl biguanide, 1-ethyl biguanide, 1-n-butyl biguanide, 1-n-octadecyl biguanide, 1,1-dimethyl biguanide, 1,1-diethyl biguanide, 1-cyclohexyl biguanide, 1-allyl biguanide, 1-phenyl biguanide, 1-(o-tolyl) biguanide, etc., preferably It is dicyandiamide, 1,5,7-triazabicyclo[4.4.0]dec-5-ene.

Examples of the metal-based hardening accelerator include organometallic complexes and organometallic salts of metals such as cobalt, copper, zinc, iron, nickel, manganese, and tin. Specific examples of organometallic complexes include organocobalt complexes such as cobalt(II) acetylacetonate, cobalt(III) acetylacetonate and the like, and organocopper complexes such as copper(II) acetylacetonate. Organo-zinc complexes such as zinc(II) acetylacetonate, organo-iron complexes such as iron(III) acetylacetonate, organo-nickel complexes such as nickel(II) acetylacetonate, Organic manganese complexes such as manganese (II) acetylacetonate, etc. Examples of the organic metal salt include zinc octoate, tin octoate, zinc naphthenate, cobalt naphthenate, tin stearate, zinc stearate, and the like.

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, and still more preferably 100% by mass of the nonvolatile content in the resin composition. 0.1 mass % or more. The upper limit is preferably 3 mass % or less, more preferably 2 mass % or less, and still more preferably 1 mass % or less. By making the content of the hardening accelerator into such a range, the microcircuit forming ability can be further improved and the minimum melt viscosity can be further reduced.

<(G) Thermoplastic resin> In one embodiment, the resin composition may contain (G) thermoplastic resin. However, (G) thermoplastic resin referred to herein does not include (C) polyimide resin.

Thermoplastic resins include, for example, phenoxy resins, polyvinyl acetal resins, polyolefin resins, polybutadiene resins, polyamide imide resins, polysiloxane resins, polyether resins, polyphenylene ether resins, polyamide resins Carbonate resins, polyetheretherketone resins, polyester resins, etc., preferably phenoxy resins. A thermoplastic resin may be used individually by 1 type, or may be used in combination of 2 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, still more 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 can be measured using LC-9A/RID-6A manufactured by Shimadzu Corporation, and Shodex K-800P/K-804L/K manufactured by Showa Denko Corporation. -804L was used as a column, chloroform or the like was used as a mobile phase, the column temperature was set to 40°C, and the calculation was performed using a calibration curve of standard polystyrene.

For example, phenoxy resins having a structure selected from the group consisting of bisphenol A skeleton, bisphenol F skeleton, bisphenol S skeleton, bisphenol acetophenone skeleton, novolak skeleton, biphenyl skeleton, perylene skeleton, dicyclopentadiene skeleton, A phenoxy resin with one or more skeletons of the group consisting of a camphene skeleton, a naphthalene skeleton, 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 and an epoxy group. A phenoxy resin may be used individually by 1 type, and may be used in combination of 2 or more types. Specific examples of phenoxy resins include "1256" and "4250" (both are phenoxy resins containing bisphenol A skeleton), "YX8100" (phenoxy resin containing bisphenol S skeleton) manufactured by Mitsubishi Chemical Corporation, And "YX6954" (phenoxy resin containing bisphenol acetophenone skeleton), others can also include "FX280" and "FX293" manufactured by Nippon Steel & Sumitomo Metal Corporation, "YL7500BH30" and "YX6954BH30" manufactured by Mitsubishi Chemical Corporation , "YX7553", "YX7553BH30", "YL7769BH30", "YL6794", "YL7213", "YL7290" and "YL7482", etc.

Examples of polyvinyl acetal resins include polyvinyl formal resins and polyvinyl butyral resins, and polyvinyl butyral resins are preferred. Specific examples of the polyvinyl acetal resin include "Denka Butyral 4000-2", "Denka Butyral 5000-A", "Denka Butyral 6000-C", "Denka Butyral 6000-EP", S-LEC BH series, BX series (such as BX-5Z), KS series (such as KS-1), BL series, BM series, etc. made by Sekisui Chemical Industry Co., Ltd.

Specific examples of the polyamide imide resin include "Vylomax HR11NN" and "Vylomax HR16NN" manufactured by Toyobo Co., Ltd. Specific examples of the polyamide imide resins include modified polyamide imide resins such as "KS9100" and "KS9300" (polyamide imide containing a polysiloxane skeleton) manufactured by Hitachi Chemical Co., Ltd. amine.

Specific examples of the polyether resin include "PES5003P" manufactured by Sumitomo Chemical Co., Ltd., and the like. Specific examples of the polyphenylene ether resin include vinyl-containing oligophenylene ether/styrene resin "OPE-2St 1200" manufactured by Mitsubishi Gas Chemical Corporation.

Specific examples of the polyresin include polyresin "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 mass % or more, more preferably 0.3 mass % or more, and still more preferably 0.5 mass % when the nonvolatile content in the resin composition is 100 mass %. mass % or more. The upper limit is preferably 10% by mass or less, more preferably 5% by mass or less, and still more preferably 3% by mass.

<(H) Arbitrary additives> In one embodiment, the resin composition may further contain other additives as required. Examples of such other additives include organic phosphorus compounds, organic nitrogen-containing phosphorus compounds, nitrogen compounds, polysiloxanes. Compounds, flame retardants such as metal hydroxides; organic fillers such as rubber particles; organic metal compounds such as organic copper compounds, organic zinc compounds and organic cobalt compounds; tackifiers, defoaming agents, leveling agents, Adhesion imparting agents, resin additives such as colorants, etc.

