JP7176551B2 - Resin composition, adhesive film, prepreg, printed wiring board and semiconductor device - Google Patents

Description

TECHNICAL FIELD The present invention relates to a resin composition, and an adhesive film, prepreg, printed wiring board and semiconductor device obtained using the resin composition.

2. Description of the Related Art As a technique for manufacturing a printed wiring board, a manufacturing method using a build-up method in which insulating layers and conductor layers are alternately stacked is known. In the build-up manufacturing method, the insulating layer is generally formed by curing a resin composition. This resin composition has been studied in the past. For example, Patent Document 1 includes (A) an epoxy resin, (B) an active ester compound, (C) a carbodiimide compound, (D) a thermoplastic resin and (E) an inorganic filler, and the content of the (E) component However, when the non-volatile component in the resin composition is taken as 100% by mass, a resin composition is disclosed in which the content is 40% by mass or more.

JP 2016-27097 A

However, it is desired to further improve the performance of the insulating layer. In particular, there is a demand for the development of a technique capable of realizing an insulating layer having a low dielectric loss tangent and high adhesion to a conductor layer by using a resin composition having a minimum melt viscosity within an appropriate range.

The present invention has been invented in view of the above problems, and provides an insulating layer having a low dielectric loss tangent and high adhesion to a conductor layer, and a resin composition having a minimum melt viscosity within an appropriate range; An object of the present invention is to provide an adhesive film and a prepreg containing the resin composition; and a printed wiring board and a semiconductor device containing a cured product of the resin composition.

As a result of intensive studies on the above problems, the present inventors have found that the above problems can be solved by a resin composition containing (A) an epoxy resin, (B) an active ester compound, and (C) a polyimide resin having an indane skeleton. This led to the completion of the present invention.
That is, the present invention includes the following contents.

[1] A resin composition containing (A) an epoxy resin, (B) an active ester compound, and (C) a polyimide resin having an indane skeleton.
[2] The resin composition of [1], wherein the component (C) has a trimethylindane skeleton.
[3] The resin composition according to [1] or [2], wherein the component (C) has a 1,1,3-trimethylindane skeleton.
[4] The amount of component (C) is 1% by mass to 20% by mass with respect to 100% by mass of the resin component in the resin composition, [1] to [3]. Resin composition.
[5] The resin composition according to any one of [1] to [4], which contains (D) an inorganic filler.
[6] The resin composition according to [5], wherein the amount of component (D) is 50% by mass or more with respect to 100% by mass of non-volatile components in the resin composition.
[7] The resin composition according to any one of [1] to [6], which is a resin composition for forming an insulating layer of a printed wiring board.
[8] An adhesive film comprising a support and a resin composition layer containing the resin composition according to any one of [1] to [7] provided on the support.
[9] A prepreg comprising a sheet-like fiber base material and the resin composition according to any one of [1] to [7] impregnated in the sheet-like fiber base material.
[10] A printed wiring board having an insulating layer containing a cured product of the resin composition according to any one of [1] to [7].
[11] A semiconductor device comprising the printed wiring board according to [10].

According to the present invention, an insulating layer having a low dielectric loss tangent and high adhesion to a conductor layer can be obtained, and a resin composition having a minimum melt viscosity in an appropriate range; an adhesive film containing the resin composition; A prepreg; and a printed wiring board and a semiconductor device containing a cured product of the resin composition can be realized.

Hereinafter, the present invention will be described in detail by showing embodiments and examples. However, the present invention is not limited to the following embodiments and examples, and can be arbitrarily modified without departing from the scope of the claims of the present invention and their equivalents.

In the following description, the amount of each component in the resin composition is a value relative to 100% by mass of non-volatile components in the resin composition, unless otherwise specified.

In the following description, the "resin component" of the resin composition refers to the non-volatile component contained in the resin composition, excluding (D) the inorganic filler.

[1. Overview of resin composition]
The resin composition of the present invention contains (A) an epoxy resin, (B) an active ester compound, and (C) a polyimide resin having an indane skeleton. In the following description, "polyimide resin having an indane skeleton" may be referred to as "indane polyimide resin". This resin composition is suitable as a resin composition for forming an insulating layer of a printed wiring board. have. By using this resin composition, an insulating layer having a low dielectric loss tangent and high adhesion to the conductor layer can be obtained.

[2. (A) Epoxy resin]
(A) Epoxy resins include, for example, bixylenol type epoxy resins, bisphenol A type epoxy resins, bisphenol F type epoxy resins, bisphenol S type epoxy resins, bisphenol AF type epoxy resins, dicyclopentadiene type epoxy resins, and trisphenol type epoxy resins. Epoxy resin, naphthol novolac type epoxy resin, phenol novolac type epoxy resin, tert-butyl-catechol type epoxy resin, naphthalene type epoxy resin, naphthol type epoxy resin, anthracene type epoxy resin, glycidylamine type epoxy resin, glycidyl ester type epoxy resin , cresol novolak type epoxy resin, biphenyl type epoxy resin, linear aliphatic epoxy resin, epoxy resin having a butadiene structure, alicyclic epoxy resin, heterocyclic epoxy resin, spiro ring-containing epoxy resin, cyclohexanedimethanol type epoxy resin , naphthylene ether type epoxy resin, trimethylol type epoxy resin, tetraphenylethane type epoxy resin and the like.

Among these, (A) the epoxy resin is preferably an epoxy resin containing an aromatic skeleton from the viewpoint of reducing the average coefficient of linear thermal expansion. Here, an aromatic backbone is a chemical structure generally defined as aromatic, including polycyclic aromatic and heteroaromatic rings. Specifically, one or more epoxy resins selected from the group consisting of bisphenol A-type epoxy resins, bisphenol F-type epoxy resins, naphthalene-type epoxy resins, biphenyl-type epoxy resins, and dicyclopentadiene-type epoxy resins are preferable. Biphenyl-type epoxy resins are more preferred.

Moreover, the resin composition preferably contains an epoxy resin having two or more epoxy groups in one molecule as (A) the epoxy resin. (A) The proportion of the epoxy resin having two or more epoxy groups in one molecule is preferably 50% by mass or more, more preferably 60% by mass or more, and particularly preferably 100% by mass of the non-volatile components of the epoxy resin. is 70% by mass or more. Among them, the resin composition has, as (A) epoxy resin, an epoxy resin that has three or more epoxy groups in one molecule and is solid at a temperature of 20° C. (hereinafter sometimes referred to as “solid epoxy resin”). .) is preferably included.

(A) Epoxy resins may be used singly or in combination of two or more at any ratio. Therefore, the resin composition may contain only a solid epoxy resin as (A) the epoxy resin, or may contain a combination of the solid epoxy resin and other epoxy resins. Among them, the resin composition has (A) an epoxy resin, a solid epoxy resin, and an epoxy resin having two or more epoxy groups in one molecule and being liquid at a temperature of 20° C. (hereinafter referred to as “liquid epoxy resin”). may be referred to.) in combination. By using a combination of a liquid epoxy resin and a solid epoxy resin as the epoxy resin (A), the flexibility of the resin composition can be improved, and the breaking strength of the cured product of the resin composition can be improved.

Examples of liquid epoxy resins include bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol AF type epoxy resin, naphthalene type epoxy resin, glycidyl ester type epoxy resin, glycidyl amine type epoxy resin, phenol novolak type epoxy resin, ester skeleton. An alicyclic epoxy resin having a type epoxy resins and naphthalene type epoxy resins are more preferred.

Specific examples of liquid epoxy resins include "HP4032", "HP4032D", and "HP4032SS" (naphthalene-type epoxy resins) manufactured by DIC; 828EL" (bisphenol A type epoxy resin); Mitsubishi Chemical Corporation "jER807", "1750" (bisphenol F type epoxy resin); Mitsubishi Chemical Corporation "jER152" (phenol novolac type epoxy resin); Mitsubishi Chemical Corporation "630", "630LSD" (glycidylamine type epoxy resin); "630LSD" (glycidylamine type epoxy resin) manufactured by Mitsubishi Chemical Corporation; "ZX1059" manufactured by Nippon Steel & Sumikin Chemical Co., Ltd. (bisphenol A type epoxy resin and bisphenol F type epoxy resin mixture); "EX-721" (glycidyl ester type epoxy resin) manufactured by Nagase ChemteX; "Celoxide 2021P" manufactured by Daicel (alicyclic epoxy resin having an ester skeleton); manufactured by Daicel "PB-3600" (epoxy resin having a butadiene structure); Nippon Steel Chemical Co., Ltd. "ZX1658" and "ZX1658GS" (liquid 1,4-glycidylcyclohexane type epoxy resin); These may be used individually by 1 type, and may be used in combination of 2 or more types by arbitrary ratios.

Solid epoxy resins include naphthalene type tetrafunctional epoxy resin, cresol novolak type epoxy resin, dicyclopentadiene type epoxy resin, trisphenol type epoxy resin, naphthol type epoxy resin, biphenyl type epoxy resin, naphthylene ether type epoxy resin, Anthracene type epoxy resin, bisphenol A type epoxy resin and tetraphenylethane type epoxy resin are preferred, and naphthalene type tetrafunctional epoxy resin, naphthol type epoxy resin and biphenyl type epoxy resin are more preferred.

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

(A) When a liquid epoxy resin and a solid epoxy resin are used in combination as the epoxy resin, the mass ratio (liquid epoxy resin: solid epoxy resin) is preferably 1:0.1 to 1:15, More preferably 1:0.5 to 1:10, particularly preferably 1:1 to 1:8. When the mass ratio of the liquid epoxy resin and the solid epoxy resin is within the above range, it is possible to obtain appropriate adhesiveness when used in the form of an adhesive film. In addition, when used in the form of an adhesive film, sufficient flexibility is obtained and handling properties are improved. Furthermore, the breaking strength of the cured product of the resin composition can be effectively increased.

(A) The epoxy equivalent of the epoxy resin is preferably 50-5000, more preferably 50-3000, even more preferably 80-2000, still more preferably 110-1000. (A) When the epoxy equivalent of the epoxy resin is within the above range, the crosslink density of the cured product of the resin composition is sufficient, and an insulating layer with a small surface roughness can be obtained.
An epoxy equivalent is the mass of a resin containing one equivalent of epoxy groups, and can be measured according to JIS K7236.

(A) The weight average molecular weight of the epoxy resin is preferably 100 to 5,000, more preferably 250 to 3,000, still more preferably 400 to 1,500, from the viewpoint of significantly obtaining the desired effects of the present invention.
The weight average molecular weight of the resin can be measured as a polystyrene-equivalent value by gel permeation chromatography (GPC). Specifically, the weight-average molecular weight of the resin is measured by LC-9A/RID-6A manufactured by Shimadzu Corporation as a measuring device, Shodex K-800P/K-804L/K-804L manufactured by Showa Denko Co., Ltd. as a column, and a mobile phase. Chloroform or the like is used as the temperature, the column temperature is measured at 40° C., and calculation can be performed using a standard polystyrene calibration curve.

