TWI780250B - resin composition - Google Patents

Abstract

The present invention provides a resin composition and the like that can have both the insulating performance and laser processability when the insulating layer is a thin film. The resin composition of the present invention is a resin composition comprising (A) epoxy resin, (B) active ester compound and (C) inorganic filler, wherein (C) component has a coefficient of variation of particle size distribution of 30%. Hereinafter, the average particle diameter is not less than 0.01 μm and not more than 5 μm.

Description

resin composition

The present invention relates to resin compositions. In addition, the present invention relates to a resin sheet, a printed wiring board, and a semiconductor device using the resin composition.

As a manufacturing technique of a printed wiring board, for example, a manufacturing method of a build-up method in which an insulating layer and a conductive layer are alternately stacked is known. In the manufacturing method of the build-up method, generally, the insulating layer is formed by thermosetting the resin composition. For example, Patent Document 1 discloses using a support-attached resin sheet comprising a support and a resin composition layer containing silica particles disposed on the support, laminating the resin composition on the inner substrate, and then A technique in which the resin composition layer is thermally cured, and the resulting hardened body is roughened to form an insulating layer.

Also, for example, Patent Document 2 discloses a technique of reducing the coefficient of thermal expansion of an insulating layer formed by increasing the content of inorganic fillers such as silica particles in a resin composition. [Prior Art Literature] [Patent Document]

[Patent Document 1] International Publication No. 2010/35451 [Patent Document 2] Japanese Patent Laid-Open No. 2010-202865

[Problem to be Solved by the Invention]

In recent years, in order to achieve miniaturization of electronic equipment, the thinner printed wiring boards have been promoted. Accordingly, thinning of the insulating layer is required.

Patent Document 1 discloses that during the roughening treatment, the silicon dioxide particles on the surface of the hardened body are detached, and an insulating layer exhibiting sufficient peel strength with respect to the conductor layer is realized. However, as a result of careful examination by the present inventors, it was found that only the silicon dioxide particles were detached, and a uniform low-roughness roughened surface could not be obtained. Uniform roughening of the surface. When the insulating layer is a thin film, due to the size of the detachment traces, it penetrates the rough surface of the insulating layer and the opposite side surface, and through the detachment traces, one conductor layer is connected to the other conductor layer, and the insulation performance is maintained. Difficult to get. On the other hand, the present inventors have found that when the resin composition contains a hydrophobic resin such as an active ester compound, a roughened surface with low roughness can be formed by performing roughening treatment.

However, the insulating layer may form a via hole for interlayer connection. Via holes are generally formed by laser machining. During laser processing, residues may be generated, but such residues are usually removed during roughening. However, hydrophobic resins such as active ester compounds have high resistance to chemical solutions for roughening treatment. Therefore, when an active ester compound is used, the residue removal tends to be insufficient. If the removal of residues is insufficient, via holes may be clogged with residues, resulting in poor connection between layers and poor conduction reliability.

When using a resin composition containing a hydrophobic resin such as an active ester compound for roughening treatment, in order to improve the residue removability, it is considered that the chemical solution used for the roughening treatment is stronger than usual, or the temperature is higher. Coarser treatment conditions create a severe condition. However, the inorganic filler contained in the resin composition is easily detached due to harsh conditions, and as in Patent Document 1, it becomes a rough surface with large detachment marks, and it may become difficult to maintain insulating performance.

Thus, when active ester compounds are used, formation of via holes tends to be insufficient by laser processing under normal roughening conditions. In addition, under harsh roughening conditions, laser processing can stably form via holes, but due to the detachment of inorganic fillers, there are unintended openings in the insulating layer, and the insulating performance is easily reduced. Therefore, when an active ester compound is used, it is difficult to achieve both insulating performance and laser processability.

Here, the laser processability means the easiness of forming via holes by processing including laser irradiation and subsequent roughening.

These problems, especially when the insulating layer is thin, unintended holes are likely to be formed due to detachment of the inorganic filler during roughening treatment, so it is particularly difficult to solve the above-mentioned problems.

The present invention has been accomplished in view of the aforementioned problems. The object of the present invention is to provide a resin composition having both insulating performance and laser processability even if the insulating layer is a thin film; A resin sheet; a printed wiring board including an insulating layer formed of a cured product of the aforementioned resin composition; and a semiconductor device including a cured product of the aforementioned resin composition. [Means to solve the problem]

As a result of careful examination by the present inventors in order to solve the aforementioned problems, it was found that the aforementioned problems can be solved by a resin composition comprising (A) an epoxy resin, (B) an active ester compound, and (C) a specific inorganic filler, and Complete the present invention. That is, the present invention includes the following.

[1] A resin composition comprising (A) an epoxy resin, (B) an active ester compound, and (C) an inorganic filler, wherein the coefficient of variation of the particle size distribution of the component (C) is 30 % or less, the average particle size is not less than 0.01 μm and not more than 5 μm. [2] The resin composition according to the aforementioned [1], wherein the content of the component (C) is 50% by mass or more when the non-volatile components in the resin composition are taken as 100% by mass. [3] The resin composition according to the aforementioned [1] or [2], wherein the average particle diameter of the component (C) is not less than 0.1 μm and not more than 3 μm. [4] The resin composition according to any one of the aforementioned [1] to [3], which is used for forming an insulating layer of a printed wiring board. [5] The resin composition according to any one of the aforementioned [1] to [4], wherein the ratio (L/S) of the circuit width (L (μm)) to the circuit width (S (μm)) is For circuit formation of 10μm/10μm or less. [6] The resin composition according to any one of [1] to [5] above, which is a resin composition for forming an insulating layer having a surface having an arithmetic average roughness (Ra) of 150 nm or less. [7] The resin composition according to any one of [1] to [6] above, which is a resin composition for forming via holes by laser irradiation. [8] The resin composition according to any one of the above-mentioned [1]~[7], which is to select any 10 places on the surface of the hardened product after the resin composition is cured at 200°C for 90 minutes, and perpendicular to the place. In the sectional image (sectional image) of the surface of the hardened object, when observing the range of arbitrarily selected width 100 μm and depth 5 μm, When the maximum particle size of component (C) is R1 (μm) and the average particle size of component (C) is R2 (μm), the The relationship of R1<1.4×R2. [9] The resin composition according to any one of the aforementioned [1] to [8], which is to select any 10 positions on the surface of the cured product that are cured at 200°C for 90 minutes, and perpendicular to the position In the cross-sectional view of the surface of the hardened material, when observing the range of arbitrarily selected width 100 μm and depth 5 μm, (C) When the average particle size of the component is R2 (μm), The number of particles having a particle diameter of (1.2×R2) μm or more is 4 or less. [10] A resin sheet comprising a support, and a resin composition layer comprising the resin composition according to any one of the aforementioned [1] to [9] provided on the support. [11] The resin sheet according to the aforementioned [10], wherein the thickness of the resin composition layer is 15 μm or less. [12] A resin sheet comprising a support, and a resin composition layer provided on the support and containing a resin composition containing (C) an inorganic filler, The resin composition contains 50% by mass or more of the (C) inorganic filler when the non-volatile components in the resin composition are taken as 100% by mass. Select any 10 places on the surface of the cured product that have been cured by heat at 200°C for 90 minutes, and observe the randomly selected range with a width of 100 μm and a depth of 5 μm in a cross-sectional view perpendicular to the surface of the hardened product , (C) When the maximum particle size of the inorganic filler is R1 (μm), and (C) the average particle size of the inorganic filler is R2 (μm), Satisfy the relationship of R1<1.4×R2. [13] A resin sheet comprising a support, and a resin composition layer provided on the support and containing a resin composition containing (C) an inorganic filler, The resin composition contains 50% by mass or more of the (C) inorganic filler when the non-volatile components in the resin composition are taken as 100% by mass. Select any 10 places on the surface of the cured product that have been cured by heat at 200°C for 90 minutes, and observe the randomly selected range with a width of 100 μm and a depth of 5 μm in a cross-sectional view perpendicular to the surface of the hardened product , (C) When the maximum particle size of the inorganic filler is R2 (μm), The number of particles having a particle diameter of (1.2×R2) μm or more is 4 or less. [14] 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, The insulating layer is a cured product of the resin composition according to any one of the aforementioned [1] to [9]. [15] A semiconductor device comprising the printed wiring board described in [14] above. [Invention effect]

According to the present invention, it is possible to provide a resin composition having both insulation performance and laser processability even if the insulating layer is a thin film; a resin sheet having a resin composition layer comprising the aforementioned resin composition; and a resin composition comprising the aforementioned resin composition. A printed wiring board with an insulating layer formed of a cured product of the resin composition; and a semiconductor device including a cured product of the aforementioned resin composition.

Embodiments and illustrations are shown below to describe the present invention in detail. However, the present invention is not limited to the embodiments and exemplified objects listed below, and can be implemented with arbitrary modifications within the range not departing from the scope of claims and equivalents of the present invention.