<Physical properties and applications of resin composition> The resin composition of the present invention can provide an insulating layer (cured product of the resin composition layer) with excellent microcircuit formation ability and low dielectric tangent. Therefore, 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 can be more suitably used as a resin composition for forming a printed wiring board The resin composition of the interlayer insulating layer (the resin composition for the interlayer insulating layer of the printed wiring board). In addition, since the resin composition of the present invention can obtain an insulating layer with good component embedment, it can also be suitably used when the printed wiring board is a component embeddable circuit board.

The cured product obtained by thermally curing the resin composition at 100° C. for 30 minutes and then at 180° C. for 30 minutes exhibits the characteristic of being excellent in the ability to form a fine circuit. That is, an insulating layer excellent in the ability to form a fine circuit can be obtained. Since the ability to form fine circuits is excellent, the minimum L (line: wiring width)/S (gap: space width) is preferably 8 μm/8 μm or less, more preferably 7 μm/7 μm or less, and still more preferably 6 μm/6 μm or less . The lower limit is not particularly limited, and may be 1 μm/1 μm or more. In addition, the minimum wiring pitch is preferably 10 μm or less, more preferably 8 μm or less, and still more preferably 6 μm or less. The lower limit is not particularly limited, and may be 1 μm or more. The microcircuit forming ability can be measured according to the method described in <Measurement of microcircuit forming ability> described later.

The cured product obtained by thermally curing the resin composition at 200° C. for 90 minutes exhibited a low dielectric tangent characteristic. That is, an insulating layer with a low dielectric tangent is obtained. The dielectric tangent is preferably 0.1 or less, more preferably 0.05 or less, and still more preferably 0.015 or less. The lower limit is not particularly limited, and may be 0.0001 or more. The measurement of the dielectric tangent can be performed in accordance with the method described in <Measurement of the dielectric tangent> described later.

From the viewpoint of improving lamination properties, the minimum melt viscosity at 120° C. of the resin composition is preferably 7000 poise or less, more preferably 6000 poise or less, and still more preferably 5000 poise or less. The lower limit is not particularly limited, and may be 100 poise or more. The minimum melt viscosity can be measured according to the method described in the later-mentioned <Evaluation of Lamination Properties>.

Since the resin composition has a low minimum melt viscosity, the embedding property is improved, and as a result, the property of suppressing the generation of voids is exhibited. Even if the resin composition is laminated in a comb-tooth pattern of L/S=160 μm/160 μm, for example, voids are not generated. The presence or absence of voids can be measured in accordance with the method described in <Evaluation of Lamination Properties> described later.

[Resin Sheet] The resin sheet of the present invention comprises a support, and a resin composition layer formed of the resin composition of the present invention provided on the support.

From the viewpoint of thinning the printed wiring board, the thickness of the resin composition layer is preferably 200 μm or less, more preferably 100 μm or less, still more preferably 50 μm or less, still more preferably 20 μm or less, or 15 μm or less, or 10μm or less. The lower limit of the thickness of the resin composition layer is not particularly limited, and it is usually 1 μm or more, 3 μm or more, or the like.

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

When a film made of a plastic material is used as the support, the plastic material includes polyethylene terephthalate (hereinafter abbreviated as "PET"), polyethylene naphthalate (hereinafter abbreviated as "PET"), Polyester such as "PEN"), polycarbonate (hereinafter referred to as "PC"), acrylic resin such as polymethyl methacrylate (PMMA), cyclic polyolefin, triacetate fiber Acetate (TAC), polyether sulfide (PES), polyether ketone, polyimide, etc. Among them, polyethylene terephthalate and polyethylene naphthalate are particularly preferred, and polyethylene terephthalate with low price is particularly preferred.

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

A matte treatment, a corona treatment, and an antistatic treatment may be performed on the surface of the support which is bonded to the resin composition layer.

Moreover, a support body can also be used for the support body with a mold release layer which has a mold release layer on the surface joined to the resin composition layer. For example, the release agent used for the release layer of the release layer-attached support includes at least one selected from the group consisting of alkyd resins, polyolefin resins, urethane resins, and polysiloxane resins. the release agent. Commercially available products may also be used as the support with a release layer, for example, a PET film having a release layer mainly composed of an alkyd resin-based release agent, that is, "SK-1" manufactured by Lintec Co., Ltd. , "AL-5", "AL-7", "Lumirror T60" manufactured by Toray Corporation, "Purex" manufactured by Teijin Corporation, "Unipeel" manufactured by Unitika Corporation, etc.

The thickness of the support is not particularly limited, but is preferably in the range of 5 μm to 75 μm, more preferably in the range of 10 μm to 60 μm. Furthermore, when the support with a mold release layer is used, it is preferable that the thickness of the whole support with a mold release layer is in the above-mentioned range.

In one embodiment, the resin sheet may further include other layers as required. As this other layer, the protective film etc. of the quasi-support provided on the surface (that is, the surface opposite to the support) of the resin composition layer which is not joined to the support, for example, can be mentioned. The thickness of the protective film is not particularly limited, and is, for example, 1 μm to 40 μm. By laminating the 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 produced, for example, by preparing a resin coating obtained by dissolving a resin composition in an organic solvent, applying the resin coating on a support using a die coater or the like, and further drying to form a resin composition layer.

Examples of the organic solvent include ketones such as acetone, methyl ethyl ketone (MEK), and cyclohexanone; ethyl acetate, butyl acetate, celosyl acetate, propylene glycol monomethyl ether acetate, and carbitol Acetates such as alcohol acetates; carbitols such as serosol and butyl carbitol; aromatic hydrocarbons such as toluene and xylene; dimethylformamide, dimethylacetamide (DMAc) and amide-based solvents such as N-methylpyrrolidone and the like. The organic solvent may be used alone or in combination of two or more.

