CN108727942A - Resin combination - Google Patents

Abstract

The resin combination etc. that the issue of the present invention is to provide minimum melt viscosities is low, plyability is excellent, even if the resin combination if average grain diameter is small or the inorganic filling material of large specific surface area using can obtain the solidfied material that fine circuits Forming ability is excellent, dielectric loss angle tangent is low.The solution of the present invention is a kind of resin combination, is contained：(A) epoxy resin, (B) active ester system curing agent, (C) polyimide resin and (D) average grain diameter are 100nm inorganic filling materials below, wherein, when resin component is set as 100 mass %, the content of (C) ingredient is 0.1 mass % or more and 6 mass % or less.

Description

resin composition

technical field

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

Background technique

As a manufacturing technique of a printed wiring board, a manufacturing method based on a buildup system in which insulating layers and conductor layers are alternately laminated is known. In the manufacturing method based on the stacking method, the insulating layer is usually formed by curing the resin composition. For example, Patent Document 1 describes forming an insulating layer by curing a resin composition containing an epoxy resin, an active ester compound, a carbodiimide compound, a thermoplastic resin, and an inorganic filler.

prior art literature

patent documents

Patent Document 1: Japanese Patent Laid-Open No. 2016-27097.

Contents of the invention

The problem to be solved by the invention

As a result of further studies on the resin composition, the inventors of the present invention obtained the following findings. When a large amount of the inorganic filler is contained in the resin composition, the minimum melt viscosity of the resin composition increases, and the embedding property of the film decreases. As a result, it was recognized that it becomes difficult to control laminarity. In particular, from the viewpoint of thinning, etc., when the resin composition contains an inorganic filler with a small average particle size or a large specific surface area, the minimum melt viscosity of the resin composition further increases, and the embedding property decreases significantly.

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

means to solve the problem

In order to achieve the subject of the present invention, the present inventors have conducted intensive studies, and as a result, found that when a predetermined amount of component (C) is contained in the resin composition, a resin composition with a low minimum melt viscosity and excellent lamination properties can be obtained. This resin composition can obtain a cured product excellent in microcircuit forming ability and low dielectric loss tangent even if an inorganic filler having a small average particle size or a large specific surface area is used, and the present invention has been completed.

That is, the present invention includes the following contents;

[1] A resin composition comprising:

(A) epoxy resin,

(B) active ester curing agent,

(C) polyimide resin, and

(D) inorganic filler material,

Among them, the average particle diameter of the component (D) is 100 nm or less,

When the resin component is 100% by mass, the content of the component (C) is not less than 0.1% by mass and not more than 6% by mass;

[2] A resin composition comprising:

(A) epoxy resin,

(B) active ester curing agent,

(C) polyimide resin, and

(D) inorganic filler material,

Among them, the specific surface area of the component (D) is 15 m ² /g or more,

When the resin component is 100% by mass, the content of the component (C) is not less than 0.1% by mass and not more than 6% by mass;

[3] The resin composition according to [1] or [2], wherein the component (C) is a polyimide resin having a polycyclic aromatic hydrocarbon skeleton;

[4] The resin composition according to [3], wherein the polycyclic aromatic hydrocarbon skeleton is an aromatic hydrocarbon skeleton formed by condensing a five-membered ring compound and an aromatic ring;

[5] The resin composition according to [3] or [4], wherein the polycyclic aromatic hydrocarbon skeleton is at least any one of an indane skeleton and a fluorene skeleton;

[6] The resin composition according to any one of [1] to [5], wherein the weight average molecular weight of the component (C) is 5000 or more;

[7] The resin composition according to any one of [1] to [6], wherein the component (C) has a repeating unit having a polycyclic aromatic hydrocarbon skeleton and a repeating unit having an imide structure;

[8] The resin composition according to [7], wherein the mass ratio of the repeating unit having a polycyclic aromatic hydrocarbon skeleton to the repeating unit having an imide structure (the mass of the repeating unit having a polycyclic aromatic hydrocarbon skeleton/the mass ratio of the repeating unit having an imide structure) The mass of the repeating unit of the imine structure) is 0.5 or more and 2 or less;

[9] The resin composition according to any one of [1] to [8], wherein the content of component (C) is 0.1% by mass when the non-volatile matter in the resin composition is 100% by mass Above and below 3% by mass;

[10] The resin composition according to any one of [1] to [9], wherein the content of component (B) is 1% by mass when the non-volatile matter in the resin composition is 100% by mass Above and below 25% by mass;

[11] The resin composition according to any one of [1] to [10], wherein the content of component (D) is 30% by mass when the non-volatile matter in the resin composition is 100% by mass More than 80% by mass;

[12] The resin composition according to any one of [1] to [11], further comprising (E) a curing agent;

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

[14] The resin composition according to any one of [1] to [13], which is used to form an insulating layer for forming a conductor layer;

[15] The resin composition according to any one of [1] to [14], which is used to form an insulating layer of a printed wiring board;

[16] The resin composition according to any one of [1] to [15], which is used to form an interlayer insulating layer of a printed wiring board;

[17] A resin sheet comprising a support, and a resin composition layer according to any one of [1] to [16] provided on the support;

[18] A printed wiring board comprising a first conductor layer, a second conductor layer, and an insulating layer formed between the first conductor layer and the second conductor layer, wherein,

The insulating layer is a cured product of the resin composition described in any one of [1] to [16];

[19] A semiconductor device including the printed wiring board according to [18].

The effect of the invention

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

Description of drawings

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

Detailed ways

Hereinafter, the resin composition, resin sheet, printed wiring board, and semiconductor device of this invention are demonstrated in detail.

[resin composition]

The resin composition of the first embodiment of the present invention contains (A) epoxy resin, (B) active ester curing agent, (C) polyimide resin, and (D) inorganic filler, (D) component The average particle diameter is 100 nm or less, and when the resin component is 100 mass %, content of (C)component is 0.1 mass % or more and 6 mass % or less. By making the resin composition of the first embodiment contain the component (C), a resin composition with a low minimum melt viscosity and excellent lamination properties can be obtained even if the resin composition contains (D) a component having an average particle diameter of 100 nm or less Inorganic fillers can also be used to obtain a cured product with excellent fine circuit forming ability and low dielectric loss tangent. In addition, the resin composition of the second embodiment is a resin composition containing (A) epoxy resin, (B) active ester curing agent, (C) polyimide resin, and (D) inorganic filler, ( The specific surface area of D) component is 15 m< ² >/g or more, and content of (C) component is 0.1 mass % or more and 6 mass % or less when the resin component is 100 mass %. By including the component (C) in the resin composition of the second embodiment, a resin composition having a low minimum melt viscosity and excellent lamination properties can be obtained even if the resin composition contains (D) with a specific surface area of 15 m ² /g With the above inorganic fillers, a cured product having excellent fine circuit forming ability and low dielectric loss tangent can be obtained.

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

＜(A) Epoxy resin＞

The resin composition contains (A) epoxy resin. Examples of epoxy resins include bixylenol epoxy resins, bisphenol A epoxy resins, bisphenol F epoxy resins, bisphenol S epoxy resins, and bisphenol AF epoxy resins. Epoxy resin, dicyclopentadiene type epoxy resin, triphenol type epoxy resin, naphthol novolac type epoxy resin, phenol novolac type epoxy resin, tert-butyl-o-phenyl Diphenol type epoxy resin, naphthalene type epoxy resin, naphthol type epoxy resin, anthracene type epoxy resin, glycidyl amine type epoxy resin, glycidyl ester type epoxy resin, cresol novolac ) type epoxy resin, biphenyl type epoxy resin, linear aliphatic epoxy resin, epoxy resin with butadiene structure, alicyclic epoxy resin, heterocyclic epoxy resin, spiro ring-containing ring Oxygen resins, cyclohexane-type epoxy resins, cyclohexanedimethanol-type epoxy resins, naphthylene ether-type epoxy resins, trimethylol-type epoxy resins, tetraphenylethane-type epoxy resins, and the like. The epoxy resins may be used alone or in combination of two or more.

The epoxy resin preferably includes an epoxy resin having two or more epoxy groups in one molecule. When the non-volatile content of an epoxy resin is 100 mass %, it is preferable that at least 50 mass % or more is an epoxy resin which has 2 or more epoxy groups in 1 molecule. Among them, the resin composition preferably contains, in combination, an epoxy resin that is liquid at a temperature of 20°C (hereinafter referred to as "liquid epoxy resin") and an epoxy resin that is solid at a temperature of 20°C (hereinafter also referred to as "liquid epoxy resin"). Solid Epoxy Resins".). The liquid epoxy resin is preferably a liquid epoxy resin having two or more epoxy groups in one molecule, more preferably an aromatic liquid epoxy resin having two or more epoxy groups in one molecule. The solid epoxy resin is preferably a solid epoxy resin having three or more epoxy groups in one molecule, more preferably an aromatic solid epoxy resin having three or more epoxy groups in one molecule. In the present invention, the term "aromatic epoxy resin" refers to an epoxy resin having an aromatic ring in its molecule.

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

As the solid epoxy resin, bixylenol type epoxy resin, naphthalene type epoxy resin, naphthalene type tetrafunctional epoxy resin, cresol novolak type epoxy resin, dicyclopentadiene type epoxy resin, triphenol Type epoxy resin, naphthol type epoxy resin, biphenyl type epoxy resin, naphthylene ether type epoxy resin, anthracene type epoxy resin, bisphenol A type epoxy resin, bisphenol AF type epoxy resin, Tetraphenylethane type epoxy resin, more preferably bixylenol type epoxy resin, naphthalene type epoxy resin, bisphenol AF type epoxy resin, naphthol type epoxy resin, biphenyl type epoxy resin and ethylene oxide resin The naphthyl ether-type epoxy resin is more preferably a bixylenol-type epoxy resin, a naphthol-type epoxy resin, or a biphenyl-type epoxy resin. Specific examples of solid epoxy resins include "HP4032H" (naphthalene-type epoxy resin), "HP-4700", "HP-4710" (naphthalene-type tetrafunctional epoxy resin) manufactured by DIC Corporation, "N -690" (cresol novolac epoxy resin), "N-695" (cresol novolac epoxy resin), "HP-7200" (dicyclopentadiene epoxy resin), "HP-7200HH" , "HP-7200H", "EXA-7311", "EXA-7311-G3", "EXA-7311-G4", "EXA-7311-G4S", "HP6000" (naphthylene ether type epoxy resin) , "EPPN-502H" (triphenol type epoxy resin), "NC7000L" (naphthol novolac type epoxy resin), "NC3000H", "NC3000", "NC3000L", "NC3100" ( Biphenyl type epoxy resin), "ESN475V" (naphthalene type epoxy resin) manufactured by Nippon Steel Sumikin Chemical Co., Ltd., "ESN485" (naphthol novolac type epoxy resin), "YX4000H" manufactured by Mitsubishi Chemical Corporation, " YX4000", "YL6121" (biphenyl type epoxy resin), "YX4000HK" (bixylenol type epoxy resin), "YX8800" (anthracene type epoxy resin), manufactured by Osaka Gas Chemical Co., Ltd. "PG-100", "CG-500", "YL7760" (bisphenol AF type epoxy resin) manufactured by Mitsubishi Chemical Corporation, "YL7800" (fluorene type epoxy resin), "jER1010" manufactured by Mitsubishi Chemical Corporation (solid bisphenol A type epoxy resin), "jER1031S" (tetraphenylethane type epoxy resin), etc. These may be used individually by 1 type, and may use it in combination of 2 or more types.