The amount of (A) epoxy resin in the resin composition is preferably 5% by mass with respect to 100% by mass of the resin component in the resin composition, from the viewpoint of obtaining an insulating layer exhibiting good mechanical strength and insulation reliability. Above, more preferably 10% by mass or more, still more preferably 20% by mass or more. (A) The upper limit of the amount of the epoxy resin is arbitrary as long as the effects of the present invention are exhibited, and is preferably 70% by mass or less, more preferably 65% by mass or less, and particularly preferably 60% by mass or less.

[3. (B) Active ester compound]
(B) The active ester compound is a compound having one or more active ester groups in one molecule. Generally, such (B) active ester compound can function as a curing agent that reacts with (A) epoxy resin to cure the resin composition. By using the active ester compound (B), the dielectric loss tangent of the cured product of the resin composition can be lowered, and an insulating layer with a small surface roughness can be obtained in general.

(B) The active ester compound preferably has two or more active ester groups in one molecule. Such (B) active ester compounds include, for example, phenol esters, thiophenol esters, N-hydroxyamine esters, esters of heterocyclic hydroxy compounds, etc., and ester groups with high reaction activity in one molecule. are compounds having two or more. Moreover, one type of active ester compound may be used alone, or two or more types may be used in combination at an arbitrary ratio.

From the viewpoint of improving heat resistance, the active ester compound (B) is more preferably an active ester compound obtained by condensation reaction of a carboxylic acid compound and/or a thiocarboxylic acid compound with a hydroxy compound and/or a thiol compound. Among them, an active ester compound obtained by reacting a carboxylic acid compound with one or more selected from the group consisting of a phenol compound, a naphthol compound and a thiol compound is more preferable. Furthermore, 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 is more preferable. Among them, an aromatic compound obtained by reacting a carboxylic acid compound having at least two or more carboxyl groups in one molecule with an aromatic compound having a phenolic hydroxyl group, and having two or more carboxyl groups in one molecule. Aromatic compounds having an active ester group of are particularly preferred. In addition, (B) the active ester compound may be linear or multi-branched. Furthermore, if the carboxylic acid compound having two or more carboxyl groups in one molecule is a compound containing an aliphatic chain, the compatibility with the resin composition can be increased, and if it is a compound having an aromatic ring, heat resistance can be increased.

Examples of carboxylic acid compounds include aliphatic carboxylic acids having 1 to 20 carbon atoms (preferably 2 to 10, more preferably 2 to 8) and aromatic compounds having 7 to 20 carbon atoms (preferably 7 to 10). Carboxylic acids are mentioned. Examples of aliphatic carboxylic acids include acetic acid, malonic acid, succinic acid, maleic acid and itaconic acid. Examples of aromatic carboxylic acids include benzoic acid, phthalic acid, isophthalic acid, terephthalic acid, and pyromellitic acid. Among them, succinic acid, maleic acid, itaconic acid, phthalic acid, isophthalic acid, and terephthalic acid are preferred, and isophthalic acid and terephthalic acid are more preferred, from the viewpoint of heat resistance. Moreover, one type of carboxylic acid compound may be used alone, or two or more types may be used in combination at an arbitrary ratio.

Examples of thiocarboxylic acid compounds include thioacetic acid and thiobenzoic acid. Moreover, one type of thiocarboxylic acid compound may be used alone, or two or more types may be used in combination at an arbitrary ratio.

Examples of phenolic compounds include phenolic compounds having 6 to 40 carbon atoms (preferably 6 to 30, more preferably 6 to 23, and even more preferably 6 to 22). Preferred specific examples of phenol compounds include hydroquinone, resorcinol, bisphenol A, bisphenol F, bisphenol S, phenolphthalin, methylated bisphenol A, methylated bisphenol F, methylated bisphenol S, phenol, o-cresol, m- cresol, p-cresol, catechol, dihydroxybenzophenone, trihydroxybenzophenone, tetrahydroxybenzophenone, phloroglucine, benzenetriol, dicyclopentadiene type diphenol and the like. Here, "dicyclopentadiene-type diphenol" refers to a phenol compound obtained by condensing one molecule of dicyclopentadiene with two molecules of phenol. As the phenol compound, a phenol novolak and a phosphorus atom-containing oligomer having a phenolic hydroxyl group described in JP-A-2013-40270 may also be used. Moreover, a phenol compound may be used individually by 1 type, and may be used in combination of 2 or more types by arbitrary ratios.

Examples of naphthol compounds include naphthol compounds having 10 to 40 carbon atoms (preferably 10 to 30, more preferably 10 to 20). Preferred specific examples of naphthol compounds include α-naphthol, β-naphthol, 1,5-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 2,6-dihydroxynaphthalene and the like. Naphthol novolacs may also be used as naphthol compounds. Moreover, one type of naphthol compound may be used alone, or two or more types may be used in combination at an arbitrary ratio.

Among them, from the viewpoint of improving heat resistance and solubility, 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, phloroglucine, benzenetriol, dicyclopentadiene-type diphenol, phenol novolac, phosphorus having a phenolic hydroxyl group Atom-containing oligomers are preferred. Furthermore, catechol, 1,5-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, dihydroxybenzophenone, trihydroxybenzophenone, tetrahydroxybenzophenone, phloroglucine, benzenetriol, dicyclopentadiene-type diphenol, phenol Novolacs and phosphorus atom-containing oligomers having phenolic hydroxyl groups are more preferred. Among them, 1,5-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, dihydroxybenzophenone, trihydroxybenzophenone, tetrahydroxybenzophenone, dicyclopentadiene-type diphenol, phenol novolac, having a phenolic hydroxyl group Phosphorus atom-containing oligomers are more preferred. Further, 1,5-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, dicyclopentadiene-type diphenol, phenol novolak, and phosphorus atom-containing oligomers having phenolic hydroxyl groups are even more preferred. Among them, 1,5-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, dicyclopentadiene-type diphenol, and phosphorus atom-containing oligomers having phenolic hydroxyl groups are particularly preferred. Furthermore, dicyclopentadiene-type diphenol is particularly preferred.

Examples of thiol compounds include benzenedithiol and triazinedithiol. Moreover, a thiol compound may be used individually by 1 type, and may be used in combination of 2 or more types by arbitrary ratios.

Preferred specific examples of the active ester compound include an active ester compound containing a dicyclopentadiene type diphenol structure, an active ester compound containing a naphthalene structure, an active ester compound containing an acetylated phenol novolac, and a benzoylated phenol novolak. Examples include active ester compounds and active ester compounds obtained by reacting an aromatic carboxylic acid with a phosphorus atom-containing oligomer having a phenolic hydroxyl group. Among them, an active ester compound containing a dicyclopentadiene type diphenol structure, an active ester compound containing a naphthalene structure, and an active ester compound obtained by reacting an aromatic carboxylic acid with a phosphorus atom-containing oligomer having a phenolic hydroxyl group are more preferred. . Here, the "dicyclopentadiene-type diphenol structure" represents a divalent structural unit consisting of phenylene-dicyclopentylene-phenylene.

A particularly preferred specific example of the active ester compound containing a dicyclopentadiene-type diphenol structure is the compound of the following formula (B1).

In formula (B1), each R independently represents a phenyl group or a naphthyl group. Among them, R is preferably a naphthyl group from the viewpoint of reducing the dielectric loss tangent and improving the heat resistance.
In formula (B1), k represents 0 or 1. Among them, k is preferably 0 from the viewpoint of reducing the dielectric loss tangent and improving the heat resistance.
In formula (B1), n is the average number of repeating units and is 0.05 to 2.5. Above all, n is preferably 0.25 to 1.5 from the viewpoint of reducing the dielectric loss tangent and improving the heat resistance.

(B) As the active ester compound, an active ester compound disclosed in JP-A-2004-277460 or JP-A-2013-40270 may be used. Moreover, as (B) the active ester compound, a commercially available active ester compound may be used. Commercially available active ester compounds include, for example, DIC's "EXB9451", "EXB9460", "EXB9460S", "HPC-8000-65T", and "HPC-8000L-65M" (dicyclopentadiene type diphenol structure Active ester compound containing); "EXB9416-70BK" manufactured by DIC (active ester compound containing naphthalene structure); "DC808" manufactured by Mitsubishi Chemical Corporation (active ester compound containing acetylated phenol novolak); Mitsubishi Chemical Corporation "YLH1026" (active ester compound containing a benzoylated phenol novolac) manufactured by DIC Corporation; and "EXB9050L-62M" (phosphorus atom-containing active ester compound) manufactured by DIC Corporation.

(B) The active group equivalent of the active ester compound is preferably 120-500, more preferably 150-400, particularly preferably 180-300. When the active group equivalent of (B) the active ester compound is within the above range, the crosslink density of the cured product of the resin composition is sufficient, and an insulating layer with a small surface roughness can be obtained. Here, the active group equivalent indicates the mass of the resin containing one equivalent of active group.

Moreover, one type of the active ester compound may be used alone, or two or more types may be used in combination at an arbitrary ratio.

The amount of the active ester compound (B) in the resin composition is preferably 1% by mass or more, more preferably 2% by mass or more, and even more preferably 3% by mass or more, relative to 100% by mass of the non-volatile components in the resin composition. , 4% by mass or more, 5% by mass or more, 6% by mass or more, or 7% by mass or more is particularly preferable, and 30% by mass or less is preferable, 25% by mass or less is more preferable, and 20% by mass or less is even more preferable. % by mass or less, or 10% by mass or less is particularly preferred. When the amount of the active ester compound (B) is at least the lower limit of the range, the adhesion between the conductor layer and the insulating layer can be particularly enhanced, and when it is at most the upper limit of the range, heat resistance is improved. and suppress smear generation.

When the number of epoxy groups in the epoxy resin (A) is 1, the number of active groups in the active ester compound (B) is preferably 0.1 or more, more preferably 0.1 or more, from the viewpoint of obtaining an insulating layer with good mechanical strength. It is 2 or more, more preferably 0.3 or more, particularly preferably 0.4 or more, preferably 2 or less, more preferably 1.5 or less, and still more preferably 1 or less. Here, the "epoxy group number of the epoxy resin" is the sum of the values obtained by dividing the solid mass of each epoxy resin present in the resin composition by the epoxy equivalent for all the epoxy resins. Further, "active group" means a functional group capable of reacting with an epoxy group, and "the number of active groups in the active ester compound" means the solid mass of the active ester compound present in the resin composition. It is the sum of all the values divided by the active group equivalent.

[4. (C) Polyimide resin having an indane skeleton]
(C) Indane polyimide resin is a polyimide resin having an indane skeleton. An indane skeleton is a carbon skeleton represented by the following formula (C1). By containing (C) an indane polyimide resin in combination with (A) an epoxy resin and (B) an active ester compound, the resin composition of the present invention has a low dielectric loss tangent while having a minimum melt viscosity within an appropriate range. In addition, it is possible to obtain the desired effect that an insulating layer having high adhesion to the conductor layer can be realized.

(C) The indane polyimide resin may have an unsubstituted indane skeleton in which hydrogen atoms are bonded to the carbon atoms of the indane skeleton, or has a substituted indane skeleton in which some or all of the hydrogen atoms are substituted with substituents. It may have a combination of an unsubstituted indane skeleton and a substituted indane skeleton. As the substituent, a hydrocarbon group is preferable from the viewpoint of effectively lowering the minimum melt viscosity of the resin composition and from the viewpoint of effectively reducing the dielectric loss tangent of the cured product of the resin composition. The number of carbon atoms in the above hydrocarbon group is generally 1-6, preferably 1-4, more preferably 1-2. Examples of suitable hydrocarbon groups include alkyl groups such as methyl, ethyl and propyl groups.