Drying can be carried out by known methods such as heating and hot air blowing. The drying conditions are not particularly limited, but drying is performed so that the content of the organic solvent in the resin composition layer is 10 mass % or less, preferably 5 mass % or less. Although it also depends on the boiling point of the organic solvent in the resin coating, for example, when using a resin coating containing an organic solvent of 30% by mass to 60% by mass, it can be formed by drying at 50° C. to 150° C. for 3 minutes to 10 minutes. resin composition layer.

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

[Printed Wiring Board] The printed wiring board of the present invention includes an insulating layer, a first conductor layer, and a second conductor layer formed of a cured product of the resin composition of the present invention. The insulating layer is provided between the first conductor layer and the second conductor layer, and insulates the first conductor layer and the second conductor layer (there is a conductor layer 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 still more preferably 5 μm or less. The lower limit is not particularly limited, and may be 0.1 μm or more. The distance between the first conductor layer and the second conductor layer (the thickness of the insulating layer between the first and second conductor layers), as shown in FIG. 1, refers to the main surface 11 of the first conductor layer 1 and the second conductor layer 2 The thickness t1 of the insulating layer 3 between the main surfaces 21. The first and second conductor layers are conductor layers adjacent to each other with an insulating layer interposed therebetween, and the main surfaces 11 and 21 are opposed to each other.

Furthermore, the thickness t2 of the entire insulating layer is preferably 15 μm or less, more preferably 13 μm or less, and still more preferably 10 μm or less. The lower limit is not particularly limited, and generally, it may be 1 μm or more, 1.5 μm or more, 2 μm or more, and the like.

A printed wiring board can be manufactured by the method including the steps of the following (I) and (II) using the above-mentioned resin sheet. (I) The step of laminating the resin composition layer of the resin sheet on the inner layer substrate so that the resin composition layer of the resin sheet is bonded to the inner layer substrate (II) The step of thermosetting the resin composition layer to form the insulating layer

The "inner layer substrate" used in the step (I) refers to a member serving as a substrate of a printed wiring board, for example, glass epoxy substrates, metal substrates, polyester substrates, polyimide substrates, BT resin substrates, thermosetting type polyphenylene ether substrate, etc. In addition, the substrate may have a conductor layer on one side or both sides thereof, and the conductor layer may also be patterned. An inner layer substrate in which a conductor layer (circuit) is formed on one side or both sides of the substrate is called an "inner layer circuit substrate". Moreover, when manufacturing a printed wiring board, the intermediate product which intends to further form an insulating layer and/or a conductor layer is also included in the "inner-layer board|substrate" called by this invention. When the printed wiring board is a circuit board with built-in components, an inner-layer substrate with built-in components can be used.

The lamination of the inner layer substrate and the resin sheet can be performed, for example, by thermocompression bonding of the resin sheet to the inner layer substrate from the support side. The member (henceforth "thermocompression bonding member") which thermocompresses a resin sheet to an inner-layer board|substrate is mentioned, for example, a heated metal plate (SUS mirror board etc.), a metal roll (SUS roll), etc. are mentioned. Furthermore, it is preferable to press through an elastic material such as heat-resistant rubber so that the resin sheet is sufficiently attached to the surface unevenness of the inner layer substrate, rather than pressing the thermocompression member directly on the resin sheet.

The lamination of the inner layer substrate and the resin sheet can be carried out by a vacuum lamination method. In the vacuum lamination method, the heating and crimping temperature is preferably in the range of 60℃~160℃, more preferably 80℃~140℃, and the heating and crimping pressure is preferably 0.098MPa~1.77MPa, more preferably 0.29MPa~ In the range of 1.47MPa, the heating and crimping time is preferably in the range of 20 seconds to 400 seconds, and more preferably in the range of 30 seconds to 300 seconds. The lamination is preferably carried out under reduced pressure at a pressure of 26.7 hPa or less.

Lamination can be performed by a commercially available vacuum laminating machine. As a commercially available vacuum laminating machine, a vacuum pressure laminating machine manufactured by Meiki Seisakusho Co., Ltd., a vacuum applicator manufactured by Nikko-Materials Co., Ltd., a batch type vacuum pressure laminating machine, etc. are mentioned, for example.

After lamination, the laminated resin sheet can also be smoothed by pressing the thermocompression-bonding member under normal pressure (at atmospheric pressure), for example, from the support side. The pressing conditions of the smoothing treatment can be set to the same conditions as the thermocompression bonding conditions of the above-mentioned laminate. The smoothing process can be performed by a commercially available laminator. In addition, the lamination and smoothing process can also be performed continuously using the said commercially available vacuum laminating machine.

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

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

The thermosetting conditions of the resin composition layer are not particularly limited, and conditions generally employed when forming an insulating layer of a printed wiring board can be used.

For example, the thermal curing conditions of the resin composition layer vary depending on the type of the resin composition, and the curing temperature can be in the range of 120°C to 240°C (preferably in the range of 150°C to 220°C, more preferably 170°C). ~200°C range), and the hardening time may 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 pre-heated at a temperature lower than the curing temperature. For example, before thermally curing the resin composition layer, the resin can be heated 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). The composition layer is preliminarily heated for 5 minutes or more (preferably 5 minutes to 150 minutes, more preferably 15 minutes to 120 minutes, and still more preferably 15 minutes to 100 minutes).