When a liquid epoxy resin and a solid epoxy resin are used together as (A) component, it is preferable that these quantity ratios (liquid epoxy resin: solid epoxy resin) are the range of 1:0.1-1:20 by mass ratio. By making the amount ratio of the liquid epoxy resin to the solid epoxy resin within the above range, the following effects can be obtained: i) when used in the form of a resin sheet, moderate adhesiveness can be brought; ii) when used in the form of a resin When used in the form of a sheet, sufficient flexibility can be obtained to improve handling; and, iii) a cured product with sufficient breaking strength can be obtained; and the like. From the viewpoint of the effects of i) to iii) above, the mass ratio of the liquid epoxy resin to the solid epoxy resin (liquid epoxy resin: solid epoxy resin) is more preferably 1:0.2 to 1:5 in terms of mass ratio The range of , more preferably the range of 1:0.3 to 1:1.

The content of component (A) in the resin composition is preferably It is 15 mass % or more, More preferably, it is 20 mass % or more, More preferably, it is 25 mass % or more. The upper limit of the content of the epoxy resin is not particularly limited as long as the effect of the present invention can be exerted, and it is preferably 60% by mass or less, more preferably 45% by mass or less, 40% by mass or less, or 35% by mass or less .

(A) The epoxy equivalent of a component becomes like this. Preferably it is 50-5000, More preferably, it is 50-3000, More preferably, it is 80-2000, More preferably, it is 110-1000. Within this range, the crosslink density of the cured product becomes sufficient, and an insulating layer with a small surface roughness can be formed. In addition, epoxy equivalent can be measured according to JISK7236, and is the mass of resin containing 1 equivalent of epoxy groups.

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

＜(B) Active ester curing agent＞

The resin composition contains (B) active ester type hardening|curing agent. The active ester-based curing agent is an active ester compound having one or more active ester groups in one molecule. As the active ester-based curing agent, an active ester-based curing agent having two or more active ester groups in one molecule is preferred, for example, phenol esters, thiophenol esters, N -Active ester-based curing agents having two or more highly reactive ester groups in one molecule, such as hydroxyamine esters and esters of heterocyclic hydroxy compounds. The active ester-based curing agent may be used alone or in combination of two or more.

From the viewpoint of improving heat resistance, an active ester-based curing agent obtained by condensation reaction of a carboxylic acid compound and/or a thiocarboxylic acid compound with a hydroxyl compound and/or a thiol compound is preferable. Wherein, more preferably make carboxylic acid compound and be selected from phenol (phenol, phenol) compound, naphthol compound and thiol compound more than 1 kinds of active ester curing agent that react and obtain, more preferably make carboxylic acid compound and have An aromatic compound having two or more active ester groups in one molecule obtained by reacting an aromatic compound with a phenolic hydroxyl group, and more preferably a carboxylic acid compound having at least two or more carboxyl groups in one molecule and a carboxylic acid compound having a phenolic hydroxyl group An aromatic compound having two or more active ester groups in one molecule obtained by reacting a hydroxy aromatic compound. The active ester curing agent may be linear or branched. Moreover, when the carboxylic acid compound which has at least 2 or more carboxyl groups in 1 molecule is a compound containing an aliphatic chain, the compatibility with a resin composition can be improved, and when it is a compound which has an aromatic ring, heat resistance can be improved.

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

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

The phenol compound preferably has 6 to 40 carbon atoms, more preferably 6 to 30 carbon atoms, still more preferably 6 to 23 carbon atoms, and still more preferably 6 to 22 carbon atoms. Preferable specific examples of phenolic compounds include hydroquinone, resorcinol, bisphenol A, bisphenol F, bisphenol S, phenolphthalein, methylated bisphenol A, and methylated bisphenol F. , methylated bisphenol S, phenol, o-cresol, m-cresol, p-cresol, catechol, dihydroxybenzophenone, trihydroxybenzophenone, tetrahydroxybenzophenone, m-cresol Trisphenol, glucinol, dicyclopentadiene type diphenol, etc. As the phenol compound, a phenol novolac resin (phenol novolac) and a phosphorus atom-containing oligomer having a phenolic hydroxyl group described in JP 2013-40270 A can also be used.

The naphthol compound preferably has 10 to 40 carbon atoms, more preferably 10 to 30 carbon atoms, and still more preferably 10 to 20 carbon atoms. Preferred specific examples of the naphthol compound include α-naphthol, β-naphthol, 1,5-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, and the like. As the naphthol compound, naphthol novolac can also be used.

Among them, bisphenol A, bisphenol F, bisphenol S, methylated bisphenol A, methylated bisphenol F, methylated bisphenol S, catechol, α-naphthol, and β-naphthol are preferable. , 1,5-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, dihydroxybenzophenone, trihydroxybenzophenone, tetrahydroxybenzophenone, phloroglucinol , Glycinol, dicyclopentadiene-type diphenol, phenol novolac resin, oligomers containing phosphorus atoms with phenolic hydroxyl groups, more preferably catechol, 1,5-dihydroxynaphthalene, 1,6- Dihydroxynaphthalene, 2,6-dihydroxynaphthalene, dihydroxybenzophenone, trihydroxybenzophenone, tetrahydroxybenzophenone, phloroglucinol, glucinol, dicyclopentadiene type diphenol , phenol phenolic resin, oligomers containing phosphorus atoms with phenolic hydroxyl groups, more preferably 1,5-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, dihydroxybenzophenone , trihydroxybenzophenone, tetrahydroxybenzophenone, dicyclopentadiene-type diphenol, phenol novolac resin, oligomers containing phosphorus atoms with phenolic hydroxyl groups, further more preferably 1,5-dihydroxy Naphthalene, 1,6-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, dicyclopentadiene type diphenol, phenol novolac resin, oligomer containing phosphorus atom with phenolic hydroxyl group, especially more preferably 1,5 - dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, dicyclopentadiene-type diphenols, oligomers containing phosphorus atoms with phenolic hydroxyl groups, particularly preferably dicyclopentadiene type diphenol.

It does not specifically limit as a thiol compound, For example, benzene dithiol, a triazine dithiol, etc. are mentioned.

Preferred specific examples of active ester curing agents include active ester curing agents containing a dicyclopentadiene-type diphenol structure, active ester curing agents containing a naphthalene structure, and acetylated products containing phenol novolac resins. Active ester-based curing agents, active ester-based curing agents including benzoyl compounds of phenol novolac resins, active ester-based curing agents obtained by reacting aromatic carboxylic acids with phosphorus atom-containing oligomers having phenolic hydroxyl groups, etc. , wherein, more preferably the active ester curing agent comprising a dicyclopentadiene type diphenol structure, the active ester curing agent comprising a naphthalene structure, and the oligomer containing a phosphorus atom having a phenolic hydroxyl group made of an aromatic carboxylic acid The active ester curing agent obtained by the reaction. In addition, in this invention, a "dicyclopentadiene type diphenol structure" means the divalent structural unit which consists of phenylene-dicyclopentylene (dicyclopentylene)-phenylene.

As the active ester-based curing agent, the active ester-based curing agents disclosed in JP-A-2004-277460 and JP-A-2013-40270 can be used, and commercially available active ester-based curing agents can also be used. Examples of commercially available active ester-based curing agents include "EXB9451", "EXB9460", "EXB9460S", "HPC-8000-65T", and "HPC-8000L-65M" (containing bicyclic pentadiene-type diphenol structure active ester curing agent), DIC Corporation's "EXB9416-70BK" (active ester curing agent containing naphthalene structure), Mitsubishi Chemical Corporation's "DC808" ( Active ester curing agent for acetylated compounds), "YLH1026" manufactured by Mitsubishi Chemical Corporation (active ester curing agent for active ester curing agent).

The content of the active ester-based curing agent is preferably 1% when the non-volatile content in the resin composition is 100% by mass, from the viewpoint of obtaining a cured product having excellent fine circuit forming ability and a low dielectric loss tangent. mass % or more, more preferably 5 mass % or more, still more preferably 10 mass % or more. The upper limit of the content of the active ester-based curing agent is not particularly limited, but is preferably 25% by mass or less, more preferably 20% by mass or less, and even more preferably 15% by mass or less.

In addition, when the number of epoxy groups of the (A) epoxy resin is 1, the number of reactive groups of the (B) active ester curing agent is preferably 0.1 to 10, more preferably 0.1 to 10 from the viewpoint of obtaining an insulating layer with good mechanical strength. Preferably it is 0.1-5, More preferably, it is 0.1-1. Here, the so-called "epoxy group number of epoxy resin" refers to the solid content mass of each epoxy resin present in the resin composition calculated for all the epoxy resins in the resin composition and divided by the epoxy equivalent. The resulting value is the sum of the values. In addition, the so-called "reactive group" refers to a functional group that can react with epoxy groups, and the so-called "reactive group number of active ester curing agent" refers to the number of active ester curing agents present in the resin composition. The value obtained by adding the value obtained by dividing the solid content mass by the reactive group equivalent.

＜(C)Polyimide resin＞

The resin composition of this invention contains (C) polyimide resin. When an inorganic filler having a small average particle diameter or a large specific surface area is contained in the resin composition, the melt viscosity of the resin composition generally increases. On the other hand, the resin composition of this invention containing (C)component can suppress the raise of the melt viscosity of a resin composition. It is considered that the aforementioned suppression of the increase in the melt viscosity is obtained due to the effects of the low polarity of the polyimide resin and the high compatibility between the epoxy resin and the polyimide resin. In addition, thermoplastic resins containing phenoxy resins, aliphatic resins, etc. generally tend to generate highly polar components such as alcohols during curing, and as a result, the dielectric loss tangent of the cured product of the resin composition may become high. On the other hand, the polarity of the cured product of the resin composition of the present invention containing the component (C) is lower than that of a thermoplastic resin such as a phenoxy resin, and as a result, the dielectric loss tangent of the cured product is considered to be lower. . In addition, for the resin composition of the present invention, it is considered that since a rough surface including minute unevenness can be formed by roughening treatment, a sufficient anchoring effect can be obtained even when a fine circuit is formed, As a result, fine circuit forming ability becomes excellent.