[Resin composition] The resin composition of the present invention is a resin composition comprising (A) epoxy resin, (B) active ester compound, and (C) inorganic filler, wherein the coefficient of variation of particle size distribution of component (C) is 30% or less , the average particle size is not less than 0.01 μm and not more than 5 μm. By combining the aforementioned (A) epoxy resin, (B) active ester compound, and (C) specific inorganic filler, it is possible to obtain the present invention that has both insulating performance and laser processability even if the insulating layer is a thin film the desired effect. Even if the surface of the cured product of this resin composition is roughened under harsher conditions than usual, the traces of (C) inorganic filler detachment on the roughened surface are uniform and small. As a result, even if the insulating layer is thin, the insulation can be improved. reliability. Therefore, the cured product of this resin composition can exhibit its excellent properties and is suitable for use as an insulating layer of a printed wiring board.

In addition, the above-mentioned resin composition may combine components (A) to (C) and further include optional components. Examples of optional components include (D) curing agent, (E) curing accelerator, (F) thermoplastic resin, (G) flame retardant, and (H) other additives.

＜(A) Epoxy resin＞ The resin composition contains (A) epoxy resin as (A) component. (A) Epoxy resins include, for example, bis-xylenol-type epoxy resins, bisphenol-A-type epoxy resins, bisphenol-F-type epoxy resins, bisphenol-S-type epoxy resins, and bisphenol-AF-type epoxy resins. , dicyclopentadiene type epoxy resin, triphenol type epoxy resin, naphthol novolak type epoxy resin, phenol novolak type epoxy resin, tert-butyl-catechol type epoxy resin, naphthalene type Epoxy resin, naphthol type epoxy resin, anthracene type epoxy resin, glycidyl amine type epoxy resin, glycidyl ester type epoxy resin, cresol novolac epoxy resin, biphenyl type epoxy resin, Linear aliphatic epoxy resin, epoxy resin with butadiene structure, alicyclic epoxy resin, heterocyclic epoxy resin, spiro ring-containing epoxy resin, cyclohexane epoxy resin, cyclohexane Dimethanol type epoxy resin, pernaphthyl ether type epoxy resin, trimethylol type epoxy resin, tetraphenylethane type epoxy resin, etc. Among them, bisphenol A type epoxy resin and biphenyl type epoxy resin are preferable. One type of epoxy resin may be used alone, or two or more types may be used in combination.

(A) Epoxy resins preferably have two or more epoxy groups in one molecule. When the non-volatile content of the epoxy resin is 100% by mass, at least 50% by mass or more is preferably an epoxy resin having two or more epoxy groups in one molecule. Wherein, the resin composition system includes a liquid epoxy resin at a temperature of 20°C (hereinafter also referred to as "liquid epoxy resin") and a solid epoxy resin at a temperature of 20°C (hereinafter also referred to as "liquid epoxy resin"). Solid epoxy resin") is preferred. The liquid epoxy resin is preferably a 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. Furthermore, the liquid epoxy resin and the solid epoxy resin are preferably aromatic epoxy resins.

Liquid epoxy resin is based on bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol AF type epoxy resin, naphthalene type epoxy resin, glycidyl ester type epoxy resin, glycidyl amine Type epoxy resin, phenol novolak type epoxy resin, alicyclic epoxy resin with ester skeleton, cyclohexane type epoxy resin, cyclohexanedimethanol type epoxy resin, glycidylamine type epoxy resin , aliphatic epoxy resins, and epoxy resins with a butadiene structure are preferred, more preferably aliphatic epoxy resins, bisphenol A epoxy resins, and bisphenol F epoxy resins.

Specific examples of liquid epoxy resins include "HP4032", "HP4032D", and "HP4032SS" (naphthalene-type epoxy resin) manufactured by DIC Corporation, "828US", "jER828EL", and "825" manufactured by Mitsubishi Chemical Co., Ltd. , "Epikote828EL" (bisphenol A type epoxy resin), "jER807", "1750" (bisphenol F type epoxy resin), "jER152" (phenol novolak type epoxy resin), "630", "630LSD "(glycidylamine epoxy resin), "ZX1059" manufactured by Nippon Steel & Sumitomo Metal Chemical Co., Ltd. (mixture of bisphenol A epoxy resin and bisphenol F epoxy resin), "Nagase Chemtex" manufactured EX-721" (glycidyl ester type epoxy resin), "CELLOXID2021P" (alicyclic epoxy resin with ester skeleton) manufactured by DAICEL, "PB-3600" (epoxy resin with butadiene structure) ), "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 Co., Ltd. Epoxy resin), "EXA-850CRP" (bisphenol A type epoxy resin) manufactured by DIC Corporation, "YED-216D" (aliphatic epoxy resin) manufactured by Mitsubishi Chemical Corporation, "EP-3950S" manufactured by ADEKA Corporation ", "EP-3980S" (glycidylamine type epoxy resin); "ELM-100H" (glycidylamine type epoxy resin) manufactured by Sumitomo Chemical Co., Ltd., etc. These may be used individually by 1 type, and may use it in combination of 2 or more types.

Solid epoxy resins are based on bis-xylenol-type epoxy resins, naphthalene-type epoxy resins, naphthalene-type 4-functional epoxy resins, cresol novolac epoxy resins, dicyclopentadiene-type epoxy resins, triphenol Type epoxy resin, naphthol type epoxy resin, biphenyl type epoxy resin, pernathyl ether type epoxy resin, anthracene type epoxy resin, bisphenol A type epoxy resin, bisphenol AF type epoxy resin, four The phenylethane-type epoxy resin is preferable, and bis-xylenol-type epoxy resin, naphthalene-type epoxy resin, bisphenol AF-type epoxy resin, and pernaphthylether-type epoxy resin are more preferable.

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

As (A) component, when liquid epoxy resin and solid epoxy resin are used together, their ratio (liquid epoxy resin: solid epoxy resin) is based on mass ratio, preferably 1:0.01~ 1:20 range. By setting the amount ratio of the liquid epoxy resin to the solid epoxy resin in this range, i) moderate adhesiveness, ii) sufficient flexibility can be obtained to improve workability, and iii) the The effect of obtaining a hardened product with sufficient breaking strength is obtained. From the point of view of the effects of i)~iii) above, the ratio of liquid epoxy resin to solid epoxy resin (liquid epoxy resin: solid epoxy resin) is based on mass ratio, preferably 1:0.05 The range of ~1:15, and more preferably the range of 1:0.1~1:10.

The content of the component (A) in the resin composition is preferably 1 mass % when the non-volatile components in the resin composition are 100 mass % from the viewpoint of obtaining an insulating layer exhibiting good mechanical strength and insulation reliability. % or more, more preferably 5 mass % or more, and more preferably 10 mass % or more. The upper limit of the epoxy resin content is not particularly limited as long as the effect of the present invention is exerted, but it is preferably 40% by mass or less, more preferably 30% by mass or less, and more preferably 20% by mass or less. In addition, in the present invention, the content of each component in the resin composition is a value when the non-volatile content in the resin composition is 100% by mass unless otherwise specified.

(A) The epoxy equivalent of component is preferably 50-5000, more preferably 50-3000, more preferably 80-2000, more preferably 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 obtained. Moreover, epoxy equivalent can be measured based on JISK7236, and is the mass of the resin containing the epoxy group of 1 equivalent.

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

＜(B) Active ester compound＞ The resin composition contains (B) active ester compound as (B) component. When an active ester compound is used, residue removability is generally poor. However, since the resin composition of the present invention contains the (C) inorganic filler described later, it can achieve high insulating performance even if the roughening treatment is performed under harsher conditions than usual. Therefore, roughening treatment can be performed under harsher conditions than usual, and high laser processability can be achieved.

The active ester compound has the function of hardening the (A) epoxy resin, and it is generally preferable to use phenol esters, thiophenol esters, N-hydroxylamine esters, esters of heterocyclic hydroxy compounds, etc. A compound with two or more highly reactive ester groups. The active ester compound is preferably obtained by condensation reaction of carboxylic acid compound and/or thiocarboxylic acid compound with hydroxyl compound and/or thiol compound. In particular, from the viewpoint of improving heat resistance, an active ester compound obtained from a carboxylic acid compound and a hydroxyl compound is preferred, and an active ester compound obtained from a carboxylic acid compound, a phenol compound and/or a naphthol compound is more preferred. Examples of the carboxylic acid compound include benzoic acid, acetic acid, succinic acid, maleic acid, itaconic acid, phthalic acid, isophthalic acid, terephthalic acid, and pyromellitic acid. Phenol compounds or naphthol compounds include, for example, hydroquinone, resorcinol, bisphenol A, bisphenol F, bisphenol S, phenolphthalein, methylated bisphenol A, methylated bisphenol F, methylated bisphenol Phenol S, phenol, o-cresol, m-cresol, p-cresol, catechol, α-naphthol, β-naphthol, 1,5-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 2,6-Dihydroxynaphthalene, Dihydroxybenzophenone, Trihydroxybenzophenone, Tetrahydroxybenzophenone, Phloroglucinol, Glycerol, Dicyclopentadiene type diphenol compound, Phenol novolac Varnish etc. Here, the "dicyclopentadiene-type diphenol compound" means the diphenol compound obtained by condensation of 1 molecule of dicyclopentadiene and 2 molecules of phenol.

Specifically, the component (B) is an active ester compound containing dicyclopentadiene-type diphenol structure, an active ester compound containing naphthalene structure, an active ester compound containing acetylated phenol novolac, an active ester compound containing phenol novolak The active ester compound of the benzoyl compound is preferable, among them, the active ester compound containing the naphthalene structure and the active ester compound containing the dicyclopentadiene type diphenol structure are more preferable. The "dicyclopentadiene-type diphenol structure" means a divalent structural unit composed of phenylene-dicyclopentyl-phenylene.