When manufacturing a printed wiring board, (III) the step of opening a hole to the insulating layer, (IV) the step of roughening the insulating layer, and (V) the step of forming the conductor layer may be further performed. These steps (III) to (V) can be implemented in accordance with various methods known to those skilled in the art in accordance with those used in the manufacture of printed wiring boards. Furthermore, when removing the support after step (II), the removal of the support can be between step (II) and step (III), between step (III) and step (IV), or between step (IV) ) and step (V). In addition, the formation of the insulating layer and the conductor layer in steps (II) to (V) may be repeated as necessary to form a multilayer wiring board. At this time, the thickness of the insulating layer between the respective conductor layers (t1 in FIG. 1 ) is preferably within the above-mentioned range.

The step (III) is a step of opening the insulating layer, whereby holes such as via holes and through holes can be formed in the insulating layer. The step (III) can be implemented by, for example, using a drill, laser, plasma, etc., depending on the composition of the resin composition used for forming the insulating layer. The size or shape of the holes can be appropriately determined according to the design of the printed wiring board.

Step (IV) is a step of roughening the insulating layer. The order and conditions of the roughening treatment are not particularly limited, and well-known procedures and conditions generally used when forming an insulating layer of a printed wiring board can be adopted. For example, a swelling treatment with a swelling liquid, a roughening treatment with an oxidizing agent, and a neutralization treatment with a neutralizing liquid can be sequentially performed to roughen the insulating layer. The swelling liquid used for the roughening treatment is not particularly limited, and examples thereof include an alkaline solution, a surfactant solution, and the like, and an alkaline solution is preferred, and the alkaline solution is more preferably a sodium hydroxide solution and a potassium hydroxide solution. Examples of commercially available swelling liquids include "Swelling Dip Securiganth P" and "Swelling Dip Securiganth SBU" manufactured by Atotech Japan. The swelling treatment with the swelling liquid is not particularly limited, and for example, it can be performed by immersing the insulating layer in the swelling liquid at 30° C. to 90° C. for 1 minute to 20 minutes. From the viewpoint of suppressing the resin swelling of the insulating layer to an appropriate level, it is preferable to immerse the insulating layer in a swelling liquid at 40° C. to 80° C. for 5 minutes to 15 minutes. The oxidizing agent used for the roughening treatment is not particularly limited, and for example, an alkaline permanganic acid solution in which potassium permanganate or sodium permanganate is dissolved in an aqueous solution of sodium hydroxide can be mentioned. The roughening treatment with an oxidizing agent such as an alkaline permanganic acid solution is preferably performed by immersing the insulating layer in an oxidizing agent solution heated to 60° C. to 80° C. for 10 minutes to 30 minutes. In addition, the concentration of the permanganate in the alkaline permanganic acid solution is preferably 5% by mass to 10% by mass. Examples of commercially available oxidizing agents include alkaline permanganic acid solutions such as "Concentrate Compact CP" and "Dosing Solution Securiganth P" manufactured by Atotech Japan. In addition, the neutralizing liquid used for the roughening treatment is preferably an acidic aqueous solution, and as a commercial product, for example, "Reduction Solution Securiganth P" manufactured by Atotech Japan can be mentioned. The treatment with the neutralizing solution can be performed by immersing the treated surface roughened by the oxidizing agent in the neutralizing solution at 30° C. to 80° C. for 5 minutes to 30 minutes. From the viewpoint of workability and the like, a method of immersing the object subjected to the roughening treatment of the oxidizing agent in the neutralizing liquid at 40° C. to 70° C. for 5 minutes to 20 minutes is preferable.

In one embodiment, the arithmetic mean roughness (Ra) of the surface of the insulating layer after the roughening treatment is preferably 400 nm or less, more preferably 350 nm or less, and still more preferably 300 nm or less. The lower limit is not particularly limited, but preferably 0.5 nm or more, more preferably 1 nm or more, or the like. 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 still more preferably 300 nm or less. The lower limit is not particularly limited, but preferably 0.5 nm or more, more preferably 1 nm or more, or the like. The arithmetic mean roughness (Ra) and the root mean square roughness (Rq) of the surface of the insulating layer can be measured using a non-contact surface roughness meter.

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

The conductor material used for the conductor layer is not particularly limited. In a suitable embodiment, the conductor layer contains at least one selected from the group consisting of gold, platinum, palladium, silver, copper, aluminum, cobalt, chromium, zinc, nickel, titanium, tungsten, iron, tin, and indium. Metal. The conductor layer may be a single metal layer or an alloy layer, and the alloy layer may be formed of, for example, an alloy of two or more metals selected from the above group (eg, nickel/chromium alloy, copper/nickel alloy, and copper/titanium alloy). layer. Among them, from the viewpoints of the versatility, cost, and ease of patterning of the conductor layer formation, especially a single metal layer of chromium, nickel, titanium, aluminum, zinc, gold, palladium, silver or copper, or nickel/ Alloy layer of chromium alloy, copper/nickel alloy, copper/titanium alloy is preferred; more preferably a single metal layer of chromium, nickel, titanium, aluminum, zinc, gold, palladium, silver or copper, or alloy of nickel/chromium alloy layer; more preferably a single metal layer of copper.

The conductor layer may be a single-layer structure, or may be a multi-layer structure in which a single metal layer or an alloy layer composed of different kinds of metals or alloys is laminated with two or more layers. When the conductor layer is a multi-layer structure, the layer adjacent to the insulating layer is preferably a single metal layer of chromium, zinc or titanium, or an alloy layer of nickel/chromium alloy.

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

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

First, a plating seed layer is formed on the surface of the insulating layer by electroless plating. Next, on the formed plating seed layer, a mask pattern for exposing a part of the plating seed layer is formed in accordance with a desired wiring pattern. On the exposed plating seed layer, after forming a metal layer by electrolytic plating, the mask pattern is removed. After that, the unnecessary plating seed layer is removed by etching or the like, and a conductor layer having a desired wiring pattern can be formed.