In the substituted indane skeleton, the substituent may be attached to the 5-membered ring or the 6-membered ring of the indane skeleton. Further, the substituted indane skeleton may have a combination of substituents attached to the 5-membered ring and substituents attached to the 6-membered ring. Among them, the substituent is preferably bonded to the 5-membered ring of the indane skeleton from the viewpoint of significantly obtaining the desired effects of the present invention.

The number of substituents is usually 1 to 6, preferably 3, per indane skeleton. By adjusting the number of substituents per indane skeleton as described above, the desired effect of the present invention can be significantly obtained.

Among them, from the viewpoint of significantly obtaining the desired effect of the present invention, (C) the indane polyimide resin preferably has a trimethylindane skeleton in which three methyl groups are bonded per indane skeleton, and has the following formula (C2) It is particularly preferred to have a 1,1,3-trimethylindane skeleton represented by

The indane skeleton is usually included in (C) the indane polyimide resin as a group having a valence of 1 or more (indane group). The valence of the indane group is usually 2 or more. Above all, from the viewpoint of significantly obtaining the desired effects of the present invention, (C) the indane polyimide resin preferably contains the indane skeleton as a divalent group. The position of the bond of the indane group is arbitrary, but when the indane skeleton is a divalent group, it is preferred that each of the 5-membered ring and the 6-membered ring of the indane skeleton has one bond.

(C) Indane polyimide resin can be obtained by polymerizing a diamine compound and a tetracarboxylic acid compound. Therefore, (C) the indane polyimide resin usually contains a diamine structural unit and a tetracarboxylic acid structural unit in its molecule. Here, the diamine structural unit refers to a repeating unit having a structure formed by polymerizing a diamine compound. Moreover, the tetracarboxylic acid structural unit refers to a repeating unit having a structure formed by polymerizing a tetracarboxylic acid compound. (C) The indane polyimide resin may contain the indane skeleton in the diamine structural unit or in the tetracarboxylic acid structural unit. Among them, (C) the indane polyimide resin preferably contains the above-described indane skeleton in the diamine structural unit from the viewpoint of significantly obtaining the desired effects of the present invention.

Diamine compounds containing an indane skeleton include, for example, 5-(4-aminophenoxy)-3-[4-(4-aminophenoxy)phenyl]-1,1,3-trimethylindane, 5-amino-1-( 4-aminophenyl)-1,3,3-trimethylindane, 6-amino-1-(4-aminophenyl)-1,3,3-trimethylindane and the like. Among them, 5-(4-aminophenoxy)-3-[4-(4-aminophenoxy)phenyl]-1,1,3-trimethylindane is a long carbon atom containing both aromatic and aliphatic cyclic structures. Since it has chains, it is possible to effectively lower the dielectric loss tangent while increasing the mechanical strength and heat resistance of the (C) indane polyimide resin. The diamine compound containing the indane skeleton and the diamine structural unit corresponding to the diamine compound may be used singly or in combination of two or more at any ratio.

(C) The proportion of the diamine compound containing an indane skeleton in all the diamine compounds that are raw materials for the indane polyimide resin is 50 mol from the viewpoint of improving the heat resistance, mechanical strength and dielectric loss tangent of the cured product of the resin composition. % or more, more preferably 80 mol % or more.

(C) Indane polyimide resin may contain a diamine structural unit that does not contain an indane skeleton, if necessary. Examples of such diamine compounds that do not contain an indane skeleton include aromatic compounds such as 4,4′-diaminodiphenyl ether, 1,4-phenylenediamine, and 2,2-bis[4-(4-aminophenoxy)phenyl]propane. group diamine; 1,2-diaminoethane, 1,3-diaminopropane, 1,4-diaminobutane, 1,5-diaminopentane, 1,6-hexanediamine, 1,7-heptanediamine, 1,8-octane Linear aliphatic diamines such as diamine, 1,9-nonanediamine, 1,10-decanediamine, 1,11-undecanediamine, 1,12-dodecanediamine; 1,2-diaminopropane, 1,2-diamino- Branches such as 2-methylpropane, 1,3-diamino-2-methylpropane, 1,3-diamino-2,2-dimethylpropane, 1,3-diaminopentane, 1,5-diamino-2-methylpentane type aliphatic diamine; 5-amino-1,3,3-trimethylcyclohexanemethylamine (isophoronediamine), 1,4-diaminocyclohexane, 1,3-diaminocyclohexane, 1,4-cyclohexanebis(methylamine), 1 ,3-cyclohexanebis(methylamine), 4,4′-diaminodicyclohexylmethane, bis(4-amino-3-methylcyclohexyl)methane, 3(4),8(9)-bis(aminomethyl)tricyclo[5 .2.1.0 ^2,6 ]decane, 2,5(6)-bis(aminomethyl)bicyclo[2.2.1]heptane, 1,3-diaminoadamantane, 3,3′-diamino-1, alicyclic diamines such as 1′-biadamantyl and 1,6-diaminoadamantane; The diamine compound containing no indane skeleton and the diamine structural unit corresponding to this diamine compound may be used singly or in combination of two or more at any ratio.

Examples of tetracarboxylic acid compounds include bis(3,4-dicarboxyphenyl)ether dianhydride, 2,2-bis[4-(3,4-dicarboxyphenoxy)phenyl]propane dianhydride, 3, 3',4,4'-biphenyltetracarboxylic dianhydride, pyromellitic dianhydride, 3,3',4,4'-benzophenonetetracarboxylic dianhydride, 3,3',4,4' -Aromatic tetracarboxylic dianhydrides such as diphenylsulfonetetracarboxylic dianhydride. Among these, 2,2-bis[4-(3,4-dicarboxyphenoxy)phenyl]propane dianhydride has mechanical strength, heat resistance, chemical resistance and electrical insulation of the cured product of the resin composition. can be effectively increased, which is preferable. Further, 3,3',4,4'-biphenyltetracarboxylic dianhydride is preferable because it can effectively improve the heat resistance and mechanical strength of the cured product of the resin composition. Furthermore, bis (3,4-dicarboxyphenyl) ether dianhydride can effectively improve the mechanical strength, heat resistance, chemical resistance and electrical insulation of the cured product of the resin composition, and further It is preferable because the dielectric loss tangent can be remarkably lowered. The tetracarboxylic acid compound and the tetracarboxylic acid structural unit corresponding to this tetracarboxylic acid compound may be used singly or in combination of two or more at any ratio.

(C) The polymerization structure of the indane polyimide resin is not limited, and may be a random polymer, an alternating polymer, or a block polymer.

(C) As the indane polyimide resin, for example, polyimide resins described in JP-A-2015-214680, JP-A-2015-209461, or JP-A-2015-209455 may be employed.

(C) Indane polyimide resin may be used singly or in combination of two or more at any ratio.

(C) The weight average molecular weight of the indane polyimide resin is preferably 5,000 to 100,000, more preferably 8,000 to 50,000, and still more preferably 10,000 to 30,000, from the viewpoint of significantly obtaining the desired effects of the present invention.

The (C) indane polyimide resin as described above can be produced, for example, by polymerizing a diamine compound and a tetracarboxylic acid compound. In this case, the desired indane polyimide resin can be obtained by using one or both of the diamine compound and the tetracarboxylic acid compound that contain an indane skeleton. In addition, in the above polymerization, any copolymer component may be polymerized as necessary. Usually, by polymerizing a diamine compound containing an indane skeleton, a tetracarboxylic acid compound, and optionally an optional copolymerization component (e.g., a diamine compound containing no indane skeleton), (C) an indane polyimide resin to manufacture. In addition, (C) the indane polyimide resin is obtained by, for example, polymerizing a diamine compound, a tetracarboxylic acid compound, and, if necessary, an optional copolymerization component to obtain a polyamic acid, and then dehydrating and dehydrating the polyamic acid. It may be prepared by imidization by cyclization.

The amounts of the diamine compound and the tetracarboxylic acid compound can be arbitrarily set within the range that the desired (C) indane polyimide resin can be obtained. Among them, from the viewpoint of sufficiently increasing the molecular weight of the (C) indane polyimide resin, it is preferable to adjust the acid anhydride group of the tetracarboxylic acid compound to 0.9 equivalent or more with respect to the amino group of the diamine compound. . Usually, the diamine compound and the tetracarboxylic acid compound are used in the polymerization in amounts such that the total amount of the diamine compound and the total amount of the tetracarboxylic acid compound are approximately equimolar. Said polymerization is usually carried out in a suitable reaction solvent at a reaction temperature of 80° C. or less under atmospheric or nitrogen atmosphere.

When a polyamic acid is obtained by the above polymerization, the desired (C) indane polyimide resin is obtained by imidating the polyamic acid. Imidization can be carried out, for example, by a chemical ring closure method involving dehydration using a dehydrating agent and a catalyst. Examples of dehydrating agents include aliphatic carboxylic anhydrides such as acetic anhydride, and aromatic carboxylic anhydrides such as phthalic anhydride. Examples of catalysts include heterocyclic tertiary amine compounds such as pyridine, picoline and quinoline; aliphatic tertiary amine compounds such as triethylamine; aromatic tertiary amine compounds such as N,N-dimethylaniline. ; and the like. Each of the dehydrating agent and the catalyst may be used alone, or two or more of them may be used in combination at any ratio.

Furthermore, imidization can be carried out, for example, by a thermal ring closure method with thermal dehydration. The heating temperature in the thermal ring closure method is generally 100°C to 400°C, preferably 200°C to 350°C, more preferably 250°C to 300°C. The heating time is usually 1 minute to 6 hours, preferably 5 minutes to 2 hours, more preferably 15 minutes to 1 hour. The heating atmosphere is not particularly limited, but an inert atmosphere such as a nitrogen gas atmosphere or a nitrogen/hydrogen mixed gas atmosphere is preferable from the viewpoint of suppressing coloration.

The amount of (C) indane polyimide resin in the resin composition is preferably 1% by mass or more, more preferably 4% by mass or more, and particularly preferably 8% by mass or more, relative to 100% by mass of the resin component in the resin composition. , preferably 20% by mass or less, more preferably 18% by mass or less, and particularly preferably 15% by mass or less. (C) When the amount of the indane polyimide resin is at least the lower limit of the above range, the dielectric loss tangent of the cured product of the resin composition can be effectively reduced. Further, when the amount of (C) the indane polyimide resin is equal to or less than the upper limit of the above range, the adhesion between the conductor layer and the conductive layer can be effectively enhanced.

[5. (D) Inorganic filler]
The resin composition may further contain (D) an inorganic filler as an optional component in addition to the components described above. (D) By using the inorganic filler, the thermal expansion coefficient of the cured product of the resin composition can be reduced, so that reflow warping of the insulating layer can be suppressed.