The content of component (C) is 0.1 mass % or more, preferably 0.3 mass % or more, more preferably It is 0.5 mass % or more, More preferably, it is 0.8 mass % or more. The upper limit is 6% by mass or less, preferably 5.8% by mass or less, more preferably 5.5% by mass or less, and even more preferably 5.2% by mass or less, from the viewpoint of obtaining a cured product excellent in fine circuit forming ability.

The term "resin component" refers to components other than the inorganic filler among the non-volatile components constituting the resin composition.

The component (C) is not particularly limited as long as it is a polyimide resin. As the component (C), polyimide resins such as "RIKACOAT SN20" and "RIKACOAT PN20" manufactured by Nippon Chemical Co., Ltd.; difunctional hydroxyl-terminated polybutadiene, diisocyanate compound and tetrabasic acid anhydride The linear polyimide obtained by the reaction (the polyimide recorded in Japanese Patent Application Publication No. 2006-37083), the polyimide containing polysiloxane skeleton (Japanese Patent Application Publication No. 2002-12667 and Japanese Patent Application Publication No. Modified polyimides such as polyimides described in KOKAI Publication No. 2000-319386, etc.; polyimide resins containing structures obtained by reacting dimer diamine and polycarboxylic acid compounds (Hereinafter, it may be referred to as "dipolymer diamine polyimide resin."); A polyimide resin having a polycyclic aromatic hydrocarbon skeleton. Among them, as the component (C), dimer diamine polyimide resins and polyimide resins having a polycyclic aromatic hydrocarbon skeleton are preferable from the viewpoint of further improving the fine circuit forming ability and further lowering the minimum melt viscosity, A polyimide resin having a polycyclic aromatic hydrocarbon skeleton is more preferable.

(dipolymer diamine polyimide resin)

The dimer diamine polyimide resin contains, in its molecular structure, a structural unit having a structure formed by polymerizing dimer diamine, and a structural unit having a structure formed by polymerizing a polyvalent carboxylic acid compound. In the following description, the structural unit which has the structure formed by superposing|polymerizing dimer diamine may be called a "dimer diamine unit." Moreover, the structural unit which has the structure formed by superposing|polymerizing a polyhydric carboxylic acid compound may be called "polyhydric carboxylic acid unit." Usually, in the molecule of a dimer diamine polyimide resin, a dimer diamine unit and a polyhydric carboxylic acid unit are bonded via a cyclic imide bond.

A dimer diamine is a dimer of an aliphatic amine, and contains two amino groups in 1 molecule. These amino groups are usually primary amino groups represented by -NH ₂ .

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

The dimer diamine generally includes a main chain formed by an aliphatic hydrocarbon group connecting two amino groups, and side locks formed by two aliphatic hydrocarbon groups bonded to the main chain. Therefore, the dimer diamine unit usually contains two side locks formed by aliphatic hydrocarbon groups per one dimer diamine unit, and the aliphatic hydrocarbon groups as side locks are preferably straight-chain fatty acids without branches. family of hydrocarbon groups. In addition, the number of carbon atoms per side-locked aliphatic hydrocarbon group is preferably 2 or more, preferably 19 or less, more preferably 18 or less, from the viewpoint of remarkably obtaining the desired effect of the present invention. In addition, from the viewpoint of remarkably obtaining the desired effect of the present invention, preferably one or more of the two side locks are saturated aliphatic hydrocarbon groups per one dimer diamine unit, particularly preferably all The side locks are saturated aliphatic hydrocarbon groups.

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

For specific dimer diamines, the dimer diamines described in Japanese Patent No. 5534378 can be referred to.

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

The polyvalent carboxylic acid compound means a carboxylic acid compound having a valence of 2 or more, and examples thereof include carboxylic acids having 2 or more carboxyl groups per molecule and their anhydrides (acid anhydrides). Among them, tetracarboxylic acid compounds are preferable as the polyvalent carboxylic acid, and aromatic tetracarboxylic acid compounds are particularly preferable from the viewpoint of remarkably obtaining the desired effects of the present invention.

Examples of aromatic tetracarboxylic acid compounds include pyromellitic acid, pyromellitic dianhydride, 4,4'-oxydiphthalic dianhydride, 3,3',4,4'-di Benzophenone tetracarboxylic dianhydride, 3,3',4,4'-diphenylether tetracarboxylic dianhydride, 3,3',4,4'-diphenylsulfone tetracarboxylic dianhydride, 1 ,2,3,4-Pyrene tetracarboxylic anhydride, 1,4,5,8-naphthalene tetracarboxylic anhydride, 2,3,6,7-naphthalene tetracarboxylic anhydride, 3,3',4,4'-biphenyl Tetracarboxylic dianhydride, 2,2',3,3'-biphenyltetracarboxylic dianhydride, 2,3,3',4'-biphenyltetracarboxylic dianhydride, 2,3,3',4'-di Benzophenone tetracarboxylic dianhydride, 2,3,3',4'-diphenyl ether tetracarboxylic dianhydride, 2,3,3',4'-diphenylsulfone tetracarboxylic dianhydride, 2 ,2-bis(3,3',4,4'-tetracarboxyphenyl)tetrafluoropropane dianhydride, 2,2'-bis(3,4-dicarboxyphenoxyphenyl)sulfone dianhydride, 2 ,2-bis(2,3-dicarboxyphenyl)propane dianhydride, 2,2-bis(3,4-dicarboxyphenyl)propane dianhydride, cyclopentane tetracarboxylic anhydride, butane-1,2 ,3,4-tetracarboxylic acid, 2,3,5-tricarboxycyclopentylacetic anhydride, 4,4'-[propane-2,2-diylbis(1,4-phenyleneoxy)] Diphthalic dianhydride, etc.

For particularly preferable structural units contained in the dimer diamine polyimide resin, Japanese Patent No. 5534378 can be referred to.

In the dimer diamine polyimide resin, the molar ratio of the dimer diamine unit and the polyvalent carboxylic acid unit is arbitrary as long as the effect of the present invention is not significantly impaired. Usually, the amount ratio of the dimer diamine unit and the polycarboxylic acid unit in the dimer diamine polyimide resin is the same as the dimer diamine used as a raw material for manufacturing the dimer diamine polyimide resin. The charging ratio of the diamine and the polycarboxylic acid compound is the same. The molar ratio represented by "the number of moles of polycarboxylic acid units/the number of moles of dimer diamine units" is specifically preferably 0.6 or more, particularly preferably 0.8 or more, preferably 1.4 or less, particularly preferably Below 1.2. By controlling the aforementioned quantitative ratio within the aforementioned range, the desired effect of the present invention can be remarkably obtained.

The dimer diamine polyimide resin may contain arbitrary structural units other than a dimer diamine unit and a polyhydric carboxylic acid unit as needed. A dimer diamine polyimide resin may be used individually by 1 type, and may use it in combination of 2 or more types by arbitrary ratios.

The dimer diamine polyimide resin can be manufactured by polymerizing a dimer diamine and a polyhydric carboxylic acid compound, for example. In addition, the dimer diamine polyimide resin can be obtained by, for example, polymerizing dimer diamine and a polycarboxylic acid compound to obtain a polyamic acid, and then imidizing the polyamic acid by dehydration and cyclization. to manufacture. In addition, for the manufacturing method of dimer diamine polyimide resin, after the polyimide resin is obtained by polymerization of dimer diamine and polycarboxylic acid compound, chain extender-based chain reaction. For the manufacturing method of dimer diamine polyimide resin, Japanese Patent No. 5534378 can be referred to, for example.

(Polyimide resin having polycyclic aromatic hydrocarbon skeleton)

The so-called polycyclic aromatic hydrocarbons refer to hydrocarbons that contain two or more ring structures in one molecule and at least one of the ring structures is an aromatic ring. The two or more ring structures may be fused or not. combine.

The polycyclic aromatic hydrocarbon skeleton may have no substituent or may have a substituent. The substituent is not particularly limited, and examples include halogen atoms, -OH, -OC _1-6 alkyl, -N(C _1-6 alkyl) ₂ , C _1-6 alkyl, C _6-10 aryl -NH ₂ , -CN, -C(O)OC _1-6 alkyl, -COOH, -C(O)H, -NO ₂ etc., preferably C _1-6 alkyl, more preferably methyl. A substituent may have only 1 type, and may have multiple types.

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

Examples of polycyclic aromatic hydrocarbon skeletons include indane skeletons such as 1,1,3-trimethylindan skeletons, and aromatic hydrocarbon skeletons in which five-membered ring compounds such as fluorene skeletons are condensed with aromatic rings; naphthalene An aromatic hydrocarbon skeleton formed by condensing aromatic rings such as a skeleton and anthracene skeleton; an aromatic hydrocarbon skeleton such as a biphenyl skeleton with two or more aromatic rings that have not been fused (non-condensed aromatic hydrocarbon skeleton), etc., from further improving microcircuits From the viewpoint of forming ability and further lowering of the minimum melt viscosity, an aromatic hydrocarbon skeleton in which a five-membered ring compound and an aromatic ring are fused is preferable. Among them, the polycyclic aromatic hydrocarbon skeleton is preferably at least any one of an indane skeleton and a fluorene skeleton from the viewpoint of reducing the linear thermal expansion coefficient of the cured product of the resin composition and increasing the glass transition temperature and peel strength.

As the imide resin having a polycyclic aromatic hydrocarbon skeleton, polyimide resins having a polycyclic aromatic hydrocarbon skeleton and a cyclic imide structure are preferable from the viewpoint of further improving the ability to form fine circuits and further reducing the minimum melt viscosity. .

Examples of the cyclic imide structure include phthalimide, succinimide, glutarimide, 3-methylglutarimide, maleimide, dimethyl Maleimide, trimellitic imide, pyromellitic imide, preferably phthalimide, succinimide, among them, polyamides having an aromatic imide structure are preferred. An imide resin, more preferably phthalimide.

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

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

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

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

D in formula (1) represents a single bond or a divalent linking group, preferably a divalent linking group. Examples of the divalent linking group include an oxygen atom, a sulfur atom, an alkylene group, an arylene group, -NH-, -C(=O)-, -SO-, or two or more of them. Groups formed by combinations, etc.

The alkylene group is preferably an alkylene group having 1 to 10 carbon atoms, more preferably an alkylene group having 1 to 6 carbon atoms, and still more preferably an alkylene group having 1 to 3 carbon atoms. The alkylene group may be any of linear, branched and cyclic. As such an alkylene group, a methylene group, an ethylene group, a propylene group, a butylene group, a pentylene group, a hexylene group etc. are mentioned, for example, A methylene group is preferable.