Since the resin sheet of the present invention can obtain an insulating layer with good parts embeddability, even when the printed wiring board is a part embeddable circuit board, it can be suitably used. The component-embedded circuit board can be manufactured by a known manufacturing method.

The printed wiring board manufactured using the resin sheet of the present invention may be an insulating layer including 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 supplied to electrical products (eg, computers, mobile phones, digital cameras, televisions, etc.) and vehicles (eg, locomotives, automobiles, trains, ships, aircraft, etc.).

The semiconductor device of the present invention can be manufactured by assembling a component (semiconductor chip) on a conductive portion of a printed wiring board. "Conduction part" refers to "a part in the printed wiring board that conducts electrical signals", and the place may be either a surface or a buried part. In addition, the semiconductor wafer is not particularly limited as long as it is a circuit element using a semiconductor as a material.

There is no particular limitation on the method for mounting a semiconductor wafer when manufacturing a semiconductor device, as long as the semiconductor wafer functions effectively. Specifically, there are wire bonding mounting methods, flip-chip mounting methods, and bumpless build-up methods. The packaging method of layer (BBUL), the packaging method of anisotropic conductive film (ACF), the packaging method of non-conductive film (NCF), etc. Here, "the mounting method using a bumpless build-up layer (BBUL)" means "the semiconductor chip is directly embedded in the concave portion of the printed wiring board, and the semiconductor chip is connected to the wiring on the printed wiring board. method of construction". [Example]

Hereinafter, the present invention will be specifically described by way of examples. However, the present invention is not limited to these embodiments. In addition, the following "part" and "%" indicating the amount mean "part by mass" and "% by mass", respectively, unless otherwise specified.

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

<Measurement of Microcircuit Formability> (Preparation of samples for measurement) (1) Substrate treatment of inner-layer circuit substrate Preparation of glass cloth base material with inner-layer circuit formed Epoxy resin double-sided copper-clad laminate (thickness of copper foil: 18 μm) , The thickness of the substrate is 0.8mm, "R1766" manufactured by Panasonic Corporation) was used as an inner layer circuit substrate, and both sides were immersed in "CZ8101" manufactured by MEC Corporation, and the copper surface was roughened (copper etching amount: 1.0μm).

(2) Lamination of resin sheets The resin sheets with a thickness of 10 μm of the resin composition layers prepared in the examples and comparative examples were laminated using a batch vacuum pressure laminating machine (manufactured by Nikko-Materials, Inc., two-step build-up layer). Machine, CVP700), and lamination processing is performed on both sides of the inner-layer circuit board so that the resin composition layer is bonded to the inner-layer circuit board. The lamination process was carried out by reducing the pressure for 30 seconds to make the air pressure 13 hPa or less, and then performing pressure bonding at 100° C. and a pressure of 0.74 MPa for 30 seconds. Next, hot pressing was performed at 100° C. and a pressure of 0.5 MPa for 60 seconds.

(3) Curing of the resin composition layer After the resin sheets are laminated, the resin composition layer is thermally cured at 100°C for 30 minutes and then at 180°C for 30 minutes to form an insulating layer. After that, the support is peeled off to expose the insulating layer.

(4) Roughening treatment The substrate with the exposed insulating layer was immersed in a swelling solution (“Swelling Dip Securiganth P” manufactured by Atotech Japan, an aqueous sodium hydroxide solution containing diethylene glycol monobutyl ether) at 60°C for 10 minutes, Next, it was immersed in an oxidizing agent (“Concentrate Compact CP” manufactured by Atotech Japan, an aqueous solution with a potassium permanganate concentration of about 6 mass % and a sodium hydroxide concentration of about 4 mass %) at 80° C. for 20 minutes, and finally in a neutralizing solution (Atotech Japan "Reduction Solution Securiganth P" manufactured by the company, a hydroxylamine sulfate aqueous solution) was immersed at 40°C for 5 minutes. Then, it dried at 80 degreeC for 15 minutes. The obtained board|substrate is called "substrate a".

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

1. Alkaline cleaning (cleaning and charge adjustment of the surface of the insulating layer provided with through holes) The surface of the substrate a was cleaned with Cleaning Cleaner Securiganth 902 (trade name) at 60°C for 5 minutes. 2. Soft etching (cleaning in the through hole) The surface of the substrate a is treated with a sulfuric acid acid sodium peroxodisulfate aqueous solution at 30°C for 1 minute. 3. Pre-impregnation (adjustment of the electric charge on the surface of the insulating layer of Pd) The surface of the substrate a was treated with Pre. Dip Neoganth B (trade name) at room temperature for 1 minute. 4. Activator application (Pd application to the surface of the insulating layer) The surface of the substrate a was treated with Activator Neoganth 834 (trade name) at 35°C for 5 minutes. 5. Reduction (reduction of Pd applied to the insulating layer) The surface of the substrate a was treated with a mixed solution of Reducer Neoganth WA (trade name) and Reducer Acceralator 810 mod. (trade name) at 30°C for 5 minutes. 6. Step of electroless copper plating (precipitating Cu on the surface of the insulating layer (Pd surface)) The surface of the substrate a, using Basic Solution Printganth MSK-DK (trade name), Copper solution Printganth MSK (trade name), Stabilizer Printganth The mixed solution of MSK-DK (trade name) and Reducer Cu (trade name) was treated at 35°C for 30 minutes. The thickness of the formed electroless copper plating layer was 1 μm.