Commercially available active ester compounds, including active ester compounds with a dicyclopentadiene-type diphenol structure, include "EXB9451", "EXB9460", "EXB9460S", "HPC-8000-65T", "HPC-8000H -65TM", "EXB-8000L-65TM" (manufactured by DIC Corporation), active ester compounds containing naphthalene structure, examples include "EXB-8150-60T", "EXB9416-70BK" (manufactured by DIC Corporation), containing phenol novolac The active ester compound of the acetylated compound includes "DC808" (manufactured by Mitsubishi Chemical), and the active ester compound of the benzoyl compound including phenol novolac includes "YLH1026" (manufactured by Mitsubishi Chemical), which includes phenol novolac The active ester compound of the acetylated compound of the varnish includes "DC808" (manufactured by Mitsubishi Chemical Co.), and the active ester-based hardener of the benzoyl compound of the phenol novolac includes "YLH1026" (manufactured by Mitsubishi Chemical Company), " "YLH1030" (manufactured by Mitsubishi Chemical Co., Ltd.), "YLH1048" (manufactured by Mitsubishi Chemical Co., Ltd.), and the like.

(A) The amount ratio of epoxy resin and (B) active ester compound is based on the ratio of [the total number of epoxy groups of epoxy resin]: [the total number of reactive groups of active ester compound], preferably 1: The range of 0.01~1:5 is more preferably 1:0.05~1:2, and more preferably 1:0.1~1:1. Here, the reactive group of the active ester compound refers to an active ester group. In addition, the total number of epoxy groups in epoxy resins refers to the value obtained by dividing the solid content mass of each epoxy resin by the epoxy equivalent, which is the total value for all epoxy resins, and the total number of reactive groups in active ester compounds The value obtained by dividing the solid content mass of each active ester compound by the reactive group equivalent is the total value for all active ester compounds. By setting the molar ratio of the epoxy resin and the active ester compound within this range, the heat resistance of the cured product of the resin composition can be further improved.

(B) The content of the active ester compound is preferably at least 1% by mass, more preferably at least 3% by mass, and more preferably at least 5% by mass when the non-volatile components in the resin composition are 100% by mass. Moreover, the upper limit is preferably at most 30% by mass, more preferably at most 20% by mass, and still more preferably at most 15% by mass. By setting content of (B) component in this range, the hardened|cured material excellent in residue removability can be obtained.

＜(C) Inorganic filler＞ The resin composition contains (C) inorganic filler as (C) component. Usually, the (C) inorganic filler is contained in the resin composition in the state of particles. (C) The average particle diameter of the inorganic filler is 0.01 μm or more, preferably 0.05 μm or more, more preferably 0.1 μm or more, 0.3 or more. The upper limit is 5 μm or less, preferably 3 μm or less, more preferably 1 μm or less or 0.5 μm or less. (C) When the average particle size of the inorganic filler is not more than this upper limit, insulation reliability can be improved even if the insulating layer is thin. Moreover, by being more than the lower limit, the filling property of (C) inorganic filler in a resin composition can be improved more, and the desired effect of this invention can be acquired remarkably.

(C) The average particle size of the particles of the inorganic filler can be measured by the laser diffraction and scattering method based on the Mie scattering theory. Specifically, the particle size distribution of the particles is produced on a volume basis with a laser diffraction scattering type particle size distribution measuring device, and the average particle size is measured as the median particle size from the particle size distribution. It is preferable to use a measurement sample in which particles are dispersed in a solvent such as water by ultrasonic waves. As the laser diffraction scattering type particle size distribution measuring device, "LA-500" manufactured by Horiba Corporation, "SALD-2200" manufactured by Shimadzu Corporation, etc. can be used.

(C) The coefficient of variation of the particle size distribution of the inorganic filler is 30% or less, preferably 20% or less, more preferably 10% or less, and more preferably 5% or less. The lower limit is not particularly limited, but may be 0% or more. The coefficient of variation of the particle size distribution is as close to 0% as possible. By setting the coefficient of variation of the particle size distribution of the (C) inorganic filler within this range, the particle size distribution of the (C) inorganic filler becomes sharp (Sharp). Therefore, even if the roughening treatment is performed under harsher conditions than usual, the (C) inorganic filler will be detached, and the detachment marks on the roughened surface will become uniform. The roughened side of a layer and its opposite side. As a result, insulation reliability can be improved even if the insulating layer is thin. The particle size distribution is the particle size distribution based on volume.

(C) The coefficient of variation of the particle size distribution of the inorganic filler particles can be obtained by multiplying the standard deviation of the average particle size by the arithmetic mean of the average particle size and multiplying by 100(%). The aforementioned standard deviation is preferably at least 0.0001, more preferably at least 0.001, more preferably at least 0.01, preferably at most 0.5, more preferably at most 0.1, and more preferably at most 0.05. In addition, the arithmetic mean is preferably at least 0.01, more preferably at least 0.05, more preferably at least 0.1, preferably at most 5, more preferably at most 3, and more preferably at most 1. By setting the standard deviation and arithmetic mean within this range, the coefficient of variation can be set within a specific range.

Consider selecting any 10 places on the surface of the cured product where the resin composition is cured at 200°C for 90 minutes, and observe the randomly selected range of 100 μm in width and 5 μm in depth in the cross-sectional view perpendicular to the surface of the hardened product situation. In this case, let the maximum particle diameter of (C) inorganic filler be R1 (micrometer), and the average particle diameter of (C) inorganic filler should be R2 (micrometer). At this time, the maximum particle diameter R1 and the average particle diameter R2 preferably satisfy the relationship of the following formula (1), more preferably satisfy the relationship of the following formula (2), and more preferably satisfy the following formula (3) relationship. By satisfying this relationship between the maximum particle size R1 and the average particle size R2, even if the roughening treatment is performed under harsher conditions than usual, the (C) inorganic filler will be detached, and the traces of detachment on the roughened surface will become smaller. As a result, even if the insulation Thin layers can also improve insulation reliability. The above-mentioned cross-sectional view can be observed, for example, using a FIB-SIM composite device, and the maximum particle diameter R1 and the average particle diameter R2 can also be measured from this image. R1<1.4×R2 (1) R1<1.3×R2 (2) R1<1.2×R2 (3)

Consider selecting any 10 places on the surface of the cured product where the resin composition is cured at 200°C for 90 minutes, and observe the randomly selected range of 100 μm in width and 5 μm in depth in the cross-sectional view perpendicular to the surface of the hardened product situation. In this case, let the average particle diameter of (C) inorganic filler be R2 (micrometer). In this case, the number of particles having a particle diameter of (1.2×R2) μm or more is preferably small. The specific number is preferably 4 or less, more preferably 3 or less, still more preferably 2 or less, and 1 or less. The number of (C) inorganic fillers observed within a specific range having a particle diameter of 1.2 times or more the average particle diameter of the (C) inorganic filler is within this range, even under harsher conditions than usual With the roughening treatment, (C) the inorganic filler is detached, and the traces of detachment on the roughened surface are also reduced. As a result, even if the insulating layer is thin, the insulation reliability can be improved. The above-mentioned cross-sectional view is observed, for example, using a FIB-SIM composite device, and the average particle diameter R2 and the number of particles having a particle diameter of (1.2×R2) μm or more can be measured from the image.

(C) The material of the inorganic filler is to use an inorganic compound. (C) Materials for inorganic fillers include, for example, silica, alumina, glass, smilax, silicon oxide, barium sulfate, barium carbonate, talc, clay, mica powder, zinc oxide, hydrotalcite, water Aluminum stone, aluminum hydroxide, magnesium hydroxide, calcium carbonate, magnesium carbonate, magnesium oxide, boron nitride, aluminum nitride, manganese nitride, aluminum borate, strontium carbonate, strontium titanate, calcium titanate, magnesium titanate, Bismuth titanate, titanium oxide, zirconium oxide, barium titanate, barium titanate zirconate, barium zirconate, calcium zirconate, zirconium phosphate, and zirconium phosphotungstate, etc. Among them, silicon dioxide is particularly preferable from the viewpoint of remarkably obtaining the desired effect of the present invention. Examples of silica include amorphous silica, fused silica, crystalline silica, synthetic silica, and hollow silica. Also, silica is preferably spherical silica. (C) The inorganic fillers may be used alone or in combination of two or more of them in arbitrary ratios.

As mentioned above (C) inorganic filler, for example, "seahosterKE-S10", "seahosterKE-S20", "seahosterKE-S30", "seahosterKE-S50", "KE-P30" manufactured by Nippon Shokubai Co., Ltd.; NIPPON "SP60-05", "SP507-05" manufactured by STEEL & SUMIKIN MATERIALS; "YC100C", "YA050C", "YA050C-MJE", "YA010C" manufactured by admatechs; "UFP-30" manufactured by Denka ; "SilFileNSS-3N", "SilFileNSS-4N", "SilFileNSS-5N" manufactured by Tokuyama Corporation; "SC2500SQ", "SO-C4", "SO-C2", "SO-C1" manufactured by admatechs Corporation; Wait.

(C) The inorganic filler can be adjusted within the range of the coefficient of variation of the specific particle size distribution and within the range of the specific average particle size by, for example, classifying.