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

The alkylene group and the arylene group may not have a substituent or may have a substituent. As a substituent, it is the same as the substituent which a polycyclic aromatic hydrocarbon skeleton may have.

As a group formed by a combination of two or more of these, a group formed by a combination of two or more of an oxygen atom, an arylene group, and an alkylene group is preferable. Such a group includes, for example, a group in which one or more arylene groups are bonded to one or more alkylene groups (a group formed by a combination of an arylene group and an alkylene group), one or more oxygen A group in which an atom is bonded to one or more arylene groups (a group consisting of a combination of an oxygen atom and an arylene group), etc. Examples of groups in which one or more arylene groups are bonded to one or more alkylene groups include divalent groups consisting of phenylene-methylene, divalent groups consisting of phenylene-dimethyl A divalent group formed from a methylene group, etc. Examples of the group in which one or more oxygen atoms are bonded to one or more arylene groups include a divalent group consisting of phenylene-oxygen atom-phenylene, a group consisting of oxygen atom-phenylene A divalent group formed from a radical, a divalent group formed from an oxygen atom-naphthylene group, and the like.

As a preferred example of the repeating unit having a polycyclic aromatic hydrocarbon skeleton, the following repeating units can be mentioned;

.

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

Examples of the cyclic imide structure include phthalimide, succinimide, glutarimide, 3-methylglutarimide, maleimide, dimethyl Maleimide, trimellitic imide, pyromellitic imide, preferably phthalimide, succinimide, among them, the aromatic imide structure is preferred, more preferred Phthalimide. The repeating unit having an imide structure may be a form in which the above-mentioned imide structure is bonded to a divalent linking group. As a divalent linking group, it is the same as the divalent linking group represented by D in General formula (1).

As a preferred example of the repeating unit having an imide structure, the following repeating units can be mentioned;

.

The mass ratio of the repeating unit having a polycyclic aromatic hydrocarbon skeleton to the repeating unit having an imide structure (the mass of the repeating unit having a polycyclic aromatic hydrocarbon skeleton/the mass of the repeating unit having an imide structure) is preferably 0.5 or more, It is more preferably 0.6 or more, still more preferably 0.8 or more, preferably 2 or less, more preferably 1.8 or less, still more preferably 1.5 or less. By making this mass ratio into the said range, the linear thermal expansion coefficient of the hardened|cured material of a resin composition can be made low, and glass transition temperature and peeling strength can be improved.

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

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

＜(D) Inorganic filler＞

The resin composition of the first embodiment contains (D) an inorganic filler having an average particle diameter of 100 nm or less. Moreover, the resin composition of 2nd Embodiment contains (D) the inorganic filler whose specific surface area is 15 m< ² >/g or more. (D) The material of the component is not particularly limited, and examples thereof include silica, alumina, glass, cordierite, silicon oxide, barium sulfate, barium carbonate, talc, clay, mica powder, zinc oxide, hydrotalcite, boron Boronite, 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 titanate zirconate, barium zirconate, calcium zirconate, zirconium phosphate, and zirconium tungstate phosphate, etc. Of these, silica is particularly preferred. Examples of silica include amorphous silica, fused silica, crystalline silica, synthetic silica, and hollow silica. In addition, as silica, spherical silica is preferable. The inorganic filler may be used alone or in combination of two or more.

The average particle diameter of the inorganic filler in the first embodiment is 100 nm or less, preferably 90 nm or less, more preferably 80 nm or less, from the viewpoint of thinning the film and improving the ability to form a fine circuit. The lower limit of the average particle diameter is not particularly limited, but may be preferably 1 nm or more, more preferably 5 nm or more, still more preferably 10 nm or more, and the like from the viewpoint of improving lamination properties.

In addition, the average particle diameter of the inorganic filler in the second embodiment is preferably 100 nm or less, more preferably 90 nm or less, and still more preferably 80 nm or less from the viewpoint of thinning the film and improving the ability to form a fine circuit. . The lower limit of the average particle diameter is not particularly limited, and may be preferably 1 nm or more, more preferably 5 nm or more, still more preferably 10 nm or more, and the like.

As a commercial item of the inorganic filler which has such an average particle diameter, "UFP-30" by Denki Kagaku Kogyo Co., Ltd. etc. are mentioned, for example.

The average particle size of the inorganic filler can be measured by the laser diffraction-scattering method using the Mie scattering theory. Specifically, the particle size distribution of the inorganic filler can be prepared on a volume basis using a laser diffraction scattering type particle size distribution measuring device, and the median particle size can be measured as the average particle size. As a measurement sample, one obtained by dispersing an inorganic filler in methyl ethyl ketone by ultrasonic waves can be preferably used. As a laser diffraction scattering type particle size distribution analyzer, "LA-500" by Horiba Corporation, "SALD-2200" by Shimadzu Corporation, etc. can be used.

The specific surface area of the inorganic filler in the second embodiment is 15 m ² /g or more, more preferably 20 m ² /g or more, and still more preferably 30 m ² /g or more from the viewpoint of improving the ability to form fine circuits . The upper limit is preferably 60 m ² /g or less, more preferably 50 m ² /g or less, and still more preferably 40 m ² /g or less, from the viewpoint of improving laminability.

In addition, the specific surface area of the inorganic filler in the first embodiment is preferably 15 m ² /g or more, more preferably 20 m ² /g or more, and still more preferably 30 m ² from the viewpoint of improving the ability to form fine circuits. /g or more. The upper limit is not particularly limited, but is preferably 60 m ² /g or less, more preferably 50 m ² /g or less, and still more preferably 40 m ² /g or less.

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

For inorganic fillers, from the viewpoint of improving moisture resistance and dispersibility, it is preferable to use fluorine-containing silane coupling agents, aminosilane coupling agents, epoxy silane coupling agents, mercaptosilane coupling agents, Treatment with one or more surface treatment agents such as silane-based coupling agents, alkoxysilanes, organosilazane compounds, titanate-based coupling agents, more preferably aminosilane-based silane coupling agents . Commercially available surface treatment agents include, for example, Shin-Etsu Chemical Co., Ltd. "KBM403" (3-glycidoxypropyltrimethoxysilane), Shin-Etsu Chemical Co., Ltd. "KBM803" (3-mercaptopropyl Trimethoxysilane), Shin-Etsu Chemical Co., Ltd. "KBE903" (3-aminopropyltriethoxysilane), Shin-Etsu Chemical Co., Ltd. "KBM573" (N-phenyl-3-aminopropyltrimethoxy Silane), Shin-Etsu Chemical Co., Ltd. "SZ-31" (hexamethyldisilazane), Shin-Etsu Chemical Co., Ltd. "KBM103" (phenyltrimethoxysilane), Shin-Etsu Chemical Co., Ltd. "KBM-4803" (long-chain epoxy-type silane coupling agent), Shin-Etsu Chemical Co., Ltd. "KBM-7103" (3,3,3-trifluoropropyltrimethoxysilane), etc.

The degree of the surface treatment with the surface treatment agent is preferably performed with 0.2 to 5 parts by mass of the surface treatment agent with respect to 100 parts by mass of the component (D) from the viewpoint of improving the dispersibility of the inorganic filler. Surface treatment is performed, preferably 0.2 to 4 parts by mass, preferably 0.3 to 3 parts by mass.

The degree of surface treatment by the surface treatment agent can be evaluated by the carbon content of the inorganic filler per unit surface area. The amount of carbon per unit surface area of the inorganic filler is preferably 0.02 ^mg /m or more, more preferably 0.1 ^mg /m or more, and even more preferably 0.2 mg from the viewpoint of improving the dispersibility of the inorganic filler. / ^m2 or more. On the other hand, from the viewpoint of suppressing the melt viscosity of the resin varnish and the melt viscosity in sheet form, it is preferably 1 mg/m ² or less, more preferably 0.8 mg/m ² or less, even more preferably 0.5 mg / ^m2 or less.

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

The content of component (D) is preferably 30% by mass or more, more preferably 35% by mass or more, from the viewpoint of reducing the dielectric loss tangent, when the non-volatile components in the resin composition are 100% by mass , and more preferably 40% by mass or more. The upper limit is preferably 80% by mass or less, more preferably 70% by mass or less, and still more preferably 65% by mass or less, from the viewpoint of improving insulation performance.

＜(E) Curing agent＞

In one embodiment, the resin composition may contain (E) a curing agent. However, the so-called (E) curing agent here does not include (B) active ester-based curing agent. The (E) component is not particularly limited as long as it has the function of curing the (A) component. Examples include phenol-based curing agents, naphthol-based curing agents, benzoxazine-based curing agents, Ester-based curing agent, carbodiimide-based curing agent, etc. Among them, as the component (E), a phenolic curing agent is preferable. The curing agent may be used alone or in combination of two or more.

As the phenol-based curing agent and the naphthol-based curing agent, a phenol-based curing agent having a phenolic structure or a naphthol-based curing agent having a phenolic structure are preferable from the viewpoint of heat resistance and water resistance. In addition, from the viewpoint of adhesiveness with the conductor layer, a nitrogen-containing phenolic curing agent is preferable, and a triazine skeleton-containing phenolic curing agent is more preferable.

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

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

Examples of cyanate-based curing agents include bisphenol A dicyanate, polyphenol cyanate, oligo(3-methylene-1,5-phenylene cyanate), 4,4 '-Methylene bis(2,6-dimethylphenyl cyanate), 4,4'-ethylene diphenyl dicyanate, hexafluorobisphenol A dicyanate, 2,2 -Bis(4-cyanato)phenylpropane, 1,1-bis(4-cyanatophenylmethane), bis(4-cyanato-3,5-dimethylphenyl)methane , 1,3-bis(4-cyanatophenyl-1-(methylethylene))benzene, bis(4-cyanatophenyl)sulfide, and bis(4-cyanate Difunctional cyanate resins such as phenyl) ether, polyfunctional cyanate resins derived from phenol novolac resins and cresol novolak resins, prepolymers obtained by partially triazinating these cyanate resins, etc. Specific examples of cyanate-based curing agents include "PT30" and "PT60" (phenol novolak type polyfunctional cyanate resin), "ULL-950S" (multifunctional cyanate resin) manufactured by Lonza Japan Co., Ltd. ), "BA230", "BA230S75" (a prepolymer in which part or all of bisphenol A dicyanate is triazinated to form a trimer), etc.