(D) The material of the inorganic filler is not particularly limited, but examples include silica, alumina, glass, cordierite, silicon oxide, barium sulfate, barium carbonate, talc, clay, mica powder, zinc oxide, hydrotalcite, Boehmite, aluminum hydroxide, magnesium hydroxide, calcium carbonate, magnesium carbonate, magnesium oxide, boron nitride, aluminum nitride, manganese nitride, aluminum borate, strontium carbonate, strontium titanate, calcium titanate, magnesium titanate, bismuth titanate , titanium oxide, zirconium oxide, barium titanate, barium zirconate titanate, barium zirconate, calcium zirconate, zirconium phosphate, and zirconium tungstate phosphate. Among these, silica is particularly suitable. As silica, spherical silica is preferable. (D) Inorganic fillers may be used singly or in combination of two or more at any ratio.

(D) The inorganic filler is usually contained in the resin composition in the form of particles. (D) The average particle diameter of the particles of the inorganic filler is preferably 5 μm or less, more preferably 2.5 μm or less, and even more preferably 2 μm, from the viewpoint of improving circuit embedding properties and obtaining an insulating layer with a small surface roughness. Below, it is particularly preferably 1.5 μm or less. Although the lower limit of the average particle diameter is not particularly limited, it is preferably 0.01 μm or more, more preferably 0.05 μm or more, still more preferably 0.1 μm or more, and most preferably 0.5 μm or more.

Commercially available products of the (D) inorganic filler having the above average particle size include, for example, Nippon Steel & Sumikin Materials Co., Ltd. "SP60-05" and "SP507-05"; YA050C", "YA050C-MJE", "YA010C"; "UFP-30" manufactured by Denka; "Silfil NSS-3N", "Silfil NSS-4N", "Silfil NSS-5N" manufactured by Tokuyama; manufactured by Admatechs "SC2500SQ", "SO-C4", "SO-C2", "SO-C1";

(D) The average particle size of particles such as inorganic fillers can be measured by a laser diffraction/scattering method based on Mie scattering theory. Specifically, the particle size distribution of particles can be measured on a volume basis using a laser diffraction scattering type particle size distribution analyzer, and the average particle size can be determined as the median diameter from the particle size distribution. A measurement sample can preferably be one obtained by dispersing particles in water using ultrasonic waves. As a laser diffraction scattering type particle size distribution analyzer, "LA-500" manufactured by Horiba Ltd. can be used.

(D) The inorganic filler may be surface-treated with any surface treatment agent. Examples of surface treatment agents include aminosilane coupling agents, epoxysilane coupling agents, mercaptosilane coupling agents, alkoxysilane compounds, organosilazane compounds, and titanate coupling agents. The moisture resistance and dispersibility of the (D) inorganic filler can be enhanced by surface-treating with these surface-treating agents. Commercially available surface treatment agents include, for example, "KBM403" (3-glycidoxypropyltrimethoxysilane) manufactured by Shin-Etsu Chemical Co., Ltd., and "KBM803" (3-mercaptopropyltrimethoxysilane) manufactured by Shin-Etsu Chemical Co., Ltd. , Shin-Etsu Chemical Co., Ltd. "KBE903" (3-aminopropyltriethoxysilane), Shin-Etsu Chemical Co., Ltd. "KBM573" (N-phenyl-3-aminopropyltrimethoxysilane), Shin-Etsu Chemical Co., Ltd. "SZ-31 (hexamethyldisilazane), Shin-Etsu Chemical Co., Ltd. "KBM-103" (phenyltrimethoxysilane), Shin-Etsu Chemical Co., Ltd. "KBM-4803" (long-chain epoxy type silane coupling agent), and the like. Moreover, one type of surface treatment agent may be used alone, or two or more types may be used in combination at an arbitrary ratio.

The degree of surface treatment by the surface treatment agent can be evaluated by the amount of carbon per unit surface area of the (D) inorganic filler. (D) The amount of carbon per unit surface area of the inorganic filler is preferably 0.02 mg/m ² or more, more preferably 0.1 mg/m ² or more, from the viewpoint of improving the dispersibility of the (D) inorganic filler. 0.2 mg/m ² or more is particularly preferred. On the other hand, from the viewpoint of suppressing an increase in the melt viscosity of the resin composition and the melt viscosity in the form of a sheet, the amount of carbon is preferably 1 mg/m ² or less, more preferably 0.8 mg/m ² or less, and 0.8 mg/m 2 or less. 5 mg/m ² or less is particularly preferred.

The amount of carbon per unit surface area of the (D) inorganic filler is measured after the surface-treated (D) inorganic filler is washed with a solvent (for example, methyl ethyl ketone (hereinafter sometimes abbreviated as “MEK”)). , can be measured. Specifically, a sufficient amount of methyl ethyl ketone and (D) an inorganic filler surface-treated with a surface treatment agent are mixed, and ultrasonically cleaned at 25° C. for 5 minutes. Then, after removing the supernatant liquid and drying the solid content, the amount of carbon per unit surface area of the (D) inorganic filler can be measured using a carbon analyzer. As a carbon analyzer, "EMIA-320V" manufactured by Horiba Ltd. can be used.

From the viewpoint of obtaining an insulating layer with a low coefficient of thermal expansion, the amount of the inorganic filler (D) in the resin composition is preferably 50% by mass or more, more preferably 100% by mass of the non-volatile components in the resin composition. It is 55% by mass or more, more preferably 60% by mass or more, or 65% by mass or more. The upper limit is preferably 95% by mass or less, more preferably 90% by mass or less, and even more preferably 85% by mass or less, or 80% by mass or less, from the viewpoint of mechanical strength, particularly elongation, of the insulating layer.

[6. (E) Organic filler]
The resin composition may further contain (E) an organic filler as an optional component in addition to the components described above. (E) By using an organic filler, the flexibility of the cured product of the resin composition can be improved, so that the stretchability of the insulating layer can be improved.

(E) As the organic filler, any organic filler that can be used in forming an insulating layer of a printed wiring board can be used. (E) Organic fillers include, for example, rubber particles, polyamide particles, and silicone particles. As the rubber particles, commercially available products may be used, such as "EXL2655" manufactured by Dow Chemical Japan, "AC3816N" manufactured by Aica Kogyo Co., Ltd., and the like. The (E) organic filler may be used alone, or two or more of them may be used in an arbitrary ratio.

The average particle size of the particles of the organic filler (E) is preferably 5 μm or less, more preferably 4 μm or less, and even more preferably 3 μm or less, from the viewpoint of excellent dispersibility in the resin composition. The lower limit of the average particle size of the (E) organic filler is not particularly limited, but is preferably 0.05 μm or more, more preferably 0.08 μm or more, and particularly preferably 0.10 μm or more.

The amount of the (E) organic filler in the resin composition is preferably 0.1% to 20% by mass, more preferably 0.2% to 10% by mass, still more preferably 0.3% to 5% by mass, or 0.5% to 3% by mass.

[7. (F) Curing accelerator]
The resin composition may further contain (F) a curing accelerator as an optional component in addition to the components described above. By using (F) a curing accelerator, curing can be accelerated when curing the resin composition.

(F) Curing accelerators include, for example, phosphorus-based curing accelerators, amine-based curing accelerators, imidazole-based curing accelerators, guanidine-based curing accelerators, metal-based curing accelerators, and the like. Among them, phosphorus-based curing accelerators, amine-based curing accelerators, imidazole-based curing accelerators, and metal-based curing accelerators are preferable, and amine-based curing accelerators, imidazole-based curing accelerators, and metal-based curing accelerators are preferable. more preferred.

Phosphorus curing accelerators include, for example, triphenylphosphine, phosphonium borate compounds, tetraphenylphosphonium tetraphenylborate, n-butylphosphonium tetraphenylborate, tetrabutylphosphonium decanoate, (4-methylphenyl)triphenylphosphonium thiocyanate. , tetraphenylphosphonium thiocyanate, and butyltriphenylphosphonium thiocyanate, and triphenylphosphine and tetrabutylphosphonium decanoate are preferred.

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

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

As the imidazole-based curing accelerator, a commercially available product may be used, and examples thereof include "P200-H50" manufactured by Mitsubishi Chemical Corporation.

Guanidine curing accelerators include, for example, dicyandiamide, 1-methylguanidine, 1-ethylguanidine, 1-cyclohexylguanidine, 1-phenylguanidine, 1-(o-tolyl)guanidine, dimethylguanidine, diphenylguanidine, trimethylguanidine, Tetramethylguanidine, Pentamethylguanidine, 1,5,7-triazabicyclo[4.4.0]dec-5-ene, 7-methyl-1,5,7-triazabicyclo[4.4.0] Dec-5-ene, 1-methylbiguanide, 1-ethylbiguanide, 1-n-butylbiguanide, 1-n-octadecylbiguanide, 1,1-dimethylbiguanide, 1,1-diethylbiguanide, 1-cyclohexylbiguanide, 1 -allylbiguanide, 1-phenylbiguanide, 1-(o-tolyl)biguanide and the like, with dicyandiamide and 1,5,7-triazabicyclo[4.4.0]dec-5-ene being preferred.

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

(F) Curing accelerators may be used singly or in combination of two or more at any ratio.

The amount of the (F) curing accelerator in the resin composition is not particularly limited, but from the viewpoint of significantly obtaining the desired effects of the present invention, it is 0.01 mass% with respect to 100 mass% of the resin component in the resin composition. % to 3% by mass is preferred.

[8. (G) Curing agent]
In addition to the components described above, the resin composition may further contain (G) a curing agent other than (B) the active ester compound as an optional component.

(G) As the curing agent, any curing agent having a function of curing the epoxy resin can be used. (G) Curing agents include, for example, phenol-based curing agents, naphthol-based curing agents, cyanate ester-based curing agents, benzoxazine-based curing agents, and carbodiimide-based curing agents.

As the phenolic curing agent and the naphtholic curing agent, a phenolic curing agent having a novolac structure or a naphtholic curing agent having a novolac structure is preferable from the viewpoint of heat resistance and water resistance. In addition, from the viewpoint of obtaining an insulating layer having excellent adhesion to the conductor layer, a nitrogen-containing phenolic curing agent and a nitrogen-containing naphthol curing agent are preferable, and a triazine skeleton-containing phenolic curing agent and a triazine skeleton-containing naphthol curing agent are more preferable. preferable. Among them, a triazine skeleton-containing phenol novolak resin and a triazine skeleton-containing naphthol novolac resin are preferable from the viewpoint of highly enhancing heat resistance, water resistance, and adhesion to the conductor layer.