(C) The inorganic filler is preferably surface-treated with an appropriate surface treatment agent. The moisture resistance and dispersibility of the (C) inorganic filler can be improved by surface treatment. Surface treatment agents include, for example, fluorine-containing silane coupling agents, aminosilane coupling agents, epoxy silane coupling agents, mercaptosilane coupling agents, silane coupling agents, alkoxysilane compounds, organosilazanes compound, titanate coupling agent, etc.

Commercially available surface treatment agents include, for example, "KBM22" (dimethyldimethoxysilane) manufactured by Shin-Etsu Chemical Co., Ltd., "KBM403" (3-glycidoxypropyltrimethoxysilane) manufactured by Shin-Etsu Chemical Co., Ltd. Shin-Etsu Chemical Co., Ltd. "KBM803" (3-mercaptopropyltrimethoxysilane), Shin-Etsu Chemical Co., Ltd. "KBE903" (3-aminopropyltriethoxysilane), Shin-Etsu Chemical Co., Ltd. "KBM573" (N-phenyl-3-aminopropyltrimethoxysilane) manufactured by Shin-Etsu Chemical Co., Ltd. "KBM5783" (N-phenyl-3-aminooctyltrimethoxysilane) manufactured by Shin-Etsu Chemical Co., Ltd. "SZ-31" (hexamethyldisilazane) manufactured by Kogyo Co., Ltd., "KBM103" (phenyltrimethoxysilane) manufactured by Shin-Etsu Chemical Co., Ltd., "KBM-4803" (long-chain epoxy base type silane coupling agent), etc. Among them, a silane coupling agent containing a nitrogen atom is preferable, an aminosilane coupling agent containing a phenyl group is more preferable, and N-phenyl-3-aminoalkyltrimethoxysilane is more preferable. Moreover, a surface treatment agent may be used individually by 1 type, and may use it combining 2 or more types by arbitrary ratios.

The degree of surface treatment by the surface treatment agent can be evaluated by the amount of carbon per unit surface area of (C) the inorganic filler. (C) The amount of carbon per unit surface area of the inorganic filler is preferably at least 0.02 mg/m ² , more preferably at least 0.1 mg/m ² from the viewpoint of improving the dispersibility of the (C) inorganic filler. It is above 0.2 mg/m ² . In addition, from the viewpoint of suppressing the increase of the melt viscosity of the resin composition and the melt viscosity in the form of flakes, the aforementioned carbon content is preferably ¹ mg/m or less, more preferably 0.8 ^mg /m or less, particularly preferably 0.5 mg / ^m2 or less.

(C) The amount of carbon per unit surface area of the inorganic filler can be cleaned by washing the (C) inorganic filler after surface treatment with a solvent (for example, methyl ethyl ketone (hereinafter sometimes referred to as "MEK")) Measured after treatment. Specifically, a sufficient amount of methyl ethyl ketone was mixed with (C) the inorganic filler treated with a surface treatment agent, and cleaned by ultrasonic waves at 25° C. for 5 minutes. Then, after removing the supernatant and drying the solid content, the amount of carbon per unit surface area of (C) the inorganic filler can be measured using a carbon analyzer. As a carbon analyzer, "EMIA-320V" manufactured by HORIBA, Ltd. can be used.

The amount of (C) inorganic filler in the resin composition is relative to 100% by mass of the non-volatile components in the resin composition, preferably 50% by mass or more, more preferably 55% by mass or more, and more preferably 60% by mass % or more, preferably less than 80% by mass, more preferably less than 75% by mass, and more preferably less than 70% by mass. When the quantity of (C) inorganic filler exists in the said range, film insulation can be improved. In addition, according to the present invention, even when many inorganic fillers are contained in the thin film, insulation reliability can be improved.

＜(D) Hardener＞ The resin composition may contain (D) a curing agent as an optional component. However, (B) active ester compound is not included in (D) curing agent. The (D) curing agent is not particularly limited as long as it has the function of curing the (A) epoxy resin, and examples thereof include phenol-based curing agents, naphthol-based curing agents, benzoxazine-based curing agents, Cyanate-based hardeners, carbodiimide-based hardeners, etc. Among them, from the viewpoint of improving insulation reliability, the (D) curing agent is preferably any one or more of phenol-based curing agents, naphthol-based curing agents, cyanate-based curing agents, and carbodiimide-based curing agents, and more preferably It is preferable to contain a phenolic curing agent. The curing agent may be used alone or in combination of two or more.

The phenolic hardener and the naphthol hardener are preferably phenolic hardeners having a novolac structure or naphthol hardeners with a novolac structure from the viewpoint of heat resistance and water resistance. Also, from the viewpoint of adhesion to the conductor layer, a nitrogen-containing phenolic curing agent is preferred, and a triazine skeleton-containing phenolic curing agent is more preferred.

Specific examples of phenolic hardeners and naphthol hardeners include, for example, "MEH-7700", "MEH-7810", and "MEH-7851" manufactured by Meiwa Kasei Co., Ltd., and "NHN" 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" manufactured by DIC Corporation, "LA-7052", "LA-7054", "LA-1356", "LA-3018-50P", "EXB-9500", etc.

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.

Cyanate-based hardeners include, for example, bisphenol A dicyanate, polyphenol cyanate, oligo(3-methylene-1,5-phenylene cyanate), 4,4'- Methyl bis(2,6-dimethylphenyl cyanate), 4,4'-ethylene diphenyl dicyanate, hexafluorobisphenol A dicyanate, 2,2-bis( 4-cyanate)phenylpropane, 1,1-bis(4-cyanatephenylmethane), bis(4-cyanate-3,5-dimethylphenyl)methane, 1,3- 2 of bis(4-cyanate phenyl-1-(methylethylene))benzene, bis(4-cyanate phenyl)sulfide, and bis(4-cyanate phenyl)ether Functional cyanate resins, polyfunctional cyanate resins derived from phenol novolaks and cresol novolacs, prepolymers in which a part of these cyanate resins has been triazinated, etc. Specific examples of cyanate-based hardeners include "PT30" and "PT60" (phenol novolac type multifunctional cyanate resin) and "ULL-950S" (multifunctional cyanate resin) manufactured by Lonza Japan Co., Ltd. , "BA230", "BA230S75" (prepolymers 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 Co., Ltd., and the like.

When the resin composition contains (D) hardener, the amount ratio of epoxy resin to (D) hardener is the ratio of [the total number of epoxy groups of epoxy resin]: [the total number of reactive groups of hardener] , preferably in the range of 1:0.01~1:2, more preferably in the range of 1:0.01~1:1, and more preferably in the range of 1:0.05~1:0.5. Here, the reactive group of the curing agent is an active hydroxyl group, etc., and varies depending on the type of curing agent. In addition, the total number of epoxy groups in epoxy resins refers to the total value obtained by dividing the solid content mass of each epoxy resin by the epoxy equivalent value for all epoxy resins, and the total number of reactive groups in the hardener The value obtained by dividing the solid content mass of each curing agent by the reactive group equivalent is the total value for all curing agents. By setting the molar ratio between the epoxy resin and the curing agent in this range, the heat resistance of the cured product of the resin composition can be further improved.

When the resin composition contains (B) active ester compound and (D) hardener, the amount ratio of epoxy resin to (B) active ester compound and (D) hardener is [total number of epoxy groups in epoxy resin] : The ratio of [the total number of reactive groups of components (B) and (D)] is preferably in the range of 1:0.01 to 1:5, more preferably 1:0.01 to 1:3, and more preferably 1: 0.01~1:1.5. By making the amount ratio of an epoxy resin, (B) component, and (D) component into this range, the heat resistance of the hardened|cured material of a resin composition can be improved more.

When the resin composition contains the (D) hardener, the content of the (D) hardener is preferably 0.1% by mass or more, more preferably 0.5% by mass when the non-volatile components in the resin composition are 100% by mass. or more, more preferably 1% by mass or more. The upper limit is preferably at most 15% by mass, more preferably at most 10% by mass, and still more preferably at most 8% by mass. By making content of (D) hardening|curing agent into this range, the heat resistance of the hardened|cured material of a resin composition can be improved more.

＜(E) Hardening Accelerator＞ The resin composition may also contain (E) a hardening accelerator as an optional component. By using a hardening accelerator, when hardening a resin composition, hardening can be accelerated|stimulated.

(E) The hardening accelerator includes, for example, phosphorus-based hardening accelerators, amine-based hardening accelerators, imidazole-based hardening accelerators, guanidine-based hardening accelerators, metal-based hardening accelerators, and the like. Among them, phosphorus-based hardening accelerators, amine-based hardening accelerators, imidazole-based hardening accelerators, and metal-based hardening accelerators are preferable, and amine-based hardening accelerators, imidazole-based hardening accelerators, and metal-based hardening accelerators are more preferable. The hardening accelerator may be used alone or in combination of two or more.

Phosphorus-based hardening accelerators include, for example, triphenylphosphine, phosphonium borate compounds, tetraphenylphosphonium tetraphenylborate, n-butylphosphonium tetraphenylborate, tetrabutylphosphonium decanoate, (4- Methylphenyl)triphenylphosphonium thiocyanate, tetraphenylphosphonium thiocyanate, butyltriphenylphosphonium thiocyanate and the like. Among them, triphenylphosphine and tetrabutylphosphonium decanoate are preferred.