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

When the resin composition contains (E) component, the amount ratio of (A) component to (E) component is [the total number of epoxy groups of (A) component]: [the number of reactive groups of (E) component Total number] is preferably in the range of 1:0.01 to 1:2, more preferably 1:0.05 to 1:1.5, still more preferably 1:0.08 to 1:1. Here, the reactive group of (E) component means an active hydroxyl group etc., and it differs with the kind of (E) component. In addition, the total number of epoxy groups of the so-called (A) component refers to the value obtained by dividing the solid content mass of each (A) component by the epoxy equivalent for all (A) components. The total number of reactive groups of E) component means the value obtained by calculating the sum of the values obtained by dividing the solid content mass of each (E) component by the reactive group equivalent for all (E) components. By making the quantity ratio of (A) component and (E) component into the said range, the linear thermal expansion coefficient of the hardened|cured material of a resin composition can be reduced further, and peeling strength can be improved more.

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

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

＜(F) Curing Accelerator＞

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

Examples of phosphorus-based curing accelerators include triphenylphosphine, phosphonium borate compounds, tetraphenylphosphonium tetraphenylborate, n-butylphosphonium tetraphenylborate, tetrabutylphosphonium decanoic acid salt, (4-methylphenyl)triphenylphosphonium thiocyanate, tetraphenylphosphonium thiocyanate, butyltriphenylphosphonium thiocyanate, etc., preferably triphenylphosphine, tetrabutylphosphonium Decanoate.

Examples of the amine-based curing accelerator include trialkylamines such as triethylamine and tributylamine, 4-dimethylaminopyridine, benzyldimethylamine, 2,4,6-tris(di Methylaminomethyl)phenol, 1,8-diazabicyclo(5,4,0)-undecene, etc., preferably 4-dimethylaminopyridine, 1,8-diazabicyclo(5, 4,0)-Undecene.

Examples of imidazole-based curing accelerators include 2-methylimidazole, 2-undecylimidazole, 2-heptadecylimidazole, 1,2-dimethylimidazole, 2-ethyl-4-methylimidazole, Imidazole, 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 Base-4-methylimidazole, 1-cyanoethyl-2-phenylimidazole, 1-cyanoethyl-2-undecylimidazolium trimellitate, 1-cyanoethyl-2 -Phenylimidazolium trimellitate, 2,4-diamino-6-[2'-methylimidazolyl-(1')]-ethyl-s-triazine, 2,4-diamino-6 -[2'-undecylimidazolyl-(1')]-ethyl-s-triazine, 2,4-diamino-6-[2'-ethyl-4'-methylimidazolyl-( 1')]-ethyl-s-triazine, 2,4-diamino-6-[2'-methylimidazolyl-(1')]-ethyl-s-triazine isocyanurate adduct, 2-phenylimidazole isocyanuric acid adduct, 2-phenyl-4,5-dihydroxymethylimidazole, 2-phenyl-4-methyl-5-hydroxymethylimidazole, 2,3-dihydroxymethylimidazole Hydrogen-1H-pyrrolo[1,2-a]benzimidazole, 1-dodecyl-2-methyl-3-benzylimidazolium chloride, 2-methylimidazoline, 2-phenylimidazole imidazole compounds such as line and adducts of imidazole compounds and epoxy resins, preferably 2-ethyl-4-methylimidazole and 1-benzyl-2-phenylimidazole.

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

Examples of guanidine-based curing accelerators include dicyandiamide, 1-methylguanidine, 1-ethylguanidine, 1-cyclohexylguanidine, 1-phenylguanidine, 1-(o-tolyl)guanidine, dimethyl guanidine, diphenylguanidine, trimethylguanidine, tetramethylguanidine, pentamethylguanidine, 1,5,7-triazabicyclo[4.4.0]dec-5-ene, 7-methyl-1 ,5,7-Triazabicyclo[4.4.0]dec-5-ene, 1-methylbiguanide, 1-ethylbiguanide, 1-n-butylbiguanide, 1-n-octadecylbiguanide, 1, 1-dimethyl biguanide, 1,1-diethyl biguanide, 1-cyclohexyl biguanide, 1-allyl biguanide, 1-phenyl biguanide, 1-(o-tolyl) biguanide, etc., preferably dicyandiamide, 1,5,7-Triazabicyclo[4.4.0]dec-5-ene.

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

When the resin composition contains a curing accelerator, the content of the curing accelerator is preferably 0.01% by mass or more, more preferably 0.05% by mass or more when the non-volatile content in the resin composition is 100% by mass, and furthermore Preferably it is 0.1 mass % or more. The upper limit is preferably 3% by mass or less, more preferably 2% by mass or less, and still more preferably 1% by mass or less. By setting the content of the curing accelerator within the above range, the ability to form fine circuits can be further improved, and the minimum melt viscosity can be further reduced.

＜(G) Thermoplastic resin＞

In one embodiment, the resin composition may contain (G) a thermoplastic resin. However, (G) thermoplastic resin here does not include (C) polyimide resin.

Examples of thermoplastic resins include phenoxy resins, polyvinyl acetal resins, polyolefin resins, polybutadiene resins, polyamideimide resins, polysulfone resins, polyethersulfone resins, and polyphenylene ether resins. , polycarbonate resin, polyether ether ketone resin, polyester resin, etc., preferably phenoxy resin. A thermoplastic resin may be used individually by 1 type, or may use it in combination of 2 or more types.

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

Examples of phenoxy resins include resins having a structure selected from bisphenol A skeleton, bisphenol F skeleton, bisphenol S skeleton, bisphenol acetophenone skeleton, phenolic skeleton, biphenyl skeleton, fluorene skeleton, dicyclopentadiene A phenoxy resin having one or more skeletons selected from the group consisting of a skeleton, a norbornene skeleton, a naphthalene skeleton, an anthracene skeleton, an adamantane skeleton, a terpene skeleton, and a trimethylcyclohexane skeleton. The terminal of the phenoxy resin may be any functional group among phenolic hydroxyl groups, epoxy groups, and the like. The phenoxy resins may be used alone or in combination of two or more. Specific examples of phenoxy resins include "1256" and "4250" manufactured by Mitsubishi Chemical Corporation (both phenoxy resins containing a bisphenol A skeleton), "YX8100" (a phenoxy resin containing a bisphenol S skeleton), Oxygen resin), and "YX6954" (phenoxy resin containing a bisphenol acetophenone skeleton), in addition, "FX280" and "FX293" manufactured by Nippon Steel and Sumikin Chemical Co., Ltd., and "FX293" manufactured by Mitsubishi Chemical Corporation "YL7500BH30", "YX6954BH30", "YX7553", "YX7553BH30", "YL7769BH30", "YL6794", "YL7213", "YL7290" and "YL7482", etc.

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

Specific examples of the polyamide-imide resin include "VYLOMAX HR11NN" and "VYLOMAX HR16NN" manufactured by Toyobo Corporation. Specific examples of polyamideimide resins include modified polyamideimides such as "KS9100" and "KS9300" (polyamideimides containing a polysiloxane skeleton) manufactured by Hitachi Chemical Industries, Ltd. .

Specific examples of the polyethersulfone resin include "PES5003P" manufactured by Sumitomo Chemical Co., Ltd., and the like. Specific examples of the polyphenylene ether resin include oligophenylene ether-styrene resin "OPE-2St 1200" having a vinyl group manufactured by Mitsubishi Gas Chemical Co., Ltd., and the like.

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

When the resin composition contains a thermoplastic resin, the content of the thermoplastic resin is preferably 0.1% by mass or more, more preferably 0.3% by mass or more, and even more preferably 0.5% by mass or more. The upper limit is preferably 10% by mass or less, more preferably 5% by mass or less, and still more preferably 3% by mass or less.

＜(H)Other additives＞

In one embodiment, the resin composition may further contain other additives as needed, and examples of the other additives include organic phosphorus compounds, organic nitrogen-containing phosphorus compounds, nitrogen compounds, organosilicon compounds, etc. , and metal hydroxides and other flame retardants; organic fillers such as rubber particles; organometallic compounds such as organic copper compounds, organic zinc compounds and organic cobalt compounds; thickeners, defoamers, leveling agents, adhesion imparting Resin additives such as additives and colorants.

<Physical properties and uses of resin compositions>

The resin composition of the present invention provides an insulating layer (cured product of the resin composition layer) having excellent fine circuit forming ability and low dielectric loss tangent. Therefore, the resin composition of the present invention can be suitably used as a resin composition layer for insulating use. Specifically, the resin composition of the present invention can be suitably used as: a resin composition for forming an insulating layer of a printed wiring board (resin composition for an insulating layer of a printed wiring board); A resin composition for forming an interlayer insulating layer of a printed wiring board (resin composition for an interlayer insulating layer of a printed wiring board). Moreover, since the resin composition of this invention provides the insulating layer with favorable component embedding property, it can be used suitably also when a printed wiring board is a circuit board with built-in components. In addition, the resin composition of the present invention can be suitably used as: a resin composition for forming an insulating layer for forming a conductor layer (including a rewiring layer) on an insulating layer (resin for forming an insulating layer for forming a conductor layer) combination).

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

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

The minimum melt viscosity of the resin composition at 120° C. is preferably 7,000 poise or less, more preferably 6,000 poise or less, and still more preferably 5,000 poise or less from the viewpoint of improving laminability. The lower limit is not particularly limited, and may be 100 poise or more. The minimum melt viscosity can be measured by the method described in <evaluation of laminarity> mentioned later.

The resin composition exhibits the characteristic that embedding property is improved because the minimum melt viscosity is low, and as a result, generation of voids (voids) can be suppressed. For example, even if the resin composition is laminated on a comb-shaped pattern of L/S=160 μm/160 μm, voids are not generated. The presence or absence of voids can be measured in accordance with the method described in <Evaluation of Laminarity> to be described later.

[Resin sheet]

The resin sheet of this invention contains a support body, and the resin composition layer formed from the resin composition of this invention provided on this support body.

The thickness of the resin composition layer is preferably 200 μm or less, more preferably 100 μm or less, still more preferably 50 μm or less, still more preferably 20 μm or less, 15 μm or less, or 10 μm from the viewpoint of thinning the printed wiring board. the following. There is no particular limitation on the lower limit of the thickness of the resin composition layer, and it may be generally 1 μm or more, 3 μm or more, or the like.

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

When using a film formed of a plastic material as a support body, examples of the plastic material include polyethylene terephthalate (hereinafter sometimes abbreviated as "PET"), polyethylene naphthalate Polyesters such as esters (hereinafter sometimes abbreviated as "PEN"), polycarbonate (hereinafter sometimes abbreviated as "PC"), acrylics such as polymethyl methacrylate (PMMA), cyclic polyolefins, and triacetyl fibers (TAC), polyether sulfide (PES), polyether ketone, polyimide, etc. Among them, polyethylene terephthalate and polyethylene naphthalate are preferable, and inexpensive polyethylene terephthalate is particularly preferable.