Specific examples of phenol-based curing agents and naphthol-based curing agents include "MEH-7700", "MEH-7810", and "MEH-7851" manufactured by Meiwa Kasei; "NHN" manufactured by Nippon Kayaku; "CBN", "GPH"; Nippon Steel & Sumikin Chemical Co., Ltd. "SN-170", "SN-180", "SN-190", "SN-475", "SN-485", "SN-495", "SN-375", "SN-395"; DIC's "LA-7052", "LA-7054", "LA-3018", "LA-1356", "TD2090";

Examples of the cyanate ester curing agent include novolac type cyanate ester curing agents such as phenol novolac type and alkylphenol novolac type; dicyclopentadiene type cyanate ester curing agents; bisphenol A type, bisphenol F type, bisphenol S type, etc. and bisphenol-type cyanate ester-based curing agents; and prepolymers obtained by partially triazinizing them. Specific examples of cyanate ester curing agents include bisphenol A dicyanate, polyphenolcyanate, oligo(3-methylene-1,5-phenylenecyanate), 4,4'-methylenebis(2,6-dimethylphenylcyanate), 4, 4′-ethylidene diphenyl dicyanate, hexafluorobisphenol A dicyanate, 2,2-bis(4-cyanate)phenylpropane, 1,1-bis(4-cyanatophenylmethane), bis(4-cyanate-3,5- Difunctional cyanate resins such as dimethylphenyl)methane, 1,3-bis(4-cyanatophenyl-1-(methylethylidene))benzene, bis(4-cyanatophenyl)thioether, and bis(4-cyanatophenyl)ether; polyfunctional cyanate resins derived from phenol novolak, cresol novolak, etc.; and prepolymers in which these cyanate resins are partially triazined; and the like. Specific examples of commercially available cyanate ester curing agents include "PT30" and "PT60" (both phenol novolac type polyfunctional cyanate ester resins) and "BA230" (a part or all of bisphenol A dicyanate) manufactured by Lonza Japan. is triazined to form a trimer) and the like.

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

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

Among the above-mentioned (G) curing agents, from the viewpoint of obtaining an insulating layer exhibiting a good elongation at break by combining components (A), (B), and (C), phenol-based curing agents and naphthol-based curing agents Curing agents are preferred. Furthermore, a phenol-based curing agent is particularly preferable because an insulating layer with a small surface roughness can be obtained.

(G) Curing agents may be used singly or in combination of two or more at any ratio.

The amount of the (G) curing agent in the resin composition is preferably 0.5% by mass or more, more preferably 0.6% by mass or more, and still more preferably 0% by mass with respect to 100% by mass of non-volatile components in the resin composition. 7% by mass or more, or 1% by mass or more, preferably 10% by mass or less, more preferably 8% by mass or less, 4% by mass or less, 3% by mass or less, or 2% by mass or less.

[9. (H) thermoplastic resin]
The resin composition may further contain (H) a thermoplastic resin as an optional component in addition to the components described above.

(H) Thermoplastic resins include, for example, phenoxy resin; polyvinyl acetal resin; polyolefin resin; polybutadiene resin; polysulfone resin; polyimide resins, polyamideimide resins, and polyetherimide resins;

Examples of phenoxy resins include bisphenol A skeleton, bisphenol F skeleton, bisphenol S skeleton, bisphenolacetophenone skeleton, novolac skeleton, biphenyl skeleton, fluorene skeleton, dicyclopentadiene skeleton, norbornene skeleton, naphthalene skeleton, anthracene skeleton, adamantane skeleton, and terpene. and a phenoxy resin having one or more skeletons selected from the group consisting of a trimethylcyclohexane skeleton. The terminal of the phenoxy resin may be any functional group such as a phenolic hydroxyl group or an epoxy group. Specific examples of phenoxy resins include Mitsubishi Chemical's "1256" and "4250" (both bisphenol A skeleton-containing phenoxy resins); Mitsubishi Chemical's "YX8100" (bisphenol S skeleton-containing phenoxy resin); "YX6954" (bisphenolacetophenone skeleton-containing phenoxy resin) manufactured by Nippon Steel & Sumikin Chemical Co., Ltd.; "FX280" and "FX293" manufactured by Nippon Steel & Sumikin Chemical Co., Ltd.; "YL6794", "YL7213", "YL7290", "YL7891BH30" and "YL7482";

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

Specific examples of the polyethersulfone resin include "PES5003P" manufactured by Sumitomo Chemical Co., Ltd., and the like.

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

(C) Specific examples of the polyimide resin other than the indane polyimide resin include "Ricacoat SN20" and "Ricacoat PN20" manufactured by Shin Nippon Rika. Specific examples of these polyimide resins also include a linear polyimide resin obtained by reacting a bifunctional hydroxyl group-terminated polybutadiene, a diisocyanate compound and a tetrabasic acid anhydride (polyimide resin described in JP-A-2006-37083). , modified polyimide resins such as polysiloxane skeleton-containing polyimide resins (polyimide resins described in JP-A-2002-12667 and JP-A-2000-319386).

(C) Specific examples of polyamideimide resins other than indane polyimide resins include "VYLOMAX HR11NN" and "VYLOMAX HR16NN" manufactured by Toyobo Co., Ltd. Specific examples of these polyamideimide resins include modified polyamideimides such as "KS9100" and "KS9300" (polysiloxane skeleton-containing polyamideimides) manufactured by Hitachi Chemical Co., Ltd.

Among them, the thermoplastic resin (H) is preferably a phenoxy resin or a polyvinyl acetal resin, and particularly preferably a phenoxy resin, from the viewpoint of obtaining an insulating layer having a small surface roughness and particularly excellent adhesion to the conductor layer.

(H) Thermoplastic resins may be used singly or in combination of two or more at any ratio.

(H) The weight average molecular weight of the thermoplastic resin is preferably 8,000 to 70,000, more preferably 10,000 to 60,000, particularly preferably 20, from the viewpoint of significantly obtaining the desired effects of the present invention. ,000 to 60,000.

The amount of (H) thermoplastic resin in the resin composition is preferably 0.5% by mass to 15% by mass, more preferably 0.6% by mass to 12% by mass, relative to 100% by mass of the resin component in the resin composition. % by mass, more preferably 0.7% by mass to 10% by mass.

[10. (I) flame retardant]
The resin composition may further contain (I) a flame retardant as an optional component in addition to the components described above. (I) Flame retardants include, for example, organic phosphorus flame retardants, organic nitrogen-containing phosphorus compounds, nitrogen compounds, silicone flame retardants, and metal hydroxides. (I) As the flame retardant, a commercially available product may be used, and examples thereof include “HCA-HQ” manufactured by Sanko Co., Ltd., and “PX-200” manufactured by Daihachi Chemical Industry Co., Ltd. Moreover, (I) flame retardant may be used individually by 1 type, and may be used in combination of 2 or more types by arbitrary ratios.

The amount of (I) flame retardant in the resin composition is not particularly limited, but is preferably 0.5% by mass to 20% by mass, more preferably 0.5% by mass, relative to 100% by mass of the resin component in the resin composition. % to 15% by mass, more preferably 0.5% to 10% by mass.

[11. (J) optional additive]
The resin composition may contain (J) optional additives in addition to the components described above. Such additives include, for example, organometallic compounds such as organocopper compounds, organozinc compounds and organocobalt compounds; thickeners; antifoaming agents; leveling agents; agents.

[12. Properties of resin composition]
The resin composition has a minimum melt viscosity within a range suitable for use as a material for insulating layers of printed wiring boards. Here, the lowest melt viscosity of the resin composition means the lowest viscosity exhibited by the resin composition when the resin composition is melted. Specifically, when the resin composition is melted by heating the resin composition at a constant rate of temperature rise, the melt viscosity decreases as the temperature rises in the initial stage, and after a certain temperature rise, the melt viscosity increases as the temperature rises. Rise. The minimum melt viscosity refers to the melt viscosity at such minimum point.

Specific minimum melt viscosity of the resin composition is preferably 200 poise or more, more preferably 300 poise or more, particularly preferably 400 poise or more, preferably 3000 poise or less, more preferably 2000 poise or less, and particularly preferably 1500 poise or less. When the minimum melt viscosity of the resin composition is at least the lower limit value, the thickness of the resin composition layer can be stably maintained even if the resin composition layer is thin. You can get sex.

The minimum melt viscosity of the resin composition was measured using a dynamic viscoelasticity measuring device in a temperature range of 60°C to 200°C, with a temperature increase rate of 5°C/min, a measurement temperature interval of 2.5°C, and a vibration of 1Hz/min. It can be measured under the measurement conditions of deg.

According to the present inventors, the mechanism by which the resin composition can have a minimum melt viscosity within a range suitable for use as a material for the insulating layer of a printed wiring board is presumed to be as follows. However, the technical scope of the present invention is not limited by the mechanism described below.
(B) Active ester compounds are generally less polar. In addition, (C) the indane polyimide resin has an indane skeleton, so the ratio of aromatic rings in the molecule is large, and therefore the polarity is small. Therefore, (B) the active ester compound and (C) the indane polyimide resin have high compatibility and can be well mixed. Therefore, the melt viscosity of the resin composition as a whole is low, so that it can have a minimum melt viscosity in a low range suitable as a material for insulating layers of printed wiring boards as described above.

Moreover, a cured product having a low dielectric loss tangent can be obtained by curing the resin composition. Therefore, by using a cured product of the resin composition, an insulating layer with a low dielectric loss tangent can be realized. The dielectric loss tangent of the cured product of the resin composition is preferably as low as possible, and from the viewpoint of use as a material for an insulating layer, it is preferably 0.020 or less, more preferably 0.010 or less, still more preferably 0.009 or less, and particularly preferably 0.008 or less, 0.007 or less, or 0.006 or less. Although there is no particular lower limit, it is usually 0.001 or more.
The dielectric loss tangent of the cured product of the resin composition can be measured by the cavity resonance perturbation method under the measurement conditions of a measurement frequency of 5.8 GHz and a measurement temperature of 23°C.

According to the present inventors, the mechanism by which the dielectric loss tangent of the cured product of the resin composition can be lowered is presumed to be as follows. However, the technical scope of the present invention is not limited by the mechanism described below.
As described above, the indane polyimide resin (C) has an indane skeleton, so that the proportion of aromatic rings in the molecule is large, and therefore the polarity is small. Therefore, the polarity of the cured product of the resin composition containing (C) the indane polyimide resin in combination with (A) the epoxy resin and (B) the active ester compound is reduced. Since the polarity is small in this way, the dielectric loss tangent of the cured product of the resin composition can be lowered. In particular, when a hydrocarbon group such as a methyl group is bonded to the indane skeleton of the indane polyimide resin (C), the number of carbon atoms in the molecule of the indane polyimide resin (C) increases and the polarity can be made smaller. The dielectric loss tangent of the cured product can be particularly low.

Furthermore, by using the cured product of the resin composition, an insulating layer having excellent adhesion to the conductor layer can be realized. The adhesion between the insulating layer and the conductor layer can be evaluated by peel strength as a load when the conductor layer is peeled off by pulling it in a direction perpendicular to the insulating layer at room temperature. The peel strength is preferably as high as possible. Specifically, it is preferably 0.40 kgf/cm or more, more preferably 0.45 kgf/cm or more, still more preferably 0.50 kgf/cm or more, and particularly preferably 0.53 kgf. / cm or more. Although there is no particular upper limit, it is usually 1.2 kgf/cm or less. In particular, the insulating layer containing the cured product of the resin composition exhibits such a high peel strength even if the arithmetic mean roughness Ra (surface roughness) of the surface of the insulating layer after roughening treatment is small. It can significantly contribute to miniaturization of circuit wiring.