Amine-based hardening accelerators include, for example, trialkylamines such as triethylamine and tributylamine, 4-dimethylaminopyridine, benzyldimethylamine, 2,4,6,-tri( Dimethylaminomethyl)phenol, 1,8-diazabicyclo(5,4,0)-undecene, 4-pyrrolidinylpyridine, etc. Among them, 4-dimethylaminopyridine, 1,8-diazabicyclo(5,4,0)-undecene, and 4-pyrrolidinylpyridine are preferred.

Imidazole-based hardening accelerators include, for example, 2-methylimidazole, 2-undecylimidazole, 2-heptadecylimidazole, 1,2-dimethylimidazole, and 2-ethyl-4-methylimidazole , 2-phenylimidazole, 2-phenyl-4-methylimidazole, 1-benzyl-2-methylimidazole, 1-benzyl-2-phenylimidazole, 1-cyanoethyl-2-methyl Imidazole, 1-cyanoethyl-2-undecylimidazole, 1-cyanoethyl-2-ethyl-4-methylimidazole, 1-cyanoethyl-2-phenylimidazole, 1 -cyanoethyl-2-undecylimidazolium trimellitate, 1-cyanoethyl-2-phenylimidazolium trimellitate, 2,4-diamino-6-[ 2'-methylimidazolyl-(1')]-ethyl-s-triazine, 2,4-diamino-6-[2'-undecylimidazolyl-(1')]-ethyl Base-s-triazine, 2,4-diamino-6-[2'-ethyl-4'-methylimidazolyl-(1')]-ethyl-s-triazine, 2,4- Diamino-6-[2'-methylimidazolyl-(1')]-ethyl-s-triazine isocyanuric acid adduct, 2-phenylimidazole isocyanuric acid adduct , 2-phenyl-4,5-dihydroxymethylimidazole, 2-phenyl-4-methyl-5-hydroxymethylimidazole, 2,3-dihydro-1H-pyrrolo[1,2-a ]benzimidazole, 1-dodecyl-2-methyl-3-benzyl imidazolium chloride, 2-methylimidazoline, 2-phenylimidazoline and other imidazole compounds and imidazole compounds and epoxy resins The adduct (Adduct). Among them, 2-ethyl-4-methylimidazole and 1-benzyl-2-phenylimidazole are preferable.

As the imidazole-based hardening accelerator, a commercially available product can be used, and examples thereof include "P200-H50" manufactured by Mitsubishi Chemical Co., Ltd.; "2E4MZ" manufactured by Shikoku Chemicals; and the like.

Guanidine hardening accelerators include, for example, 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-Dimethylbiguanide, 1,1-diethylbiguanide, 1-cyclohexylbiguanide, 1-allylbiguanide, 1-phenylbiguanide, 1-(o-tolyl)biguanide, etc. Among them, dicyandiamide and 1,5,7-triazabicyclo[4.4.0]dec-5-ene are preferred.

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

When the resin composition contains the (E) hardening accelerator, the amount of the (E) hardening accelerator is preferably 0.01% with respect to 100% by mass of the resin component of the resin composition from the viewpoint of remarkably obtaining the desired effect of the present invention. Mass % or more, more preferably 0.05 mass % or more, more preferably 0.1 mass % or more, preferably 3 mass % or less, more preferably 1 mass % or less, and more preferably 0.5 mass % or less.

＜(F) Thermoplastic resin＞ The resin composition may contain (F) a thermoplastic resin as an optional component. Examples of (F) thermoplastic resins include phenoxy resins, polyvinyl acetal resins, polyolefin resins, polybutadiene resins, polyimide resins, polyamideimide resins, polyetherimide resins, and polyetherimide resins. Imine resin, polyether resin, polyether resin, polyphenylene ether resin, 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.

(F) The polystyrene-equivalent weight average molecular weight of the thermoplastic resin is preferably at least 30,000, more preferably at least 35,000, and still more preferably at least 40,000. The upper limit is preferably at most 100,000, more preferably at most 70,000, and still more preferably at most 60,000. (F) The polystyrene equivalent weight average molecular weight of a thermoplastic resin can be measured using the gel permeation chromatography (GPC) method. Specifically, (F) The polystyrene-equivalent weight average molecular weight of the thermoplastic resin used LC-9A/RID-6A manufactured by Shimadzu Corporation as a measuring device, and Shodex K-800P/K manufactured by Showa Denko Corporation as a column. -804L/ K-804L, chloroform as the mobile phase, measured at a column temperature of 40°C, can be calculated using the calibration curve of standard polystyrene.

Phenoxy resins include, for example, those having a skeleton selected from bisphenol A skeleton, bisphenol F skeleton, bisphenol S skeleton, bisphenol acetophenone skeleton, novolak skeleton, biphenyl skeleton, fennel skeleton, and dicyclopentadiene skeleton. A phenoxy resin having at least one type of skeleton consisting of a norcamphene skeleton, a naphthalene skeleton, an anthracene skeleton, an adamantane skeleton, a terpene skeleton, and a trimethylcyclohexane skeleton. The terminal of the phenoxy resin may be any functional group such as a phenolic hydroxyl group or an epoxy group. The phenoxy resins may be used alone or in combination of two or more. Specific examples of phenoxy resins include "1256" and "4250" (both phenoxy resins containing a bisphenol A skeleton) and "YX8100" (phenoxy resins containing a bisphenol S skeleton) manufactured by Mitsubishi Chemical Co., Ltd. Resin), and "YX6954" (phenoxy resin containing a bisphenol acetophenone skeleton), "FX280" and "FX293" manufactured by Nippon Steel & Sumitomo Metal Chemical Co., Ltd., and "YL7500BH30" manufactured by Mitsubishi Chemical Co., Ltd. , "YX6954BH30", "YX7553", "YX7553BH30", "YL7769BH30", "YL6794", "YL7213", "YL7290" and "YL7482", etc.

Polyvinyl acetal resins include, for example, polyvinyl formal resins and polyvinyl butyral resins, preferably polyvinyl butyral. Specific examples of polyvinyl acetal resins include "Denka Butyral 4000-2", "Denka Butyral 5000-A", "Denka Butyral 6000-C", "Denka Butyral" manufactured by Denka Kogyo Co., Ltd. Aldehyde 6000-EP", Sekisui Chemical Co., Ltd.'s 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 polyimide resin include "Rikacoat SN20" and "Rikacoat PN20" manufactured by Nippon Chemical Co., Ltd. Specific examples of polyimide resins include linear polyimides obtained by reacting bifunctional hydroxyl-terminated polybutadiene, diisocyanate compounds, and tetrabasic acid anhydrides (polyimides described in Japanese Patent Application Laid-Open No. 2006-37083). Modified polyimides such as imides), polyimides containing a polysiloxane skeleton (polyimides described in Japanese Patent Laid-Open No. 2002-12667 and Japanese Patent Laid-Open No. 2000-319386, etc.) amine.

Specific examples of the polyamideimide resin include "VylomaxHR11NN" and "VylomaxHR16NN" manufactured by Toyobo Co., Ltd. Specific examples of polyamide imide resins include modified polyamide imides such as "KS9100" and "KS9300" (polyamide imides containing a polysiloxane skeleton) manufactured by Hitachi Chemical Industries, Ltd. amine.

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" manufactured by Mitsubishi Gas Chemical Corporation.

Specific examples of the polyester resin include polystyrene "P1700" and "P3500" manufactured by Solvay Specialty Polymers, Inc., and the like.

Among them, (F) thermoplastic resins are preferably phenoxy resins and polyvinyl acetal resins. Therefore, in a preferred embodiment, the thermoplastic resin contains one or more species selected from the group consisting of phenoxy resins and polyvinyl acetal resins. Among them, the thermoplastic resin is preferably a phenoxy resin, particularly preferably a phenoxy resin with a weight average molecular weight of 30,000 or more.

When the resin composition contains (F) thermoplastic resin, the amount of (F) thermoplastic resin, from the viewpoint of significantly obtaining the desired effect of the present invention, when the non-volatile components in the resin composition are set to 100% by mass, it is preferable It is 0.1 mass % or more, More preferably, it is 0.5 mass % or more, More preferably, it is 1 mass % or more. The upper limit is preferably at most 10 mass %, more preferably at most 5 mass %, and more preferably at most 3 mass %.

＜(G) Flame Retardant＞ The resin composition may contain (G) a flame retardant as an optional component. (G) Flame retardants include, for example, phosphazene compounds, organic phosphorus-based flame retardants, organic nitrogen-containing phosphorus compounds, nitrogen compounds, polysiloxane-based flame retardants, metal hydroxides, etc., preferably phosphorus Nitrile compounds. The flame retardant may be used alone or in combination of two or more.

The phosphazene compound is a cyclic compound having nitrogen and phosphorus as constituent elements, and the phosphazene compound is preferably a phosphazene compound having a phenolic hydroxyl group. Specific examples of the phosphazene compound include "SPH-100", "SPS-100", "SPB-100", "SPE-100" manufactured by Otsuka Chemical Co., Ltd., "FP-100" manufactured by Fushimi Pharmaceutical Co., Ltd., "FP-110", "FP-300", "FP-400", etc.