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

The support body may be subjected to matte treatment, corona treatment, or antistatic treatment on the surface bonded to the resin composition layer.

Moreover, as a support body, the support body with a mold release layer which has a mold release layer on the surface bonded to a resin composition layer can be used. Examples of the release agent used in the release layer of the support with a release layer include at least one selected from the group consisting of alkyd resins, polyolefin resins, polyurethane resins, and silicone resins. release agent. A commercially available product can be used as the support body with a release layer, for example, a PET film having a release layer mainly composed of an alkyd resin release agent, that is, "SK-1" manufactured by Lintec Co., Ltd. , "AL-5", "AL-7", "Lumiller T60" manufactured by Toray Corporation, "Purex" manufactured by Teijin Corporation, "UNIPEEL" manufactured by UNITIKA Corporation, etc.

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

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

The resin sheet can be produced, for example, by preparing a resin varnish in which a resin composition is dissolved in an organic solvent, coating the resin varnish on a support using a die coater, etc., and then making it It dries to form a resin composition layer.

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

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

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

[Printed Wiring Board]

The printed wiring board of this invention contains the insulating layer formed from the hardened|cured material of the resin composition of this invention, a 1st conductor layer, and a 2nd conductor layer. The insulating layer is provided between the first conductor layer and the second conductor layer, and insulates the first conductor layer from the second conductor layer (the conductor layer is sometimes referred to as a wiring layer).

The thickness of the insulating layer between the first conductor layer and the second conductor layer is preferably 6 μm or less, more preferably 5.5 μm or less, further preferably 5 μm or less. The lower limit is not particularly limited, and may be 0.1 μm or more. As shown in an example shown in FIG. 1, the distance between the first conductor layer and the second conductor layer (the thickness of the insulating layer between the first conductor layer and the second conductor layer) refers to the main thickness of the first conductor layer 1. The thickness t1 of the insulating layer 3 between the surface 11 and the main surface 21 of the second conductor layer 2 . The first conductor layer and the second conductor layer are adjacent conductor layers with an insulating layer interposed therebetween, and the main surface 11 and the main surface 21 are opposed to each other.

It should be noted that the thickness t2 of the entire insulating layer is preferably 15 μm or less, more preferably 13 μm or less, and still more preferably 10 μm or less. There is no particular limitation on the lower limit, and generally, it may be 1 μm or more, 1.5 μm or more, 2 μm or more, and the like.

For printed wiring boards, the above-mentioned resin sheet can be used, and it can be produced by a method including the steps of (I) and (II) below,

(1) a step of laminating the resin sheet on the inner layer substrate in such a manner that the resin composition layer of the resin sheet 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 the step (I) is a member to be a substrate of a printed wiring board, and examples thereof include a glass epoxy substrate, a metal substrate, a polyester substrate, a polyimide substrate, a BT resin substrate, a thermosetting Type polyphenylene ether substrate, etc. In addition, the substrate may have a conductive layer on one or both surfaces, and the conductive layer may be patterned. An inner layer substrate in which a conductive layer (circuit) is formed on one or both surfaces of the substrate may be referred to as an "inner layer circuit board". In addition, the term "inner layer substrate" in the present invention also includes an intermediate product in which an insulating layer and/or a conductor layer should be further formed when a printed wiring board is manufactured. When the printed wiring board is a circuit board with built-in components, an inner layer substrate with built-in components can be used.

The lamination of the inner layer substrate and the resin sheet can be carried out, for example, by thermocompression-bonding the resin sheet to the inner layer substrate from the support body side. As a member for thermocompression-bonding a resin sheet to an inner layer substrate (hereinafter also referred to as "thermocompression bonding member"), for example, a heated metal plate (SUS end plate (mirror plate) etc.) or a metal roll can be mentioned. (SUS roll), etc. It should be noted that it is preferable not to press the thermocompression bonding member directly against the resin sheet, but to press through an elastic material such as heat-resistant rubber so that the resin sheet can fully follow the surface irregularities of the inner substrate. .

The lamination of the inner substrate and the resin sheet can be performed by a vacuum lamination method. In the vacuum lamination method, the thermocompression bonding temperature is preferably in the range of 60°C to 160°C, more preferably 80°C to 140°C, and the thermocompression bonding pressure is preferably 0.098MPa to 1.77MPa, more preferably 0.29MPa to 1.47MPa range, the thermocompression bonding time is preferably in the range of 20 seconds to 400 seconds, and more preferably in the range of 30 seconds to 300 seconds. Lamination is preferably carried out under reduced pressure conditions with a pressure of 26.7 hPa or less.

Lamination can be performed using a commercially available vacuum laminator. As a commercially available vacuum laminator, for example, a vacuum pressure laminator manufactured by Meiji Co., Ltd., a vacuum applicator (vacuum applicator) manufactured by Nikko-Materials Co., Ltd., a batch type vacuum pressure laminator, etc. .

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

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

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

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

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

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

When manufacturing a printed wiring board, (III) the process of opening a hole in an insulating layer, (IV) the process of roughening an insulating layer, and (V) the process of forming a conductor layer can also be implemented. The said process (III) - process (V) can be implemented by various methods well-known to those skilled in the art which can utilize for manufacture of a printed wiring board. It should be noted that when the support is removed after the step (II), the removal of the support can be between the step (II) and the step (III), between the step (III) and the step (IV), or the step ( Implement between IV) and step (V). In addition, if necessary, the formation of the insulating layer and the conductor layer in the steps (II) to (V) may be repeated to form a multilayer wiring board. In this case, the thickness of the insulating layer (t1 in FIG. 1 ) between the conductor layers is preferably within the above range.

Step (III) is a step of opening holes in the insulating layer, thereby forming holes such as via holes and through holes in the insulating layer. Step (III) can be implemented using, for example, a drill, laser, plasma, etc., depending on the composition of the resin composition used for the formation of the insulating layer. The size and shape of the hole can 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 known procedures and conditions generally used when forming an insulating layer of a printed wiring board can be employed. For example, the insulating layer may be roughened by sequentially performing swelling treatment with a swelling solution, roughening treatment with an oxidizing agent, and neutralization treatment with a neutralizing solution. The swelling liquid used for the roughening treatment is not particularly limited, and examples thereof include alkali solutions, surfactant solutions, and the like, preferably alkali solutions, and more preferably sodium hydroxide solutions and potassium hydroxide solutions as the alkali solutions. As a commercially available swelling liquid, "Swelling Dip Securiganth P" and "Swelling Dip Securiganth SBU" manufactured by Atotech Japan Co., Ltd., etc. are mentioned, for example. The swelling treatment with a swelling solution is not particularly limited, and can be performed, for example, by immersing the insulating layer in a swelling solution at 30° C. to 90° C. for 1 minute to 20 minutes. From the viewpoint that the swelling of the resin of the insulating layer can be suppressed to an appropriate level, it is preferable to immerse the insulating layer in a swelling solution at 40° C. to 80° C. for 5 minutes to 15 minutes. It does not specifically limit as an oxidizing agent used for a roughening process, For example, the alkaline permanganate solution which dissolved potassium permanganate and sodium permanganate in the aqueous solution of sodium hydroxide is mentioned. The roughening treatment with an oxidizing agent such as an alkaline permanganic acid solution is preferably performed by immersing the insulating layer in an oxidizing agent solution heated to 60° C. to 80° C. for 10 minutes to 30 minutes. In addition, the concentration of permanganate in the alkaline permanganate solution is preferably 5% by mass to 10% by mass. As a commercially available oxidizing agent, alkaline permanganate solutions, such as "Concentrate Compact CP" and "Dosing Solution Securiganth P" manufactured by Atotech Japan Co., Ltd., are mentioned, for example. Moreover, as a neutralization liquid used for a roughening process, an acidic aqueous solution is preferable, and as a commercial item, "Reduction Solution Securiganth P" by ATOTECH JAPAN company is mentioned, for example. The treatment with the neutralizing solution can be carried out by immersing the treated surface subjected to the roughening treatment with an oxidizing agent in a neutralizing solution at 30° C. to 80° C. for 5 minutes to 30 minutes. From the viewpoint of workability and the like, a method of immersing the object subjected to the roughening treatment with an oxidizing agent in a neutralizing solution at 40° C. to 70° C. for 5 minutes to 20 minutes is preferable.

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

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

The conductor material used in the conductor layer is not particularly limited. In a preferred embodiment, the conductor layer contains one or more materials selected from the group consisting of gold, platinum, palladium, silver, copper, aluminum, cobalt, chromium, zinc, nickel, titanium, tungsten, iron, tin, and indium. Metal. The conductor layer can be a single metal layer or an alloy layer. As the alloy layer, for example, an alloy of two or more metals selected from the above-mentioned group (such as nickel-chromium alloy, copper-nickel alloy and copper alloy) can be mentioned. - layer formed by titanium alloy). Among them, a single metal layer of chromium, nickel, titanium, aluminum, zinc, gold, palladium, silver, or copper, or a nickel-chromium alloy is preferable from the viewpoint of the versatility of conductor layer formation, cost, and ease of pattern formation. , copper-nickel alloy, copper-titanium alloy alloy layer, more preferably a single metal layer of chromium, nickel, titanium, aluminum, zinc, gold, palladium, silver or copper, or a nickel-chromium alloy alloy layer, more preferably A single metal layer of copper.

The conductor layer may have a single-layer structure, or may have a multi-layer structure in which two or more single metal layers or alloy layers made of different types of metals or alloys are laminated. When the conductor layer has a 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 depends on the desired design of the printed wiring board, and is usually 3 μm to 35 μm, preferably 5 μm to 30 μm.

In one embodiment, the conductor layer may be formed by plating. For example, the existing known techniques such as semi-additive method and full-additive method can be used to plate on the surface of the insulating layer to form a conductor layer with a desired wiring pattern. From the viewpoint of ease of manufacture, It is preferably formed using a semiadditive method. Hereinafter, an example of forming a conductor layer by a semi-additive method will be described.

First, a plating seed layer is formed on the surface of the insulating layer by electroless plating (electroless plating). Next, on the formed plating seed layer, a mask pattern for exposing a part of the plating seed layer is formed corresponding to a desired wiring pattern. On the exposed plating seed layer, a metal layer is formed by electrolytic plating, and then the mask pattern is removed. Then, the unnecessary plating seed layer is removed by etching or the like to form a conductor layer having a desired wiring pattern.

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

A printed wiring board produced using the resin sheet of the present invention may be in the form of an insulating layer that is a cured product of the resin composition layer of the resin sheet, and a buried wiring layer embedded in the insulating layer.