According to the present inventors, the mechanism for increasing the adhesion between the insulating layer containing the cured product of the resin composition and the conductor layer is presumed to be as follows. However, the technical scope of the present invention is not limited by the mechanism described below.
(C) The indane polyimide resin has an indane skeleton, so it usually has high rigidity. In addition, (C) the indane polyimide resin can be well mixed with (A) the epoxy resin and (B) the active ester compound. Therefore, the cured product of the resin composition has high mechanical strength. Therefore, in the vicinity of the interface between the insulating layer containing the cured resin composition and the conductor layer, the cured resin composition is less likely to break. Therefore, peeling of the conductor layer due to breakage of the cured product of the resin composition is unlikely to occur, and adhesion between the insulating layer and the conductor layer can be enhanced.

A cured product of the above resin composition usually has a high glass transition temperature, and is therefore excellent in heat resistance. A specific glass transition temperature of the resin composition is preferably 130° C. or higher, more preferably 150° C. or higher, and particularly preferably 155° C. or higher, or 160° C. or higher. Although the upper limit of the glass transition temperature is not particularly limited, it is preferably 200°C or lower, more preferably 190°C or lower, and particularly preferably 180°C or lower.
The glass transition temperature of the cured product of the resin composition can be measured by a tensile loading method (JIS K7197) using a thermomechanical analyzer.

By using the cured product of the resin composition, an insulating layer having a small surface roughness after roughening treatment can be obtained. The surface roughness can be represented by arithmetic mean roughness. The arithmetic mean roughness of the surface of the insulating layer after the roughening treatment is preferably as small as possible. , 110 nm or less, 100 nm or less, 95 nm or less, or 90 nm or less. Although the lower limit of the arithmetic mean roughness is not particularly limited, it is usually 0.5 nm or more.
The arithmetic average roughness of the surface of the insulating layer can be measured with a non-contact surface roughness meter (eg, "WYKO NT3300" manufactured by Bco Instruments).

Since it has excellent properties as described above, 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). , it can be particularly suitably used as a resin composition for forming an interlayer insulating layer of a multilayer printed wiring board. Moreover, since the resin composition of the present invention can provide an insulating layer having excellent component embedding properties, it can be suitably used when the printed wiring board is a component built-in circuit board. Furthermore, the resin composition of the present invention can be used as a prepreg material.

[13. Adhesive film]
An adhesive film can be obtained by using the resin composition of the present invention. This adhesive film has a support and a resin composition layer containing the resin composition provided on the support.

The thickness of the resin composition layer is preferably 900 μm or less, more preferably 800 μm or less, still more preferably 700 μm or less, and even more preferably 600 μm or less. From the viewpoint of thinning, the thickness of the resin composition layer may be 100 μm or less, 80 μm or less, 60 μm or less, 50 μm or less, or 40 μm or less. The lower limit of the thickness of the resin composition layer is not particularly limited, but may be 1 μm or more, 1.5 μm or more, or 2 μm or more.

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

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

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

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

Further, as the support, a support with a release layer having a release layer on the surface to be bonded to the resin composition layer may be used. The release agent used in the release layer of the release layer-attached support includes, for example, one or more release agents selected from the group consisting of alkyd resins, polyolefin resins, urethane resins, and silicone resins. . As the support with a release layer, a commercially available product may be used, for example, "SK-1" manufactured by Lintec Co., Ltd., "SK-1", " AL-5", "AL-7"; "Lumirror T6AM" manufactured by Toray Industries, Inc.;

The thickness of the support is not particularly limited, but is preferably in the range of 5 μm to 75 μm, more preferably in the range of 10 μm to 60 μm. When a release layer-attached support is used, the thickness of the release layer-attached support as a whole is preferably within the above range.

For the adhesive film, for example, a resin varnish containing an organic solvent and a resin composition is prepared, the resin varnish is applied onto a support using a coating device such as a die coater, and dried to form a resin composition layer. It can be manufactured by forming.

Examples of organic solvents include ketone solvents such as acetone, methyl ethyl ketone and cyclohexanone; acetic ester solvents such as ethyl acetate, butyl acetate, cellosolve acetate, propylene glycol monomethyl ether acetate and carbitol acetate; carbitols such as cellosolve and butyl carbitol. Solvents; aromatic hydrocarbon solvents such as toluene and xylene; amide solvents such as dimethylformamide, dimethylacetamide (hereinafter sometimes abbreviated as “DMAc”) and N-methylpyrrolidone; Moreover, one type of the organic solvent may be used alone, or two or more types may be used in combination at an arbitrary ratio.

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

The adhesive film may further have optional layers in combination with the support and the resin composition layer. For example, the adhesive film further has a protective film conforming to the support on the side of the resin composition layer that is not bonded to the support (that is, the side of the resin composition opposite to the support). good too. Although the thickness of the protective film is not particularly limited, it is, for example, 1 μm to 40 μm. The protective film can suppress the adhesion of dust and the like to the surface of the resin composition layer and the suppression of scratches. Also, the adhesive film can be wound into a roll and stored. When the adhesive film has a protective film, it can usually be used by peeling off the protective film.

[14. Prepreg]
A prepreg can be obtained by using the resin composition of the present invention. This prepreg has a sheet-like fiber base material and the resin composition impregnated in the sheet-like fiber base material.

The sheet-like fiber base material is not particularly limited, and for example, those commonly used as prepreg base materials such as glass cloth, aramid nonwoven fabric, and liquid crystal polymer nonwoven fabric can be used. The thickness of the sheet-like fiber base material is preferably 900 µm or less, more preferably 800 µm or less, even more preferably 700 µm or less, and particularly preferably 600 µm or less. Moreover, from the viewpoint of thinning, the thickness of the sheet-like fiber base material may be 30 μm or less, 20 μm or less, or 10 μm or less. Although the lower limit of the thickness of the sheet-like fiber base material is not particularly limited, it can be usually 1 μm or more, 1.5 μm or more, or 2 μm or more.

A prepreg can be produced by, for example, a hot melt method, a solvent method, or the like.

The thickness of the prepreg can be in the same range as the resin composition layer in the adhesive film described above.

The prepreg can be used, for example, to form an insulating layer of a printed wiring board, and particularly preferably used to form an interlayer insulating layer of a multilayer printed wiring board.

[15. Printed wiring board]
A printed wiring board can be obtained by using the resin composition of the present invention. This printed wiring board has an insulating layer containing a cured product of the resin composition.

A printed wiring board can be manufactured, for example, using an adhesive film by a method including the following steps (I) and (II).
(I) A step of laminating an adhesive film on the inner layer substrate such that the resin composition layer of the adhesive film is bonded to the inner layer substrate.
(II) A step of thermosetting the resin composition layer to form an insulating layer.

The "inner layer substrate" used in step (I) is mainly a substrate such as a glass epoxy substrate, a metal substrate, a ceramic substrate, a polyester substrate, a polyimide substrate, a BT resin substrate, a thermosetting polyphenylene ether substrate, or one side of the substrate. Or, it refers to a circuit board on which patterned conductor layers (corresponding to circuits) are formed on both sides. Further, an inner layer circuit board, which is an intermediate product on which an insulating layer and/or a conductor layer are to be further formed when manufacturing a printed wiring board, is also included in the above-mentioned "inner layer board". When the printed wiring board is a circuit board with built-in components, an inner layer board with built-in components can be used.

The lamination of the inner layer substrate and the adhesive film can be performed, for example, by thermocompression bonding the adhesive film to the inner layer substrate from the support side. Examples of the member for thermocompression bonding the adhesive film to the inner layer substrate (hereinafter sometimes referred to as "thermocompression member") include heated metal plates (such as SUS mirror plates) and metal rolls (such as SUS rolls). . Instead of directly pressing the thermocompression member onto the adhesive film, it is preferable to press the adhesive film through an elastic material such as heat-resistant rubber so that the adhesive film can sufficiently follow the unevenness of the surface of the inner layer substrate.

Lamination of the inner layer substrate and the adhesive film may be performed by, for example, a vacuum lamination method. In the vacuum lamination method, the thermocompression temperature is preferably in the range of 60° C. to 160° C., more preferably 80° C. to 140° C., and the thermocompression pressure is preferably 0.098 MPa to 1.77 MPa, more preferably 0. .29 MPa to 1.47 MPa, and the heat pressing time is preferably 20 seconds to 400 seconds, more preferably 30 seconds to 300 seconds. Lamination is preferably carried out under reduced pressure conditions of 26.7 hPa or less.

Lamination may be performed using a commercially available vacuum laminator. Commercially available vacuum laminators include, for example, a vacuum pressurized laminator manufactured by Meiki Seisakusho, a vacuum applicator manufactured by Nikko Materials, and the like.

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

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

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

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

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

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

When manufacturing a printed wiring board, (III) the step of drilling holes in the insulating layer, (IV) the step of roughening the insulating layer, and (V) the step of forming a conductor layer may be further carried out. These steps (III) to (V) may be carried out according to various methods used in the manufacture of printed wiring boards. When the support is removed after step (II), the support may be removed between step (II) and step (III), between step (III) and step (IV), or It may be performed between (IV) and step (V).

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

Step (IV) is a step of roughening the insulating layer. The procedure and conditions of the roughening treatment are not particularly limited, and any procedure and conditions used when forming an insulating layer of a printed wiring board can be adopted. For example, the insulating layer can be roughened by performing a swelling treatment with a swelling liquid, a roughening treatment with an oxidizing agent, and a neutralizing treatment with a neutralizing liquid in this order. Examples of the swelling liquid include, but are not limited to, alkaline solutions, surfactant solutions, and the like, preferably alkaline solutions. As the alkaline solution, a sodium hydroxide solution and a potassium hydroxide solution are more preferred. Examples of commercially available swelling liquids include "Swelling Dip Securigans P" and "Swelling Dip Securigans SBU" manufactured by Atotech Japan. Moreover, one type of swelling liquid may be used alone, or two or more types may be used in combination at an arbitrary ratio. The swelling treatment with the swelling liquid is not particularly limited, but can be performed, for example, by immersing the insulating layer in the swelling liquid at 30.degree. C. to 90.degree. C. for 1 to 20 minutes. From the viewpoint of suppressing the swelling of the resin 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. Examples of the oxidizing agent include, but are not limited to, an alkaline permanganate solution in which potassium permanganate or sodium permanganate is dissolved in an aqueous solution of sodium hydroxide. Moreover, one type of oxidizing agent may be used alone, or two or more types may be used in combination at an arbitrary ratio. The roughening treatment with an oxidizing agent such as an alkaline permanganate solution is preferably carried out by immersing the insulating layer in an oxidizing agent solution heated to 60° C. to 80° C. for 10 to 30 minutes. The permanganate concentration in the alkaline permanganate solution is preferably 5% by mass to 10% by mass. Examples of commercially available oxidizing agents include alkaline permanganate solutions such as "Concentrate Compact CP" and "Dosing Solution Security P" manufactured by Atotech Japan. Moreover, as a neutralizing liquid, an acidic aqueous solution is preferable, and as a commercial product, for example, "Reduction Solution Securigant P" manufactured by Atotech Japan Co., Ltd. can be mentioned. Further, the neutralizing liquid may be used singly, or two or more types may be used in combination at an arbitrary ratio. The treatment with the neutralizing solution can be carried out by immersing the treated surface roughened with the oxidizing agent in the neutralizing solution at 30° C. to 80° C. for 5 to 30 minutes. From the viewpoint of workability, etc., a method of immersing an object roughened with an oxidizing agent in a neutralizing solution at 40° C. to 70° C. for 5 to 20 minutes is preferable.