As flame retardants other than the phosphazene compound, commercially available products can also be used, and examples thereof include "HCA-HQ" manufactured by Sanko Co., Ltd., "PX-200" manufactured by Daihachi Chemical Industry Co., Ltd., and the like. The flame retardant is preferably one that is not easily hydrolyzed, for example, 10-(2,5-dihydroxyphenyl)-10-hydro-9-oxa-10-phosphaphenanthrene-10-oxide is preferred.

When the resin composition contains (G) flame retardant, the amount of (G) flame retardant, from the viewpoint of significantly obtaining the desired effect of the present invention, when the non-volatile components in the resin composition are set to 100% by mass, It is preferably at least 0.1% by mass, more preferably at least 0.5% by mass, and more preferably at least 1% by mass. The upper limit is preferably at most 10 mass %, more preferably at most 5 mass %, and more preferably at most 3 mass %.

＜(H) Any additives＞ The resin composition may contain arbitrary additives as optional components in addition to the above components. Such additives include, for example, organometallic compounds such as organic copper compounds, organic zinc compounds, and organic cobalt compounds; thickeners; defoamers; leveling agents; adhesion imparting agents; and resin additives such as colorants. These additives may be used alone or in combination of two or more of them in arbitrary ratios.

<Physical properties and uses of resin composition> The cured product of the above-mentioned resin composition can be roughened under harsh conditions, so it exhibits excellent residue removal properties. Therefore, the laser processability of this cured product is also excellent. Therefore, an insulating layer excellent in laser processability can be obtained by using the resin composition of the present invention. For example, an insulating layer is formed using the above-mentioned resin composition, a via hole is formed using a laser, and then a roughening treatment is performed. At this time, the maximum residue length from the wall surface at the bottom of the via hole can usually be less than 3 μm.

In addition, according to the above-mentioned resin composition, even if the thickness of the cured product is thin, the insulation performance is excellent, so the characteristic of high resistance value can be exhibited. Therefore, by using the resin composition of the present invention, an insulating layer of a thin film having a high resistance value can be obtained. For example, using the above-mentioned resin composition, the resistance value of the substrate E for insulation evaluation was measured by the method described in the examples. In this case, the obtained resistance value can usually be 1×10 ⁷ Ω or more.

In addition, the surface of the cured product after the roughening treatment of the above-mentioned resin composition can exhibit a characteristic of low arithmetic average roughness (Ra). Therefore, by using the resin composition of the present invention, an insulating layer having a low arithmetic mean roughness can be provided even when wet desmearing is performed. For example, the arithmetic mean roughness (Ra) of the roughened substrate D is measured by the method described in the examples using the above-mentioned resin composition. In this case, the obtained arithmetic mean roughness is usually not more than 150 nm, preferably not more than 130 nm, more preferably not more than 100 nm. The lower limit of the arithmetic mean roughness is not particularly limited, and may be 1 nm or more.

In addition, since the surface of the cured product after the roughening treatment of the above-mentioned resin composition has uniform detachment marks, it can exhibit a characteristic of low maximum height roughness (Rz). Therefore, by using the resin composition of the present invention, an insulating layer with a low maximum height roughness can be provided even when wet desmearing is performed. For example, using the above-mentioned resin composition, the maximum height roughness (Rz) of the roughened substrate D is measured by the method described in the examples. In this case, the obtained maximum height roughness is usually not more than 1000 nm, preferably not more than 500 nm, more preferably not more than 400 nm. The lower limit of the maximum height roughness is not particularly limited, and may be 1 nm or more.

In addition, the cured product of the above-mentioned resin composition can exhibit a characteristic of high elongation at break point. Therefore, by using the resin composition of the present invention, an insulating layer having a high elongation at break can generally be provided. For example, using the above-mentioned resin composition, the elongation at break point of the hardened product B for evaluation was measured by the method described in the examples. In this case, the obtained elongation at breaking point is usually 1.5% or more, preferably 2.0% or more, more preferably 2.5% or more. The upper limit is not particularly limited, and may be 10% or less.

In addition, the above-mentioned resin composition has excellent insulating properties even if the thickness of the cured product is thin, so it can provide an insulating layer capable of forming a fine wiring circuit. Therefore, the resin composition of the present invention can be suitably used as a resin composition for forming a circuit in which the ratio (L/S) of the circuit width (L (μm)) to the width between circuits (S (μm)) is small. The above-mentioned ratio (L/S) is usually 10 μm/10 μm or less (20 μm pitch or less), preferably 5 μm/5 μm or less (10 μm pitch or less), more preferably 2 μm/2 μm (4 μm pitch or less).

Utilizing the above-mentioned advantages, the insulating layer can be formed by the cured product of the above-mentioned resin composition. Therefore, the resin composition of the present invention can be suitably used as a resin composition for forming a circuit in which the ratio (L/S) of the circuit width (L (μm)) to the width between circuits (S (μm)) is 10 μm/10 μm or less. It is suitable for use as a resin composition for forming an insulating layer having a surface having an arithmetic average roughness (Ra) of 150 nm or less, and as a resin composition for forming via holes by laser irradiation (printed wiring boards) It is used as a resin composition for forming via holes by laser irradiation). Also, the resin composition of the present invention can be suitably used as a resin composition for insulation. Specifically, it is suitable as a resin composition for forming an insulating layer (resin composition for forming an insulating layer for forming a conductive layer) for forming a conductive layer (including a rewiring layer) formed on an insulating layer, forming a printed The resin composition for the insulating layer of the wiring board (resin composition for the insulating layer of the printed wiring board), can be more suitable as the resin composition for forming the interlayer insulating layer of the printed wiring board (for the interlayer insulating layer of the printed wiring board) resin composition) use. In addition, the resin composition of the present invention can provide an insulating layer with good embedding properties of parts, so it can also be applied to the case where the printed wiring board is a circuit board with built-in parts. Also, for example, when manufacturing a semiconductor chip package through the following steps (1) to (6), the resin composition of the present invention can also be suitably used as a resin composition for a rewiring formation layer of an insulating layer for rewiring layer formation ( Resin composition for rewiring forming layer formation) and resin composition for semiconductor chip packaging (resin composition for semiconductor chip packaging). During the manufacture of semiconductor chip packaging, a redistribution layer can be formed on the packaging layer. (1) The step of laminating the temporarily fixed film on the substrate, (2) The step of temporarily fixing the semiconductor wafer on the temporary fixing film, (3) the step of forming the encapsulation layer on the semiconductor wafer, (4) The step of peeling the base material and the temporarily fixed film from the semiconductor wafer, (5) A step of forming a rewiring formation layer as an insulating layer on the surface where the substrate of the semiconductor wafer and the temporary fixing film are peeled off, and (6) Step of forming a rewiring layer as a conductor layer on the rewiring formation layer

[Resin flakes] The resin sheet of the present invention has a support and a resin composition layer provided on the support. The resin composition layer is a layer containing the resin composition of the present invention, and is usually formed of the resin composition. According to the above-mentioned resin composition, even if the thickness of the cured product is thin, the insulation performance is excellent, so the thickness of the resin composition layer can be reduced.

The thickness of the resin composition layer is preferably 15 μm or less, more preferably 13 μm or less, still more preferably 10 μm or less, from the viewpoint of thinning the printed wiring board and providing a cured product with excellent insulation properties even if it is a thin film. The lower limit of the thickness of the resin composition layer is not particularly limited, and generally, it may be 1 μm or more, 2 μm or more, or the like.

In one preferred embodiment of the resin composition layer, as the resin composition layer, from the viewpoint of improving the insulation of the film, the resin composition system contains 50% by mass or more of (C) Inorganic filler, select any 10 positions on the surface of the hardened product after the resin composition is cured at 200°C for 90 minutes, and observe any selected point in the cross-sectional view perpendicular to the surface of the hardened product at that place. In the case of a range with a width of 100 μm and a depth of 5 μm, when the maximum particle size of (C) inorganic filler is R1 (μm), and the average particle size of (C) inorganic filler is R2 (μm), the above formula ( 1) The relationship. The details of the relationship between the aforementioned R1 and the aforementioned R2 are as described above.

In another preferred embodiment of the resin composition layer, as the resin composition layer, from the viewpoint of improving the insulation of the film, the resin composition contains 50% by mass when the non-volatile components in the resin composition are 100% by mass. For the above (C) inorganic filler, select any 10 places on the surface of the cured product that have been cured at 200°C for 90 minutes, and observe any selection in the cross-sectional view perpendicular to the surface of the cured product. In the case of a range of 100 μm in width and 5 μm in depth, when the average particle size of (C) inorganic filler is R2 (μm), the number of particles having a particle size of (1.2×R2) μm or more is 4 or less. The details of the aforementioned number and the like are as above.

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

When a film made of a plastic material is used as a support, examples of the plastic material include polyethylene terephthalate (hereinafter sometimes abbreviated as "PET"), polyethylene naphthalate (hereinafter referred to as Polyesters such as polycarbonate (hereinafter sometimes referred to as "PC" for short); polymethyl methacrylate (hereinafter sometimes referred to as "PMMA") and other acrylic polymers; cyclic Polyolefin; triacetyl cellulose (hereinafter sometimes abbreviated as "TAC"); polyether sulfide (hereinafter sometimes abbreviated as "PES"); polyether ketone; polyimide; Among them, polyethylene terephthalate and polyethylene naphthalate are preferred, and inexpensive polyethylene terephthalate is particularly preferred.

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

The surface of the support that is bonded to the resin composition layer may be treated with matting treatment, corona treatment, antistatic treatment, etc.