[semiconductor device]

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

Examples of semiconductor devices include various semiconductors that can be used in electrical products (such as computers, mobile phones, digital cameras, and televisions, etc.) and vehicles (such as motorcycles, automobiles, trains, ships, and airplanes, etc.) device.

The semiconductor device of the present invention can be manufactured by mounting components (semiconductor chips) on conduction positions on a printed wiring board. The "conduction position" refers to "the position where an electric signal is transmitted in the printed wiring board", and the position may be a surface or a buried place. In addition, the semiconductor chip is not particularly limited as long as it is an electrical circuit element made of a semiconductor.

For the mounting method of the semiconductor chip when manufacturing a semiconductor device, as long as the semiconductor chip can effectively function, there is no particular limitation. Specifically, a wire bonding mounting method, a flip chip mounting method, and a solderless The mounting method of the build-up layer (Bump less Build-Up Layer, BBUL), the mounting method using the anisotropic conductive film (ACF), the mounting method using the non-conductive film (NCF), etc. Here, "a mounting method using a solderless build-up layer (BBUL)" means "a mounting method in which a semiconductor chip is directly buried in a recess of a printed wiring board, and the semiconductor chip is connected to wiring on the printed wiring board."

Example

Hereinafter, the present invention will be specifically described using examples. The present invention is not limited by these examples. In addition, in the following description, "part by mass" and "% by mass" which represent an amount represent "parts by mass" and "% by mass", respectively, unless otherwise specified.

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

＜Measurement of Microcircuit Formability＞

(Preparation of samples for measurement)

(1) Substrate treatment of inner layer circuit board

Prepare a glass cloth substrate epoxy resin double-sided copper-clad laminate (thickness of copper foil: 18 μm, thickness of substrate: 0.8 mm, “R1766” manufactured by Panasonic Co., Ltd.) on which the inner layer circuit is formed as the inner layer circuit board. It was immersed in "CZ8101" manufactured by MEC Corporation, and roughened the copper surface (copper etching amount: 1.0 μm).

(2) Lamination of resin sheets

For the resin sheet having a resin composition layer thickness of 10 μm produced in Examples and Comparative Examples, a batch vacuum pressure laminator (manufactured by Nikko Materials, 2-Stage Buildup Laminator) was used. , CVP700), in the manner that the resin composition layer is bonded to the inner layer circuit board, lamination is performed on both sides of the inner layer circuit board. The lamination process was carried out by depressurizing for 30 seconds so that the air pressure would be 13 hPa or less, and then performing pressure bonding at 100° C. under a pressure of 0.74 MPa for 30 seconds. Next, hot pressing was performed at 100° C. for 60 seconds under a pressure of 0.5 MPa.

(3) Curing of the resin composition layer

After laminating the resin sheets, 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. Then, the support body was peeled off to expose the insulating layer.

(4) Roughening treatment

The substrate with the insulating layer exposed was immersed in a swelling solution ("Swelling Dip Securiganth P" manufactured by ATOTECH JAPAN Co., Ltd., an aqueous solution of sodium hydroxide containing diethylene glycol monobutyl ether) at 60° C. for 10 minutes, and then, at 80° C. Immerse in an oxidizing agent ("Concentrate Compact CP" manufactured by ATOTECH JAPAN Co., Ltd., an aqueous solution with a concentration of potassium permanganate of about 6% by mass and a concentration of sodium hydroxide of about 4% by mass) for 20 minutes, and finally, immerse in a neutralizing solution at 40°C ("Reduction Solution Securiganth P" manufactured by ATOTECH JAPAN Co., Ltd., hydroxylamine sulfate aqueous solution) for 5 minutes. Then, drying was performed at 80° C. for 15 minutes. The obtained substrate is referred to as "substrate a".

(5) Formation of conductor layer (circuit)

According to the semi-additive method, the conductor layer is formed on the roughened surface of the insulating layer. That is, a plating process (copper plating process using a chemical solution manufactured by ATOTECH JAPAN Co., Ltd.) including the following steps 1 to 6 was performed to form a conductor layer.

1. Alkali cleaning (washing and charge adjustment of the surface of the insulating layer provided with through holes)

Using Cleaning Cleaner Securiganth 902 (trade name), the surface of the substrate a was washed at 60° C. for 5 minutes.

2. Soft etching (cleaning inside the through hole)

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

3. Prepreg (regulation of charge on the surface of the insulating layer to impart Pd)

Using Pre. Dip Neoganth B (trade name), the surface of the substrate a was treated at room temperature for 1 minute.

4. Activator application (application of Pd to the surface of the insulating layer)

Using Activator Neoganth 834 (trade name), the surface of the substrate a was treated at 35° C. for 5 minutes.

5. Reduction (reduction of Pd already provided to the insulating layer)

The surface of the substrate a was treated at 30° C. for 5 minutes using a mixed solution of Reducer Neoganth WA (trade name) and Reducer Acceralator 810 mod. (trade name).

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

Using a mixture of Basic Solution Printganth MSK-DK (trade name), Copper solution Printganth MSK (trade name), Stabilizer Printganth MSK-DK (trade name), and Reducer Cu (trade name), the surface of the substrate a was treated at 35°C. 30 minutes to process. The thickness of the formed electroless copper plating layer was 1 μm.

(6) Formation of wiring pattern

After electroless plating, the surface of the substrate was treated with 5% sulfuric acid aqueous solution for 30 seconds. Next, a dry film for pattern formation ("PHOTEC RY-3600" manufactured by Hitachi Chemical Co., Ltd., thickness 19 μm) was laminated on both sides of the substrate. The lamination was carried out by decompressing for 30 seconds until the gas pressure became 13 hPa or less, and then pressurizing at 70° C. under a pressure of 0.1 MPa for 20 seconds.

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

Wiring pattern of glass mask:

Use 10 glass masks each of the following i) to vii) comb-shaped patterns;

i) L/S=2μm/2μm, that is, a comb-shaped pattern with a wiring pitch of 4μm (wiring length 15mm, 16 lines)

ii) L/S=3μm/3μm, that is, a comb pattern with a wiring pitch of 6μm (wiring length 15mm, 16 lines)

iii) L/S=4μm/4μm, that is, a comb-shaped pattern with a wiring pitch of 8μm (wiring length 15mm, 16 lines)

iv) L/S=5μm/5μm, that is, a comb pattern with a wiring pitch of 10μm (wiring length 15mm, 16 lines)

v) L/S=6μm/6μm, that is, a comb-shaped pattern with a wiring pitch of 12μm (wiring length 15mm, 16 lines)

vi) L/S=7μm/7μm, that is, a comb pattern with a wiring pitch of 14μm (wiring length 15mm, 16 lines)

vii) L/S=8 μm/8 μm, that is, a comb-shaped pattern with a wiring pitch of 16 μm (wiring length 15 mm, 16 lines).

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

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

(7) Evaluation of Microcircuit Formability

For the comb-shaped patterns of the above i) to vii) of the evaluation substrate A, the presence or absence of peeling of the circuit was confirmed with an optical microscope, and the presence or absence of unnecessary residues of the electroless copper plating layer was confirmed by measuring the insulation resistance of the comb-shaped pattern. Moreover, the case where there was no problem in 9 or more of 10 comb patterns was judged as a pass. The ability to form fine circuits was evaluated by the minimum L/S ratio and wiring pitch judged to be acceptable. In this evaluation, the smaller the minimum L/S ratio and the wiring pitch judged to be acceptable, the better the fine circuit forming capability.

＜Evaluation of Lamination＞

(Determination of minimum melt viscosity)

About the resin composition layer (thickness 25 micrometers) of the resin sheet produced beforehand, the minimum melt viscosity was measured using the dynamic viscoelasticity measuring apparatus (UBM company make "Rheosol-G3000"). For 1 g of the sample resin composition, using a parallel plate with a diameter of 18 mm, the temperature was raised from the initial temperature of 60°C to 200°C at a heating rate of 5°C/min. The dynamic viscoelastic modulus was measured under the measurement conditions, and the melt viscosity at 120°C was measured.

(with or without empty comments)

Using a batch-type vacuum pressure laminator (manufactured by Nikko Materials, two-stage stack laminator, CVP700), the thickness of the resin composition layer produced in Examples and Comparative Examples was 25 μm, and the area was 240×320mm ² The resin sheet was laminated on a comb-shaped pattern (thickness 18 μm) of L (line: wiring width)/S (space: space width)=160 μm/160 μm. Lamination was performed by depressurizing for 30 seconds so that the air pressure would be 13 hPa or less, and then pressurizing at 100° C. under a pressure of 0.74 MPa for 30 seconds. Next, hot pressing was performed at 100° C. for 60 seconds at a pressure of 0.5 MPa. Air was introduced after lamination, and it was confirmed whether or not holes (voids) were generated in the resin composition layer. The case where voids did not occur after lamination was marked as "◯", and the case where voids were formed was marked as "×".

<Measurement of dielectric loss tangent>

The 25-μm-thick resin sheet of the resin composition layer prepared in Examples and Comparative Examples was heated at 200° C. for 90 minutes to thermally cure the resin composition layer, and then the support was peeled off to obtain a cured product for evaluation. The cured product for evaluation was cut into test pieces having a width of 2 mm and a length of 80 mm. The dielectric loss tangent of this test piece was measured at a measurement frequency of 5.8 GHz and a measurement temperature of 23° C. using “HP8362B” manufactured by Agilent Technologies, by the resonator perturbation method. It measured about 2 test pieces, and calculated the average value.

<Synthesis Example 1: Synthesis of Polyimide Resin 1>

A 500 mL detachable flask having a moisture quantitative receiver connected to a reflux condenser, a nitrogen gas introduction tube, and a stirrer was prepared. 20.3 g of 4,4'-oxydiphthalic anhydride (ODPA), 200 g of γ-butyrolactone, 20 g of toluene, and 5-(4-aminophenoxy)-3-[4 -(4-Aminophenoxy)phenyl]-1,1,3-trimethylindane 29.6 g was stirred at 45° C. for 2 hours under a nitrogen stream to perform a reaction.

Next, while raising the temperature of the reaction solution and keeping it at about 160° C., condensed water was azeotropically removed together with toluene under a nitrogen stream. It was confirmed that a prescribed amount of water remained in the moisture quantitative receiver, and that the outflow of water was no longer observed. After confirmation, the temperature of the reaction solution was further raised, and stirred at 200° C. for 1 hour. Then, cooling was performed to obtain a varnish containing 20% by mass of a polyimide resin (polyimide resin 1) having a 1,1,3-trimethylindane skeleton. The obtained polyimide resin 1 has the repeating unit represented by following formula (X1) and the repeating unit represented by formula (X2). In addition, the weight average molecular weight of polyimide resin 1 is 12000;

.