Step (V) is a step of forming a conductor layer.

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

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

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

The conductor layer may be formed by plating. For example, a conductive layer having a desired wiring pattern can be formed by plating the surface of the insulating layer by techniques such as a semi-additive method and a full-additive method. An example of forming a conductor layer by a semi-additive method is shown below.

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

When using an adhesive film whose support is a metal foil, the conductor layer may be formed by a subtractive method or a modified semi-additive method using the metal foil derived from the adhesive film.

Also, the printed wiring board may be manufactured using the prepreg described above. The method of manufacturing a printed wiring board using prepreg is basically the same as the method using an adhesive film.

[16. semiconductor device]
A semiconductor device of the present invention includes a printed wiring board. A semiconductor device can be manufactured using a printed wiring board.

Examples of semiconductor devices include various semiconductor devices used in electrical appliances (eg, computers, mobile phones, digital cameras, televisions, etc.) and vehicles (eg, motorcycles, automobiles, trains, ships, aircraft, etc.).

A semiconductor device can be manufactured, for example, by mounting a component (semiconductor chip) on a conductive portion of a printed wiring board. A "conducting part" is a "part where an electric signal is transmitted on a printed wiring board", and the place may be a surface or an embedded part. Also, the semiconductor chip may optionally use an electric circuit element made of a semiconductor.

A method for mounting a semiconductor chip when manufacturing a semiconductor device is not particularly limited as long as the semiconductor chip functions effectively. Examples of mounting methods include wire bonding mounting method, flip chip mounting method, mounting method by bumpless build-up layer (BBUL), mounting method by anisotropic conductive film (ACF), and mounting by non-conductive film (NCF). methods, and the like. Here, "a mounting method using a build-up layer without bumps (BBUL)" means "a mounting method in which a semiconductor chip is directly embedded in a concave portion of a printed wiring board and the semiconductor chip and wiring on the printed wiring board are connected." is.

EXAMPLES Hereinafter, the present invention will be specifically described with reference to Examples. However, the present invention is not limited to the examples shown below. In the following description, "parts" and "%" representing amounts are based on mass unless otherwise specified.

In the following description, "MEK" indicates methyl ethyl ketone and "PET" indicates polyethylene terephthalate unless otherwise specified.

[Synthesis Example 1]
A 500 mL separable flask equipped with a water content receiver connected to a reflux condenser, a nitrogen inlet tube, and a stirrer was prepared. The flask was charged with 20.3 g 4,4′-oxydiphthalic anhydride (ODPA), 200 g γ-butyrolactone, 20 g toluene, and 5-(4-aminophenoxy)-3-[4-(4-aminophenoxy). Phenyl]-1,1,3-trimethylindane (29.6 g) was added, and the mixture was stirred at 45° C. for 2 hours under a nitrogen stream to carry out a reaction.

Then, the temperature of this reaction solution was raised, and the condensed water was azeotropically removed together with toluene under a nitrogen stream while maintaining the temperature at about 160°C. It was confirmed that a predetermined amount of water was accumulated in the water content receiver, and that water was no longer seen to flow out. After confirmation, the reaction solution was further heated and stirred at 200° C. for 1 hour. Then, it was cooled to obtain a varnish containing 20% by mass of a polyimide resin having a 1,1,3-trimethylindane skeleton. The obtained polyimide resin had a repeating unit represented by the following formula (X1) and a repeating unit represented by (X2). Moreover, the weight average molecular weight of the polyimide resin was 12,000.

[Example 1]
30 parts of bisphenol A type epoxy resin ("828US" manufactured by Mitsubishi Chemical Corporation, epoxy equivalent of about 180) and 30 parts of biphenyl type epoxy resin ("NC3000H" manufactured by Nippon Kayaku Co., Ltd., epoxy equivalent of about 269), solvent naphtha 55 The mixture was dissolved by heating while stirring, and then cooled to room temperature to obtain a mixed solution.

As an inorganic filler, spherical silica (average particle size 0.5 μm, “SO-C2” manufactured by Admatechs) surface-treated with an aminosilane coupling agent (“KBM573” manufactured by Shin-Etsu Chemical Co., Ltd.) was prepared. 260 parts of this spherical silica and 3 parts of methacrylic butadiene styrene rubber particles (“EXL-2655” manufactured by Dow Chemical Japan) as an organic filler are added to the above mixed solution and kneaded with a triple roll. A roll dispersion was obtained by uniform dispersion.

To the roll dispersion, 40 parts of a solution of an active ester compound ("HPC-8000-65T" manufactured by DIC, an active group equivalent of the active ester compound of about 223, a toluene solution of 65% by mass of nonvolatile components), synthesized in Synthesis Example 1 60 parts of a varnish containing a polyimide resin (γ-butyrolactone solution with a solid content of 20% by mass), and a solution of a curing accelerator (4-dimethylaminopyridine as a curing accelerator, a methyl ethyl ketone solution with a solid content of 5% by mass) 6 parts were mixed and uniformly dispersed with a high-speed rotating mixer to prepare a resin varnish.

As a support, a PET film with an alkyd resin release layer (“AL5” manufactured by Lintec Corporation, thickness 38 μm) was prepared. The resin varnish was uniformly applied onto the release layer of this support so that the thickness of the resin composition layer after drying was 40 μm. After that, it was dried at 80° C. to 120° C. (average 100° C.) for 5 minutes to obtain an adhesive film having a support and a resin composition layer.

[Example 2]
In Example 1, 14 parts of a solution of a triazine skeleton-containing phenolic curing agent (“LA-3018-50P” manufactured by DIC, a 2-methoxypropanol solution with a hydroxyl equivalent of about 151 and a solid content of 50%) was added to the roll dispersion. , further mixed. A resin varnish and an adhesive film were produced in the same manner as in Example 1 except for the above matters.

[Example 3]
In Example 2, 30 parts of biphenyl type epoxy resin ("NC3000H" manufactured by Nippon Kayaku Co., Ltd., epoxy equivalent of about 269) was changed to 30 parts of naphthol type epoxy resin ("ESN475V" manufactured by Nippon Steel & Sumikin Chemical Co., Ltd., epoxy equivalent of 332). did. A resin varnish and an adhesive film were produced in the same manner as in Example 2 except for the above matters.

[Example 4]
In Example 2, 30 parts of biphenyl-type epoxy resin ("NC3000H" manufactured by Nippon Kayaku Co., Ltd., epoxy equivalent of about 269) was added to 30 parts of bixylenol-type epoxy resin ("YX4000HK" manufactured by Mitsubishi Chemical Corporation, epoxy equivalent of about 185). changed. A resin varnish and an adhesive film were produced in the same manner as in Example 2 except for the above matters.

[Example 5]
In Example 2, 60 parts of the varnish containing the polyimide resin synthesized in Synthesis Example 1 (γ-butyrolactone solution with a solid content of 20% by mass) was added to the varnish containing the polyimide resin synthesized in Synthesis Example 1 (solid content of 20% by mass). γ-butyrolactone solution) and 20 parts of a solution containing a phenoxy resin ("YX6954BH30" manufactured by Mitsubishi Chemical Corporation, a solution with a solid content of 30% by mass, the solvent being a 1:1 mixed solvent of MEK and cyclohexanone). A resin varnish and an adhesive film were produced in the same manner as in Example 2 except for the above matters.

[Comparative Example 1]
In Example 1, 60 parts of the varnish containing the polyimide resin synthesized in Synthesis Example 1 (γ-butyrolactone solution with a solid content of 20% by mass) was added to a phenoxy resin (“YX6954BH30” manufactured by Mitsubishi Chemical Corporation, a solution with a solid content of 30% by mass). , the solvent was changed to 40 parts of a 1:1 mixed solvent of MEK and cyclohexanone). A resin varnish and an adhesive film were produced in the same manner as in Example 1 except for the above matters.

[Comparative Example 2]
In Example 1, the amount of spherical silica (average particle size 0.5 μm, “SO-C2” manufactured by Admatechs) surface-treated with an aminosilane coupling agent (“KBM573” manufactured by Shin-Etsu Chemical Co., Ltd.) was changed to 109 changed to department. In addition, the amount of the active ester compound solution ("HPC-8000-65T" manufactured by DIC, active group equivalent of the active ester compound of about 223, and a toluene solution containing 65% by mass of non-volatile components) was changed to 48 parts. Further, a polyimide resin solution (Arakawa Chemical Co., Ltd. "PIAD200" manufactured by Kogyo Co., Ltd., a solution with a solid content of 30% by mass, and the solvent was changed to 433 parts of a mixed solvent of cyclohexanone, dimethyl glycol and methylcyclohexane). A resin varnish and an adhesive film were produced in the same manner as in Example 1 except for the above matters.

[Evaluation method]
The adhesive films produced in the Examples and Comparative Examples described above were evaluated by the following methods.

[Preparation of sample for measurement]
(1) Surface treatment of inner layer circuit board:
A glass cloth-based epoxy resin double-sided copper-clad laminate (copper foil thickness 18 μm, substrate thickness 0.4 mm, Panasonic "R1515A") having copper foil on both sides as an inner layer circuit is used as an inner layer circuit board. prepared. Both surfaces of the inner layer circuit board were etched with an etching agent (“CZ8101” manufactured by MEC Co., Ltd.) at a copper etching amount of 1 μm to roughen the copper surface.

(2) Lamination of adhesive film:
The adhesive films prepared in Examples and Comparative Examples are bonded to the inner layer circuit board using a batch-type vacuum pressure laminator ("MVLP-500" manufactured by Meiki Seisakusho Co., Ltd.) so that the resin composition layer is bonded to the inner layer circuit board. Both sides of the substrate were laminated. The lamination process was carried out by pressure bonding for 30 seconds at 100° C. and pressure of 0.74 MPa after reducing the pressure for 30 seconds to adjust the atmospheric pressure to 13 hPa or less.

(3) Curing of the resin composition:
After laminating the inner layer circuit board and the adhesive film, the resin composition layer was 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 was peeled off to expose the insulating layer. As a result, a multi-layer substrate having an insulating layer, an inner layer circuit board, and an insulating layer in this order was obtained.

(4) Roughening treatment:
The multilayer substrate having the exposed insulating layer is immersed in a swelling liquid (“Swelling Dip Securigant P” manufactured by Atotech Japan Co., Ltd., an aqueous sodium hydroxide solution containing diethylene glycol monobutyl ether) at 60° C. for 10 minutes, and then Immersed in an oxidizing agent ("Concentrate Compact CP" manufactured by Atotech Japan Co., Ltd., an aqueous solution with a potassium permanganate concentration of about 6% by mass and a sodium hydroxide concentration of about 4% by mass) at 80 ° C. for 20 minutes, and then a neutralizing solution. ("Reduction Solution Securigant P" manufactured by Atotech Japan, hydroxylamine sulfate aqueous solution) at 40°C for 5 minutes. Then, it was dried at 80° C. for 30 minutes to obtain a multi-layer substrate having a roughened surface. This multilayer substrate subjected to the roughening treatment may be hereinafter referred to as "evaluation substrate a".