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 also be used. The release agent used for the release layer of the support with release layer includes, for example, one or more types selected from the group consisting of alkyd resins, polyolefin resins, urethane resins, and silicone resins release agent. As a commercial item of a release agent, an alkyd resin type release agent, "SK-1", "AL-5", and "AL-7" by Lintec Corporation etc. are mentioned, for example. Moreover, as a support body with a release layer, for example, "lumirror T60" manufactured by Toray Corporation; "Purex" manufactured by Teijin Corporation; "unipeel" manufactured by Unitika Corporation;

The thickness of the support is preferably in the range of 5 μm to 75 μm, more preferably in the range of 10 μm to 60 μm. Moreover, when using the support body with a release layer, it is preferable that the thickness of the whole support body with a release layer exists in the said range.

The resin sheet can be produced, for example, by applying a resin composition to a support using a coating device such as a die coater. Also, if necessary, the resin composition is dissolved in an organic solvent to prepare a resin varnish, and the resin varnish is applied to produce a resin sheet. By using a solvent to adjust the viscosity, the coating property can be improved. When a resin varnish is used, usually after coating, the resin varnish is dried to form a resin composition layer.

Examples of organic solvents include ketone solvents such as acetone, methyl ethyl ketone, and cyclohexanone; ethyl acetate, butyl acetate, cellolytic acetate, propylene glycol monomethyl ether acetate, and carbitol acetic acid Acetate solvents such as esters; carbitol solvents such as cellosolve and butyl carbitol; aromatic hydrocarbon solvents such as toluene and xylene; dimethylformamide, dimethylacetamide (DMAc ) and amide-based solvents such as N-methylpyrrolidone; etc. An organic solvent may be used individually by 1 type, and may use it combining 2 or more types by arbitrary ratios.

Drying can be carried out by known methods such as heating and blowing hot air. Drying conditions are such that the content of the organic solvent dried to the resin composition layer is usually 10% by mass or less, preferably 5% by mass or less. It also depends on the boiling point of the organic solvent in the resin varnish. For example, when using a resin varnish containing 30% by mass to 60% by mass of an organic solvent, it can be formed by drying at 50°C to 150°C for 3 minutes to 10 minutes. resin composition layer.

The resin sheet may contain any layers other than the support and the resin composition layer, if necessary. For example, in the resin sheet, a protective film corresponding to the support may be provided on the surface of the resin composition layer that is not bonded to the support (that is, the surface opposite to the support). The thickness of the protective film is, for example, 1 μm˜40 μm. The protective film can prevent adhesion or scratches of dirt and the like on the surface of the resin composition layer. When the resin sheet has a protective film, the resin sheet becomes usable by peeling off the protective film. In addition, the resin sheet can be wound and stored in a roll shape.

[Printed Wiring Board] The printed wiring board of the present invention includes an insulating layer formed of a cured product of the resin composition of the present invention, a first conductor layer, and a second conductor layer. The insulating layer is provided between the first conductor layer and the second conductor layer to insulate the first conductor layer and the second conductor layer (the conductor layer may be called a wiring layer).

The insulating layer is formed by the cured product of the resin composition of the present invention. The thickness of the insulating layer between the first and second conductor layers is preferably at most 15 μm, more preferably at most 13 μm, and still more preferably at most 10 μm. The lower limit is not particularly limited, and may be 0.1 μm or more. The distance between the first conductor layer and the second conductor layer (the thickness of the insulating layer between the first and second conductor layers) refers to the example shown in Figure 1, the main surface 11 of the first conductor layer 1 and the second conductor layer 2 The thickness t1 of the insulating layer 3 between the main surfaces 21. The first and second conductor layers pass through insulating layers, and the main surfaces 11 and 21 of the adjacent conductive layers face each other.

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

A printed wiring board can be manufactured by the method including the process of following (I) and (II) using the said resin sheet. (I) The step of bonding the resin composition layer of the resin sheet to the inner substrate to be laminated on the inner substrate (II) Step of thermosetting the resin composition layer to form an insulating layer

The "inner layer substrate" used in step (I) is a member that becomes a substrate of a printed wiring board, and examples thereof include glass epoxy substrates, metal substrates, polyester substrates, polyimide substrates, BT resin substrates, thermosetting poly Phenyl ether substrate, etc. Also, one or both sides of the substrate may have a conductive layer, and the conductive layer may also be patterned. An inner layer substrate in which a conductor layer (circuit) is formed on one or both sides of the substrate is sometimes referred to as an "inner layer circuit board". In addition, when manufacturing a printed wiring board, an intermediate product that should further form an insulating layer and/or a conductive layer is also included in the so-called "inner layer substrate" in the present invention. When the printed wiring board is a circuit board with built-in parts, an inner substrate with built-in parts can also be used.

The lamination of the inner layer substrate and the resin sheet can be performed, for example, by heat-compression bonding the resin sheet to the inner layer substrate from the support side. The member for thermocompression bonding the resin sheet to the inner layer substrate (hereinafter also referred to as "thermocompression bonding member") includes, for example, a heated metal plate (SUS mirror plate, etc.) or a metal roller (SUS roller). In addition, instead of directly pressing the thermocompression bonding member to the resin sheet, it is preferable that the resin sheet sufficiently follow the surface irregularities of the inner substrate, and that the resin sheet be pressed through an elastic material such as heat-resistant rubber.

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

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

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

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

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

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

For example, the thermosetting conditions of the resin composition layer vary depending on the type of resin composition, etc., and the curing temperature is preferably 120°C~240°C, more preferably 150°C~220°C, and more preferably 170°C~200°C . The curing time is preferably from 5 minutes to 120 minutes, more preferably from 10 minutes to 100 minutes, and more preferably from 15 minutes to 90 minutes.

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

When manufacturing a printed wiring board, (III) the step of opening a hole in the insulating layer, (IV) the step of roughening the insulating layer, and (V) the step of forming a conductor layer may be further implemented. These steps (III) to (V) can be implemented according to various methods known to those skilled in the art for the manufacture of printed wiring boards. Also, when the support is removed after step (II), the support can be removed between step (II) and step (III), between step (III) and step (IV), or step (IV) Implement between step (V). Also, if necessary, the formation of the insulating layer and the conductor layer in steps (II) to (V) are repeated to form a multilayer wiring board. In this case, the thickness of the insulating layer between the respective conductor layers (t1 in FIG. 1) is preferably within the above-mentioned range.

The step (III) is a step of opening holes in the insulating layer. By opening holes, holes such as via holes and through holes can be formed in the insulating layer. Step (III) can be implemented according to the composition of the resin composition used in the formation of the insulating layer, for example, using a drill, laser, plasma, etc. The insulating layer is formed of a cured product of the resin composition of the present invention, so it has excellent laser processability. Therefore, step (III) is preferably carried out using laser. The size or shape of the hole can be appropriately determined according to the design of the printed wiring board. The specific diameter of the pores is, for example, preferably 70 μm or less, more preferably 50 μm or less, and still more preferably 20 μm or less. The lower limit is not particularly limited, and may be 0.1 μm or more.

Step (IV) is a step of roughening the insulating layer. The order and conditions of the roughening treatment are preferably set within the range in which the residue generated in step (III) can be removed and the penetration of the insulating layer due to the unintentional detachment trace of the (C) inorganic filler can be suppressed. For specific procedures and conditions, known procedures and conditions generally used when forming an insulating layer of a printed wiring board can be employed. Also, since the insulating layer is formed of a hardened resin composition containing (B) active ester compound and (C) inorganic filler, roughening treatment can be performed using a stronger chemical solution than usual.

The roughening treatment of the insulating layer, for example, can be carried out in the order of swelling treatment with swelling solution, roughening treatment with oxidizing agent, and neutralization treatment with neutralizing solution. The swelling solution used in the roughening treatment is not particularly limited, and examples thereof include alkali solutions, surfactant solutions, etc., preferably alkali solutions, more preferably sodium hydroxide solutions, and potassium hydroxide 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 by swelling solution is not particularly limited, for example, the swelling treatment can be performed by immersing the insulating layer in a swelling solution at 30° C. to 90° C. for 1 minute to 20 minutes. From the viewpoint of suppressing the swelling of the resin of the insulating layer to an appropriate level, it is preferable to immerse the insulating layer in a swelling solution at 40° C. to 80° C. for 5 minutes to 15 minutes. The oxidizing agent used for the roughening treatment is not particularly limited, and examples thereof include an alkaline permanganate solution in which potassium permanganate or sodium permanganate is dissolved in an aqueous solution of sodium hydroxide. The roughening treatment by an oxidizing agent such as an alkaline permanganic acid solution is preferably carried out by immersing the insulating layer in an oxidizing solution heated to 60° C. to 80° C. for 10 minutes to 30 minutes. Also, the concentration of permanganate in the alkaline permanganate solution is preferably 5% by mass to 10% by mass. Examples of commercially available oxidizing agents include alkaline permanganic acid solutions such as "Concentrate Compact CP" and "Dosing Solution Securiganth P" manufactured by Atotech Japan Co., Ltd. In addition, the neutralizing solution used in the roughening treatment is preferably an acidic aqueous solution, and commercially available products include, for example, "Reduction solution Securiganth P" manufactured by Atotech Japan Co., Ltd. The treatment with the neutralizing solution can be carried out by immersing the treated surface roughened with an oxidizing agent in the neutralizing solution at 30°C to 80°C for 5 minutes to 30 minutes. From the viewpoint of workability and the like, a method of immersing the object roughened with an oxidizing agent in a neutralizing solution at 40° C. to 70° C. for 5 minutes to 20 minutes is preferred.