(6) Formation of wiring pattern After electroless plating, the surface of the substrate was treated with a 5% aqueous sulfuric acid solution for 30 seconds. Next, a dry film for pattern formation (“Photoc RY-3600” manufactured by Hitachi Chemical Co., Ltd., thickness 19 μm) was laminated on a substrate using a batch vacuum pressure bonding machine (“MVLP-500” manufactured by Meiki Seisakusho Co., Ltd.). both sides. The lamination system was depressurized for 30 seconds to make the air pressure 13 hPa or less, and then pressurized at 70° C. and a pressure of 0.1 MPa for 20 seconds.

Then, a glass mask (photomask) with a wiring pattern (details shown below) formed thereon was placed on the dry film, and light was irradiated with a projection exposure machine ("UX-2240" manufactured by USHIO Electric Co., Ltd.). Next, a 1% sodium carbonate aqueous solution at 30°C was sprayed for 30 seconds at a spray pressure of 0.15 MPa. After that, development (pattern formation) is performed by washing with water.

Wiring pattern of glass mask: Use glass masks each having 10 comb patterns of the following i) to vii). i) L/S=2μm/2μm, that is, a comb pattern with a wiring spacing of 4μm (wiring length 15mm, 16 lines) ii) L/S=3μm/3μm, that is, a comb pattern with a wiring spacing of 6μm (wiring Length 15mm, 16 lines) iii) L/S=4μm/4μm, that is, a comb pattern with a wiring spacing of 8μm (wiring length 15mm, 16 lines) iv) L/S=5μm/5μm, that is, a wiring spacing of 10μm Comb pattern (wiring length 15mm, 16 lines) v) L/S=6μm/6μm, that is, comb pattern with a wiring spacing of 12μm (wiring length 15mm, 16 lines) vi) L/S=7μm/7μm, That is, a comb pattern with a wiring spacing of 14μm (wiring length 15mm, 16 lines) vii) L/S=8μm/8μm, that is, a comb pattern with a wiring spacing of 16μm (wiring length 15mm, 16 lines)

After the development, electrolytic copper plating was performed to form an electrolytic copper plating layer (conductor layer) with a thickness of 5 μm (the total thickness with the electroless copper plating layer was about 6 μm).

Next, a 3% sodium hydroxide solution at 50° C. was sprayed at a spray pressure of 0.2 MPa, and the dry film was peeled off from both sides of the substrate. After heating at 190°C for 60 minutes for annealing treatment, an etchant for flush etching (etchant for SAC process manufactured by Ebara Denki Co., Ltd.) was used to remove the unnecessary conductor layer (copper layer) to form a circuit. The obtained board|substrate is called "evaluation board|substrate A".

(7) Evaluation of fine circuit formation capability For the comb-tooth patterns of the above-mentioned i) to vii) of the evaluation substrate A, the presence or absence of circuit peeling was confirmed by an optical microscope, and the insulation resistance of the comb-tooth pattern was measured to confirm whether or not unnecessary Residues of electroless copper plating. Then, out of 10 comb patterns, 9 or more without any problem were judged as acceptable. The ability to form a fine circuit is evaluated by the minimum L/S ratio and the wiring pitch that are judged to be acceptable. In this evaluation, the smaller the minimum L/S ratio and the wiring pitch judged to be acceptable, the better the fine circuit forming ability.

<Evaluation of Lamination Properties> (Measurement of Minimum Melt Viscosity) The minimum melt viscosity was measured using a dynamic viscoelasticity measuring apparatus (“Rheosol-G3000” manufactured by UBM Corporation) for the resin composition layer (thickness of 25 μm) of the prefabricated resin sheet. For 1 g of the sample resin composition, using a parallel plate with a diameter of 18 mm, the temperature was increased from an initial temperature of 60 °C to 200 °C at a heating rate of 5 °C/min, and the dynamics were measured under the measurement conditions of a measurement temperature interval of 2.5 °C, vibration of 1 Hz, and deformation of 5 degrees. Viscoelastic modulus, measured at 120°C melt viscosity.

(Evaluation of the presence or absence of voids) The resin composition layer produced in the Examples and Comparative Examples was 25 μm in thickness and 240×320 mm ² in area, using a batch vacuum press lamination machine (manufactured by Nikko-Materials Co., Ltd., 2-step build-up laminating machine, CVP700), laminated on the comb pattern (thickness 18μm) of L (line: wiring width)/S (gap: space width) = 160μm/160μm. The lamination was performed by reducing the pressure for 30 seconds to make the air pressure 13 hPa or less, and then pressing at 100° C. for 30 seconds at a pressure of 0.74 MPa. Next, hot pressing was performed at 100° C. and a pressure of 0.5 MPa for 60 seconds. It was confirmed whether or not air entered after lamination to generate pores (voids) in the resin composition layer. The case where no voids were formed after the lamination was determined as "○", and the case where voids were generated was determined as "x".

<Measurement of dielectric tangent> A resin sheet with 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 thermally harden the resin composition layer, and then the support was peeled off to obtain a test piece for evaluation. hardened material. The cured product for evaluation was cut into test pieces of 2 mm in width and 80 mm in length. For this test piece, "HP8362B" manufactured by Agilent Technologies was used, and the dielectric tangent was measured by the cavity resonance perturbation method at a measurement frequency of 5.8 GHz and a measurement temperature of 23°C. Two test pieces were measured, and the average value was calculated.

<Synthesis Example 1: Synthesis of Polyimide Resin 1> A 500 mL separable flask equipped with a moisture measuring receiver connected to a reflux condenser, a nitrogen introduction pipe, and a stirrer was prepared. To this flask were added 20.3 g of 4,4'-oxydiphthalic anhydride (ODPA), 200 g of γ-butyrolactone, 20 g of toluene, and 5-(4-aminophenoxy)-3-[ 29.6 g of 4-(4-aminophenoxy)phenyl]-1,1,3-trimethylindenane was stirred at 45° C. for 2 hours under a nitrogen stream to react.