(5) Formation of conductor layer:
A conductor layer was formed on the roughened surface of the insulating layer of the evaluation substrate a according to the semi-additive method. Specifically, the following operations were performed.
The roughened multilayer substrate (that is, evaluation substrate a) was immersed in an electroless plating solution containing PdCl ₂ at 40° C. for 5 minutes. After that, this multilayer substrate was immersed in an electroless copper plating solution at 25° C. for 20 minutes. Next, this multilayer substrate was subjected to an annealing treatment of heating at 150° C. for 30 minutes. After that, an etching resist was formed on the surface of this multilayer substrate, and a pattern was formed by etching. Thereafter, copper sulfate electroplating was performed to form a conductor layer with a thickness of 30 μm. After that, the substrate was annealed at 200° C. for 60 minutes to obtain an “evaluation substrate b” having a conductor layer.

[Measurement of arithmetic mean roughness (Ra)]
The average value of the arithmetic mean roughness Ra of 10 randomly selected points on the surface of the evaluation substrate a was measured as the arithmetic mean roughness Ra of the evaluation substrate a. The arithmetic average roughness Ra at each point is measured using a non-contact surface roughness meter ("WYKO NT3300" manufactured by Bcoinstruments) in VSI contact mode with a 50x lens, with a measurement range of 121 µm × 92 µm. ,gone.

[Measurement of peel strength of conductor layer]
The peel strength of the insulating layer and the conductor layer was measured for the evaluation substrate b in accordance with Japanese Industrial Standards (JIS C6481). Specifically, the procedure was as follows.
A cut was made in the conductor layer of the evaluation substrate b so as to surround a rectangular portion with a width of 10 mm and a length of 100 mm. One longitudinal end of this rectangular portion was peeled off and gripped with a gripper. At room temperature, the gripper was pulled vertically at a speed of 50 mm/min to peel off a 35 mm length of the rectangular portion, and the load (kgf/cm) when this was peeled off was measured as the peel strength. did. A tensile tester ("AC-50C-SL" manufactured by TSE) was used for the above measurements.

[Measurement of minimum melt viscosity]
The melt viscosities of the resin composition layers in the adhesive films prepared in Examples and Comparative Examples were measured using a dynamic viscoelasticity measuring device ("Rheosol-G3000" manufactured by UBM Co., Ltd.). This measurement was performed on a 1 g sample taken from the resin composition layer using a parallel plate with a diameter of 18 mm. The measurement conditions were a starting temperature of 60° C. to 200° C., a temperature increase rate of 5° C./min, a measurement temperature interval of 2.5° C., and a vibration of 1 Hz/deg. The lowest melt viscosity was obtained from the measured values of the obtained melt viscosities.

[Measurement of glass transition temperature]
The adhesive films prepared in Examples and Comparative Examples were heated at 200° C. for 90 minutes to thermally cure the resin composition layer. Thereafter, the support was peeled off to obtain a cured product obtained by curing the resin composition layer. This cured product may be hereinafter referred to as "evaluation cured product c".

A test piece having a width of about 5 mm and a length of about 15 mm was cut from the evaluation cured product c. This test piece was subjected to thermomechanical analysis by a tensile load method using a thermomechanical analyzer (“Thermo Plus TMA8310” manufactured by Rigaku Corporation). Specifically, after mounting the test piece on the thermomechanical analyzer, the measurement was continuously performed twice under the measurement conditions of a load of 1 g and a temperature increase rate of 5° C./min. Then, in the second measurement, the glass transition temperature (°C) was calculated.

[Measurement of dielectric loss tangent]
A test piece having a width of 2 mm and a length of 80 mm was cut from the evaluation cured product c. The dielectric loss tangent of these two test pieces was measured, and the average of the measured values was obtained as the dielectric loss tangent of the insulating layer. The dielectric loss tangent of the test piece was measured at a measurement frequency of 5.8 GHz and a measurement temperature of 23° C. by cavity resonance perturbation method using a measuring device ("HP8362B" manufactured by Agilent Technologies).

[result]
The results of the examples and comparative examples described above are shown in the table below. In the table below, the abbreviations have the following meanings.
828US: Bisphenol A type epoxy resin (“828US” manufactured by Mitsubishi Chemical Corporation).
NC3000H: Phenyl-type epoxy resin ("NC3000H" manufactured by Nippon Kayaku Co., Ltd.).
ESN475V: naphthol type epoxy resin (“ESN475V” manufactured by Nippon Steel & Sumikin Chemical Co., Ltd.).
YX4000HK: Bixylenol type epoxy resin ("YX4000HK" manufactured by Mitsubishi Chemical Corporation).
HPC-8000-65T: Active ester compound ("HPC-8000-65T" manufactured by DIC).
LA3018-50P: A solution of a triazine skeleton-containing phenolic curing agent (“LA-3018-50P” manufactured by DIC).
PIAD200: Polyimide resin obtained by reacting tetracarboxylic acid with diamine dimer acid (“PIAD200” manufactured by Arakawa Chemical Industries, Ltd.).
YX6954BH30: phenoxy resin (“YX6954BH30” manufactured by Mitsubishi Chemical Corporation).
SO-C2: Spherical silica ("SO-C2" manufactured by Admatechs) surface-treated with an aminosilane coupling agent ("KBM573" manufactured by Shin-Etsu Chemical Co., Ltd.).
EXL-2655: Methacryl-butadiene styrene rubber particles ("EXL-2655" manufactured by Dow Chemical Japan).
DMAP: 4-dimethylaminopyridine.
Inorganic filler content: The ratio of the inorganic filler to 100% by mass of the non-volatile components in the resin composition.
Ra: Arithmetic mean roughness of the surface of the evaluation substrate a.

[examination]
The resin composition of Example 1 and the resin composition of Comparative Example 1 have the same composition except for the type of thermoplastic resin used in combination with (A) the epoxy resin and (B) the active ester compound. Among them, in Comparative Example 1 in which (C) the indane polyimide resin is not used as the thermoplastic resin, the minimum melt viscosity is in a good range, but the peel strength of the conductor layer is low and the dielectric loss tangent is large. On the other hand, in Example 1 using (C) indane polyimide resin as the thermoplastic resin, the minimum melt viscosity is in a good range, the peel strength of the conductor layer is large, and the dielectric loss tangent can be effectively reduced. ing. Therefore, from the results of Example 1 and Comparative Example 1, it can be seen that by combining (C) indane polyimide resin with (A) epoxy resin and (B) active ester compound, the dielectric loss tangent is low and adhesion to the conductor layer is low. It was confirmed that an insulating layer having high properties can be obtained and a resin composition having a minimum melt viscosity within an appropriate range can be realized.

Further, although the compositions of the resin compositions according to Examples 1 to 5 are different, they are common in that they contain (C) an indane polyimide resin in combination with (A) an epoxy resin and (B) an active ester compound. there is The resin compositions according to these Examples 1 to 5 have the lowest melt viscosity and conductor layer strength than the resin compositions having the same compositions as those of Examples 1 to 5 except that (C) does not contain the indane polyimide resin. Good results are obtained for peel strength and dielectric loss tangent. For example, although the dielectric loss tangent of Example 5 is inferior to that of Comparative Example 1, it is superior to the case of using a resin composition having the same composition as that of Example 5 except that (C) the indane polyimide resin is not included. good results have been obtained. Therefore, from the results of Examples 1 to 5, the minimum melt viscosity is kept within an appropriate range in a resin composition having a wide range of compositions including (A) an epoxy resin, (B) an active ester compound, and (C) an indane polyimide resin. However, it was confirmed that an insulating layer having a low dielectric loss tangent and high adhesion to the conductor layer can be realized.

Comparative Example 2 is an experimental example of a conventional resin composition in which the dielectric loss tangent was particularly small within the scope investigated by the present inventors. In Comparative Example 2, although the dielectric loss tangent is particularly small, the minimum melt viscosity is too small and the peel strength is significantly inferior. Therefore, it is difficult to use the resin composition of Comparative Example 2 as a resin composition for forming an insulating layer. On the other hand, the resin compositions of Examples 1 to 5 can be said to be industrially excellent materials because they are excellent in well-balanced properties required for resin compositions for forming an insulating layer.

Claims (21)

A resin composition comprising (A) an epoxy resin, (B) an active ester compound, (C) a polyimide resin having an indane skeleton, (E) an organic filler, and (G) a curing agent,
The amount of component (E) is 0.1% by mass to 20% by mass with respect to 100% by mass of the resin component in the resin composition,
(G) the curing agent contains a phenolic curing agent (but does not contain an aromatic amine curing agent) ,
Resin composition. 2. The resin composition according to claim 1, wherein component (A) comprises a liquid epoxy resin. 3. The resin composition according to claim 1, wherein the component (A) comprises a liquid epoxy resin and a solid epoxy resin. A resin composition comprising (A) an epoxy resin, (B) an active ester compound, (C) a polyimide resin having an indane skeleton, and (G) a curing agent,
(A) component contains a liquid epoxy resin,
(G) the curing agent contains a phenolic curing agent (but does not contain an aromatic amine curing agent) ,
Resin composition. 5. The resin composition according to claim 4, wherein component (A) comprises a liquid epoxy resin and a solid epoxy resin. (E) The resin composition according to claim 4 or 5, comprising an organic filler. 7. The resin composition according to claim 6, wherein the amount of component (E) is 0.1% by mass to 20% by mass with respect to 100% by mass of the resin component in the resin composition. 8. The resin composition according to any one of claims 1 to 3, 6 and 7, wherein component (E) is one or more selected from rubber particles, polyamide particles and silicone particles. The resin composition according to any one of claims 1 to 3 and 6 to 8, wherein the particles of component (E) have an average particle size of 5 µm or less. The resin composition according to any one of claims 1 to 9, wherein component (C) has a trimethylindane skeleton. The resin composition according to any one of claims 1 to 10, wherein component (C) has a 1,1,3-trimethylindane skeleton. The resin composition according to any one of claims 1 to 11, wherein the amount of component (C) is 1% by mass to 20% by mass with respect to 100% by mass of the resin component in the resin composition. (D) The resin composition according to any one of claims 1 to 12, comprising an inorganic filler. 14. The resin composition according to claim 13, wherein the amount of component (D) is 50% by mass or more with respect to 100% by mass of non-volatile components in the resin composition. The resin composition according to any one of claims 1 to 14, which has a minimum melt viscosity of 200 poise or more. The resin composition according to any one of claims 1 to 15, which is a resin composition for forming an insulating layer of a printed wiring board. A resin composition comprising (A) an epoxy resin, (B) an active ester compound, (C) a polyimide resin having an indane skeleton, and (G) a curing agent,
(G) the curing agent contains a phenolic curing agent (but does not contain an aromatic amine curing agent) ,
Resin composition. An adhesive film comprising a support and a resin composition layer containing the resin composition according to any one of claims 1 to 17 provided on the support. A prepreg comprising a sheet-like fiber base material and the resin composition according to any one of claims 1 to 17 impregnated in the sheet-like fiber base material. A printed wiring board having an insulating layer containing a cured product of the resin composition according to any one of claims 1 to 17. A semiconductor device comprising the printed wiring board according to claim 20 .