<Synthesis Example 2: Synthesis of Polyimide Resin 2>

In Synthesis Example 1, 29.6 g of 5-(4-aminophenoxy)-3-[4-(4-aminophenoxy)phenyl]-1,1,3-trimethylindan was changed to 9 , 22.9 g of 9-bis(4-aminophenyl)fluorene. Except for the above matter, it carried out similarly to the synthesis example 1, and obtained the varnish containing 20 mass % of polyimide resins (polyimide resin 2) which have a fluorene skeleton. The obtained polyimide resin 2 has the repeating unit represented by following formula (X3) and the repeating unit represented by said formula (X2). In addition, the weight average molecular weight of polyimide resin 2 is 14000;

.

<Synthesis Example 3: Synthesis of Polyimide Resin 3>

Into a reaction vessel equipped with a stirrer, a water separator, a thermometer, and a nitrogen gas introduction pipe, 65.0 g of aromatic tetracarboxylic dianhydride ("BisDA-1000" manufactured by SABIC Japan), 266.5 g of cyclohexanone, and methyl 44.4 g of cyclohexane, and the solution was heated to 60°C. Next, after dropping 43.7 g of dimer diamine (“PRIAMINE 1075” manufactured by Croda Japan Co., Ltd.) and 5.4 g of 1,3-bisaminomethylcyclohexane, imidization was carried out at 140° C. for 1 hour reaction. Thereby, the varnish (polyimide resin 3, 30 mass % of non-volatile components) containing dimer diamine polyimide resin was obtained. In addition, the weight average molecular weight of the polyimide resin 3 was 25000.

<Example 1>

While stirring, 30 parts of bisphenol A type epoxy resin ("828US" manufactured by Mitsubishi Chemical Corporation, epoxy equivalent about 180), biphenyl type epoxy resin ("NC3000H" manufactured by Nippon Kayaku Co., Ltd., epoxy equivalent about 269) 30 parts were heated and dissolved in a mixed solvent of 40 parts of solvent naphtha and 15 parts of cyclohexanone, and then cooled to room temperature. Spherical silica (average particle size: 0.078 μm, specific surface area: 30.7 m ² /g, Denki Kagaku Kogyo Co., Ltd.) surface-treated with an aminosilane-based coupling agent (Shin-Etsu Chemical Co. "UFP-30" manufactured by the company) 100 parts, a phenolic curing agent containing a triazine skeleton ("LA-3018-50P" manufactured by DIC Corporation, a hydroxyl equivalent of about 151, a 2-methoxypropanol solution with a solid content of 50% ) 14 parts, active ester curing agent ("HPC-8000-65T" manufactured by DIC Corporation, a toluene solution with an active group equivalent of about 223 and a non-volatile content of 65% by mass) 40 parts, polyimide containing polyimide synthesized in Synthesis Example 1 Amine resin 1 varnish (γ-butyrolactone solution with a solid content of 20% by mass) 25 parts, a curing accelerator (“DMAP”, 4-dimethylaminopyridine, methyl ethyl ketone with a solid content of 5% by mass ( Hereinafter referred to as "MEK") solution) 6 parts, uniformly dispersed with a high-speed rotary mixer to prepare resin varnish 1.

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

<Example 2>

In Example 1, the quantity of the varnish (gamma-butyrolactone solution of 20 mass % of solid content) containing the polyimide resin 1 synthesized in the synthesis example 1 was changed from 25 parts to 15 parts. Except for the above matter, it carried out similarly to Example 1, and the resin varnish 2 and the resin sheet 2 were produced.

<Example 3>

In Example 1, the quantity of the varnish (gamma-butyrolactone solution of 20 mass % of solid content) containing the polyimide resin 1 synthesized in the synthesis example 1 was changed from 25 parts to 5 parts. Except for the above matters, it carried out similarly to Example 1, and the resin varnish 3 and the resin sheet 3 were produced.

<Example 4>

In Example 1, 25 parts of the varnish (gamma-butyrolactone solution with a solid content of 20% by mass) composed of polyimide resin 1 synthesized in Synthesis Example 1 was changed to polyimide resin 1 synthesized in Synthesis Example 2. 15 parts of resin 2 varnish (gamma-butyrolactone solution of 20 mass % of solid content). Except for the above matters, it carried out similarly to Example 1, and the resin varnish 4 and the resin sheet 4 were produced.

<Example 5>

In Example 1, 25 parts of the varnish (gamma-butyrolactone solution with a solid content of 20% by mass) composed of polyimide resin 1 synthesized in Synthesis Example 1 was changed to polyimide resin 1 synthesized in Synthesis Example 3. 10 parts of resin 3 varnish (a mixed solution of cyclohexanone and methylcyclohexane having a solid content of 30% by mass). Except for the above matters, it carried out similarly to Example 1, and the resin varnish 5 and the resin sheet 5 were produced.

＜Comparative example 1＞

In Example 1, the quantity of the varnish (gamma-butyrolactone solution of 20 mass % of solid content) containing the polyimide resin 1 synthesized in the synthesis example 1 was changed from 25 parts to 50 parts. Except for the above matters, it carried out similarly to Example 1, and the resin varnish 6 and the resin sheet 6 were produced.

＜Comparative example 2＞

In Example 1, 25 parts of the varnish (gamma-butyrolactone solution with a solid content of 20% by mass) composed of polyimide resin 1 synthesized in Synthesis Example 1 was changed to polyimide resin 1 synthesized in Synthesis Example 2. 50 parts of resin 2 varnishes (gamma-butyrolactone solution with a solid content of 20% by mass). Except for the above matters, it carried out similarly to Example 1, and the resin varnish 7 and the resin sheet 7 were produced.

＜Comparative example 3＞

In Example 1, 25 parts of the varnish (gamma-butyrolactone solution with a solid content of 20% by mass) composed of polyimide resin 1 synthesized in Synthesis Example 1 was changed to polyimide resin 1 synthesized in Synthesis Example 3. 33 parts of resin 3 varnishes (a mixed solution of cyclohexanone and methylcyclohexane having a solid content of 30% by mass). Except for the above matters, it carried out similarly to Example 1, and the resin varnish 8 and the resin sheet 8 were produced.

＜Comparative example 4＞

In Example 1, 25 parts of the varnish (gamma-butyrolactone solution with a solid content of 20% by mass) composed of polyimide resin 1 synthesized in Synthesis Example 1 was replaced with a phenoxy resin ("YX6954BH30" manufactured by Mitsubishi Chemical Corporation). ", a 1:1 solution of MEK with a solid content of 30% by mass and cyclohexanone) 10 parts. Except for the above matters, it carried out similarly to Example 1, and the resin varnish 9 and the resin sheet 9 were produced.

The components used in the preparation of the resin compositions 1 to 9 and their compounding amounts (in terms of nonvolatile matter) are shown in the following tables. In addition, in the following table, "the content (mass %) of (C) component" shows the content of (C) component when the resin component in a resin composition is made into 100 mass %, "(D) component "Content (mass %)" shows the content of (D)component when the non-volatile matter in a resin composition is 100 mass %.

[Table 1]

.

In Examples 1-5, even when (E) component - (F) component was not contained, although there existed a difference in degree, it confirmed that the result similar to the said Example was attributed.

Explanation of reference signs

1 first conductor layer

11 Main surface of the first conductor layer

2 second conductor layer

21 Main surface of the second conductor layer

3 insulating layers

t1 Distance between the first conductor layer and the second conductor layer (thickness of the insulating layer between the first conductor layer and the second conductor layer)

t2 The overall thickness of the insulating layer.

Claims (19)

1. A resin composition comprising: (A) epoxy resin, (B) active ester curing agent, (C) polyimide resin, and (D) inorganic filler, wherein, (D) The average particle diameter of the component is 100 nm or less, When the resin component is 100 mass %, content of (C)component is 0.1 mass % or more and 6 mass % or less. 2. A resin composition comprising: (A) epoxy resin, (B) active ester curing agent, (C) polyimide resin, and (D) inorganic filler, wherein, (D) The specific surface area of the component is 15 m ² /g or more, When the resin component is 100 mass %, content of (C)component is 0.1 mass % or more and 6 mass % or less. 3. The resin composition according to claim 1 or 2, wherein the component (C) is a polyimide resin having a polycyclic aromatic hydrocarbon skeleton. 4. The resin composition according to claim 3, wherein the polycyclic aromatic hydrocarbon skeleton is an aromatic hydrocarbon skeleton in which a five-membered ring compound and an aromatic ring are fused. 5. The resin composition according to claim 3, wherein the polycyclic aromatic hydrocarbon skeleton is at least any one of an indane skeleton and a fluorene skeleton. 6. The resin composition according to claim 1 or 2, wherein the weight average molecular weight of the component (C) is 5,000 or more. 7. The resin composition according to claim 1 or 2, wherein the component (C) has a repeating unit having a polycyclic aromatic hydrocarbon skeleton and a repeating unit having an imide structure. 8. The resin composition according to claim 7, wherein, the mass ratio of the repeating unit with the polycyclic aromatic hydrocarbon skeleton and the repeating unit with the imide structure, that is, the quality of the repeating unit with the polycyclic aromatic hydrocarbon skeleton/the mass ratio of the repeating unit with the imide structure The mass of the repeating unit of the imine structure is 0.5 or more and 2 or less. 9. The resin composition according to claim 1 or 2, wherein the content of the component (C) is 0.1% by mass or more and 3% by mass or less when the non-volatile matter in the resin composition is 100% by mass. 10. The resin composition according to claim 1 or 2, wherein the content of the component (B) is 1 mass % or more and 25 mass % or less when the non-volatile matter in the resin composition is 100 mass %. 11. The resin composition according to claim 1 or 2, wherein the content of the component (D) is 30% by mass or more and 80% by mass or less when the non-volatile matter in the resin composition is 100% by mass. 12. The resin composition according to claim 1 or 2, further comprising (E) a curing agent. 13. The resin composition according to claim 12, wherein the curing agent (E) is a phenolic curing agent. 14. The resin composition according to any one of claims 1 to 13, which is used to form an insulating layer for forming a conductor layer. 15. The resin composition according to claim 1 or 2, which is used to form an insulating layer of a printed wiring board. 16. The resin composition according to claim 1 or 2, which is used to form an interlayer insulating layer of a printed wiring board. 17. A resin sheet comprising a support and the resin composition layer according to any one of claims 1 to 16 provided on the support. 18. A printed wiring board comprising a first conductor layer, a second conductor layer, and an insulating layer formed between the first conductor layer and the second conductor layer, wherein, The insulating layer is a cured product of the resin composition according to any one of claims 1 to 16. 19. A semiconductor device comprising the printed wiring board according to claim 18.