Next, this reaction solution was heated up, and, while maintaining at about 160 degreeC, the condensation water was azeotropically removed with toluene under nitrogen flow. It was confirmed that a specific amount of water was accumulated in the moisture metering receiver, and the outflow of water was not seen. After the confirmation, the temperature of the reaction solution was further increased, and the mixture was stirred at 200° C. for 1 hour. Then, it cooled and obtained the coating material containing the polyimide resin (polyimide resin 1) which has 20 mass % of 1,1,3- trimethylindanane skeletons. The obtained polyimide resin 1 has a repeating unit represented by the following formula (X1) and a repeating unit represented by (X2). Moreover, the weight average molecular weight of the polyimide resin 1 was 12,000.

<Synthesis Example 2: Synthesis of Polyimide Resin 2> In Synthesis Example 1, 5-(4-aminophenoxy)-3-[4-(4-aminophenoxy)phenyl]- 29.6 g of 1,1,3-trimethylindenane was changed to 22.9 g of 9,9-bis(4-aminophenyl)pyrene. Except for the above matters, in the same manner as in Synthesis Example 1, a coating material containing 20% by mass of a polyimide resin having a stilbene skeleton (polyimide resin 2) was obtained. The obtained polyimide resin 2 has a repeating unit represented by the following formula (X3) and a repeating unit represented by the aforementioned formula (X2). Moreover, the weight average molecular weight of the polyimide resin 2 was 14,000.

<Synthesis Example 3: Synthesis of Polyimide Resin 3> In a reaction vessel equipped with a stirrer, a water separator, a thermometer, and a nitrogen gas introduction pipe, an aromatic tetracarboxylic dianhydride ("BisDA-1000" manufactured by SABIC JAPAN Co., Ltd. ) 65.0 g, 266.5 g of cyclohexanone, and 44.4 g of methylcyclohexane were fed, and the solution was heated to 60°C. Next, after dropping 43.7 g of dimer diamine (“PRIAMINE 1075” manufactured by Croda Japan) and 5.4 g of 1,3-bisaminomethylcyclohexane, imidization reaction was performed at 140° C. for 1 hour. . Thereby, the coating material (polyimide resin 3, nonvolatile matter 30 mass %) containing dimer diamine polyimide resin was obtained. Moreover, the weight average molecular weight of the polyimide resin 3 was 25,000.

<Example 1> 30 parts of bisphenol A epoxy resin ("828US" manufactured by Mitsubishi Chemical Corporation, epoxy equivalent of about 180), biphenyl type epoxy resin ("NC3000H" manufactured by Nippon Kayaku Co., Ltd., epoxy equivalent About 269) 30 parts, stir in a mixed solvent of 40 parts of solvent naphtha and 15 parts of cyclohexanone while heating to dissolve, and then cooled to room temperature. In this mixed solution, spherical silica (average particle size 0.078 μm, specific surface area 30.7 m ² /g, Denki Chemical Industry Co., Ltd.) surface-treated with an aminosilane-based coupling agent (“KBM573” manufactured by Shin-Etsu Chemical Co., Ltd.) was mixed. "UFP-30") 100 parts, a phenol-based hardener containing a triazine skeleton ("LA-3018-50P" manufactured by DIC Corporation, hydroxyl equivalent of about 151, 50% solid content in 2-methoxypropanol solution) 14 parts, 40 parts of active ester-based hardener ("HPC-8000-65T" manufactured by DIC Corporation, toluene solution with an active group equivalent of about 223, and a nonvolatile content of 65% by mass), containing polyimide synthesized in Synthesis Example 1 Resin 1 paint (20 mass % solid content of γ-butyrolactone solution) 25 parts, hardening accelerator ("DMAP", 4-dimethylaminopyridine, 5 mass % solid content of methyl ethyl ketone ( Hereinafter abbreviated as "MEK") 6 parts of solution) were uniformly dispersed with a high-speed rotary mixer to prepare Resin Paint 1.

Two alkyd resin-based release layer-attached PET films ("AL5" manufactured by Lintec Co., Ltd., thickness 38 μm) were prepared as supports. The resin coating 1 was uniformly coated on the mold release layer of each support so that the thickness of the resin composition layer after drying was 10 μm and 25 μm, and dried at 70 to 95° C. for 2 minutes to prepare a resin sheet 1 .

<Example 2> In Example 1, the amount of the coating material (γ-butyrolactone solution with a solid content of 20 mass %) containing the polyimide resin 1 synthesized in Synthesis Example 1 was changed from 25 parts to 15 parts. Except for the above-mentioned matters, the resin paint 2 and the resin sheet 2 were produced in the same manner as in Example 1.

<Example 3> In Example 1, the amount of the coating material (γ-butyrolactone solution with a solid content of 20 mass %) containing the polyimide resin 1 synthesized in Synthesis Example 1 was changed from 25 parts to 5 parts. Except for the above-mentioned matters, the resin paint 3 and the resin sheet 3 were produced in the same manner as in Example 1.

<Example 4> In Example 1, 25 parts of the paint containing polyimide resin 1 synthesized in Synthesis Example 1 (γ-butyrolactone solution with a solid content of 20% by mass) was changed to that synthesized in Synthesis Example 2. 15 parts of the coating material containing polyimide resin 2 (20 mass % solid content of γ-butyrolactone solution). Except for the above-mentioned matters, the resin paint 4 and the resin sheet 4 were produced in the same manner as in Example 1.

<Example 5> In Example 1, 25 parts of the paint containing polyimide resin 1 synthesized in Synthesis Example 1 (γ-butyrolactone solution with a solid content of 20% by mass) was changed to that synthesized in Synthesis Example 3. 10 parts of paint containing polyimide resin 3 (a mixed solution of cyclohexanone and methylcyclohexane with a solid content of 30% by mass). Except for the above-mentioned matters, the resin paint 5 and the resin sheet 5 were produced in the same manner as in Example 1.

<Comparative Example 1> In Example 1, the amount of the coating material (γ-butyrolactone solution with a solid content of 20 mass %) containing the polyimide resin 1 synthesized in Synthesis Example 1 was changed from 25 parts to 50 parts. Except for the above-mentioned matters, the resin paint 6 and the resin sheet 6 were produced in the same manner as in Example 1.

<Comparative Example 2> In Example 1, 25 parts of the paint containing polyimide resin 1 synthesized in Synthesis Example 1 (γ-butyrolactone solution with a solid content of 20% by mass) was changed to the one synthesized in Synthesis Example 2. 50 parts of the paint containing polyimide resin 2 (γ-butyrolactone solution with a solid content of 20% by mass). Except for the above-mentioned matters, the resin paint 7 and the resin sheet 7 were produced in the same manner as in Example 1.

<Comparative Example 3> In Example 1, 25 parts of the paint containing polyimide resin 1 synthesized in Synthesis Example 1 (γ-butyrolactone solution with a solid content of 20% by mass) was changed to the one synthesized in Synthesis Example 3. 33 parts of paint containing polyimide resin 3 (a mixed solution of cyclohexanone and methylcyclohexane with a solid content of 30% by mass). Except for the above-mentioned matters, the resin paint 8 and the resin sheet 8 were produced in the same manner as in Example 1.

<Comparative Example 4> In Example 1, 25 parts of the paint containing polyimide resin 1 synthesized in Synthesis Example 1 (γ-butyrolactone solution with a solid content of 20% by mass) was changed to a phenoxy resin (Mitsubishi resin). 10 parts of "YX6954BH30" manufactured by a chemical company, a 1:1 solution of MEK and cyclohexanone with a solid content of 30% by mass. Except for the above-mentioned matters, the resin paint 9 and the resin sheet 9 were produced in the same manner as in Example 1.

The components used for the preparation of the resin compositions 1 to 9 and their blending amounts (in terms of nonvolatile components) are shown in the following table. In addition, in the following table, "(C) component content (mass %)" refers to the (C) component content when the resin component in the resin composition is 100 mass %, "(D) component content. (mass %)" means the content of (D) component when the nonvolatile matter in the resin composition is taken as 100 mass %.

It was confirmed that in Examples 1 to 5, even though the components (E) to (F) were not contained, the same results as those of the above-mentioned Examples were returned, although the degree was poor.

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‧‧‧First The distance between the conductor layer and the second conductor layer (the thickness of the insulating layer between the first and second conductor layers) t2‧‧‧Thickness of the entire insulating layer

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

Claims (18)

A resin composition comprising (A) an epoxy resin, (B) an active ester-based hardener, (C) a polyimide resin, and (D) a resin composition of an inorganic filler, wherein (D) component The average particle diameter is 100 nm or less, and when the resin component is 100 mass %, the content of the (C) component is 0.1 mass % or more and 6 mass % or less. A resin composition, which is a resin composition containing (A) epoxy resin, (B) active ester hardener, (C) polyimide resin, and (D) inorganic filler, wherein (D) component The specific surface area is 15 m ² /g or more, and the content of the (C) component is 0.1 mass % or more and 6 mass % or less when the resin component is 100 mass %. The resin composition according to claim 1 or 2, wherein the component (C) is a polyimide resin having a polycyclic aromatic hydrocarbon skeleton. The resin composition of claim 3, wherein the polycyclic aromatic hydrocarbon skeleton is an aromatic hydrocarbon skeleton obtained by condensation of a 5-membered ring compound and an aromatic ring. The resin composition according to claim 3, wherein the polycyclic aromatic hydrocarbon skeleton is at least any one of an indenane skeleton and a perylene skeleton. The resin composition according to claim 1 or 2, wherein the weight-average molecular weight of component (C) is 5,000 or more. The resin composition of claim 1 or 2, wherein the component (C) has a repeating unit having a polycyclic aromatic hydrocarbon skeleton and a repeating unit having an imide structure. The resin composition of claim 7, wherein the mass ratio of the repeating unit having a polycyclic aromatic hydrocarbon skeleton to the repeating unit having an imide structure (mass of the repeating unit having a polycyclic aromatic hydrocarbon skeleton/having an amide) The mass of the repeating unit of the imine structure) is 0.5 or more and 2 or less. The resin composition according to claim 1 or 2, wherein the content of component (C) is 0.1 mass % or more and 3 mass % or less when the non-volatile content in the resin composition is 100 mass %. The resin composition according to claim 1 or 2, wherein the content of component (B) is 1 mass % or more and 25 mass % or less when the non-volatile content in the resin composition is 100 mass %. The resin composition of claim 1 or 2, wherein the content of component (D) is 30 mass % or more and 80 mass % or less when the non-volatile content in the resin composition is 100 mass %. The resin composition according to claim 1 or 2, which further contains (E) a hardener. The resin composition of claim 12, wherein (E) the hardener is a phenol-based hardener. The resin composition according to claim 1 or 2, which is used for forming an insulating layer of a printed wiring board. The resin composition according to claim 1 or 2, which is for forming an interlayer insulating layer between printed wiring boards. A resin sheet, comprising a support, and a resin composition layer according to any one of claims 1 to 15 disposed 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, wherein the insulating layer is as claimed in item 1 to A hardened product of the resin composition according to any one of 15. A semiconductor device comprising the printed wiring board of claim 17.

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