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

The conductor material used for the conductor layer is not particularly limited. In a preferred embodiment, the conductor layer includes 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 may be a single metal layer or an alloy layer, and the alloy layer may be, for example, an alloy of two or more metals selected from the above group (such as nickel-chromium alloy, copper-nickel alloy, and copper-titanium alloy). layer. Among them, a single metal layer of chromium, nickel, titanium, aluminum, zinc, gold, palladium, silver or copper is preferred from the viewpoint of the versatility, cost, and ease of patterning of the conductor layer; or nickel. The alloy layer of chromium alloy, copper-nickel alloy, copper-titanium alloy, more preferably a single metal layer of chromium, nickel, titanium, aluminum, zinc, gold, palladium, silver or copper or an alloy layer of nickel-chromium alloy, and 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 layers of a single metal layer or an alloy layer of different types of metals or alloys are laminated. When the conductor layer has a multi-layer structure, the layer in contact with the insulating layer is preferably a single metal layer of chromium, zinc or titanium, or an alloy layer of nickel-chromium alloy.

The thickness of the conductor layer varies with the desired design of the printed wiring board, and is generally 3 μm to 35 μm, preferably 5 μm to 30 μm.

In one embodiment, the conductor layer can be formed by plating. For example, by plating on the surface of the insulating layer by conventionally known techniques such as semi-additive method and full-additive method, a conductive layer with a desired wiring pattern can be formed. From the viewpoint of ease of manufacture, by It is better to form by semi-additive method. An example of forming a conductor layer by a semi-additive method is shown below.

First, a shield layer is formed on the surface of the insulating layer by electroless plating. Then, on the formed plating protection layer, a mask pattern corresponding to a desired wiring pattern is formed to expose a part of the plating protection layer. On the exposed plating protective layer, after forming a metal layer by electroplating, the mask pattern is removed. Then, unnecessary plating resist is removed by etching or the like, and a conductor layer having a desired wiring pattern can be formed.

The resin sheet of the present invention provides an insulating layer with good embedding properties of parts, so it is also suitable for use in the case where the printed wiring board is a circuit board with built-in parts. The component built-in circuit board can be manufactured by known manufacturing methods.

The printed wiring board manufactured using the resin sheet of the present invention may have an insulating layer of a cured product of the resin composition layer of the resin sheet, and an embedded wiring layer embedded in the insulating layer.

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

Examples of semiconductor devices include electrical products (such as computers, mobile phones, digital cameras, and televisions, etc.) and various semiconductor devices that provide vehicles (such as motorcycles, automobiles, trams, ships, and airplanes, etc.).

The semiconductor device of the present invention can be manufactured by, for example, mounting components (semiconductor chips) on conduction points of circuit boards. "Conductive place" refers to "the place where the electrical signal is transmitted on the printed wiring board", and the place can be surface or buried. Also, when the semiconductor wafer is an electrical circuit element made of a semiconductor, it is not particularly limited.

The mounting method of the semiconductor chip when manufacturing a semiconductor device is not particularly limited as long as the semiconductor chip can effectively function. BBUL) installation method, anisotropic conductive film (ACF) installation method, non-conductive film (NCF) installation method, etc. Here, the "mounting method by bumpless build-up layer (BBUL)" refers to "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 by giving examples. However, the present invention is not limited to the following examples. In addition, in the following description, "parts" and "%" indicating amounts represent "parts by mass" and "% by mass", respectively, unless otherwise specified. In addition, the operations described below are performed under normal temperature and normal pressure unless otherwise specified.

＜Measurement of average particle size and variation coefficient of inorganic filler＞ The measurement of the average particle diameter R2 and the coefficient of variation of the inorganic filler is carried out by the above-mentioned method.

<Example 1: Preparation of resin composition 1> 10 parts of bisphenol A type epoxy resin ("828US" manufactured by Mitsubishi Chemical, epoxy equivalent about 180), 20 parts of biphenyl type epoxy resin ("YX4000H" manufactured by Mitsubishi Chemical, epoxy equivalent about 190), and 10 parts of bisphenol AF type epoxy resin ("YL7760" manufactured by Mitsubishi Chemical Co., Ltd., epoxy equivalent about 238), 3 parts of phosphazene resin ("SPS-100" manufactured by Otsuka Chemical Co., Ltd.), phenoxy resin ("YL7760" manufactured by Mitsubishi Chemical Co., Ltd. "YX7553BH30" manufactured by the company, a 1:1 solution of MEK with a solid content of 30% by mass and cyclohexanone) 10 parts were dissolved in 60 parts of MEK by heating while stirring.

After cooling to room temperature, 40 parts of an active ester compound ("HPC-8000-65T" manufactured by DIC Corporation, a toluene solution with an active group equivalent of about 223 and a solid content of 65% by mass), 40 parts of a phenolic hardener ("LA -3018-50P", active group equivalent of about 151, 2-methoxypropanol solution of 50% solid content) 16 parts, hardening accelerator (4-dimethylaminopyridine (DMAP), solid content 5% by mass MEK solution) 6 parts, spherical silica particles ("seahosterKE-S20" manufactured by Nippon Shokubai Co., Ltd.) surface-treated with an amine-based silane coupling agent ("KBM573" manufactured by Shin-Etsu Chemical Co., Ltd.), coefficient of variation of particle size distribution 5.0%, average particle size 0.2 μm) and 170 parts were uniformly dispersed with a high-speed rotary mixer, and filtered using a cartridge filter (manufactured by ROKITECHNO "SHP020") to prepare resin composition 1.

<Example 2: Preparation of resin composition 2> In Example 1, 6 parts of the hardening accelerator (4-dimethylaminopyridine (DMAP), MEK solution with a solid content of 5% by mass) was changed to the hardening accelerator (4-pyrrolidinylpyridine (PPY), solid Component 5% by mass of 1-methoxyl 2-propanol solution) 6 parts. Resin composition 2 was produced in the same manner as in Example 1 except for the above.

<Example 3: Preparation of resin composition 3> In Example 1, spherical silica particles ("seahoster KE-S20" manufactured by Nippon Shokubai Co., Ltd.) were surface-treated with an amine-based silane coupling agent ("KBM573" manufactured by Shin-Etsu Chemical Co., Ltd.), and the coefficient of variation of the particle size distribution was 5.0. %, average particle size 0.2μm) was changed to spherical silica particles ("seahoster KE-S30" manufactured by Nippon Shokubai Co. The coefficient of variation of the size distribution is 3.1%, and the average particle size is 0.3 μm) 170 parts. Resin composition 3 was produced in the same manner as in Example 1 except for the above.

<Example 4: Preparation of resin composition 4> In Example 3, 40 parts of the active ester compound ("HPC-8000-65T" manufactured by DIC Corporation, a toluene solution with an active group equivalent of about 223 and a solid content of 65% by mass) was changed to an active ester compound ("EXB9416-65T" manufactured by DIC Corporation). 70BK", 37 parts of MIBK (methyl isobutyl ketone) solution with an active group equivalent of about 274 and a solid content of 70% by mass. Resin composition 4 was produced in the same manner as in Example 3 except for the above.

<Example 5: Preparation of resin composition 5> In Example 3, 10 parts of a carbodiimide-based curing agent ("V-03" manufactured by Nisshinbo Chemical Co., Ltd., a toluene solution with an active group equivalent of about 216 and a solid content of 50% by mass) was added. Resin composition 5 was produced in the same manner as in Example 3 except for the above.

<Comparative Example 1: Production of Comparative Resin Composition 1> In embodiment 1, 1) Change 40 parts of the active ester-based hardener ("HPC-8000-65T" manufactured by DIC Corporation, a toluene solution with an active group equivalent of about 223 and a solid content of 65% by mass) to a naphthol-based hardener (Nippon Steel & Sumikin Chemical Co., Ltd. "SN-485" manufactured by the company, with an active group equivalent of about 215) 7.2 parts, 2) Change 16 parts of phenolic curing agent ("LA-3018-50P" manufactured by DIC Corporation, 2-methoxypropanol solution with active group equivalent of about 151, solid content 50%) to phenolic curing agent (DIC Corporation 12 parts of "LA-7054", MEK solution with active group equivalent of about 124 and solid content of 60%, 3) Spherical silica particles ("seahoster KE-S20" manufactured by Nippon Shokubai Co., Ltd.) surface-treated with an amine-based silane coupling agent ("KBM573" manufactured by Shin-Etsu Chemical Co., Ltd.), the coefficient of variation of the particle size distribution is 5.0%, and the average 170 parts of particle size (0.2 μm) was changed to 110 parts. A resin composition 1 for comparison was prepared in the same manner as in Example 1 except for the above.

<Comparative Example 2: Production of Comparative Resin Composition 2> In Comparative Example 1, spherical silica particles ("seahoster KE-S20" manufactured by Nippon Shokubai Co., Ltd.) were surface-treated with an amine-based silane coupling agent ("KBM573" manufactured by Shin-Etsu Chemical Co., Ltd.), and the coefficient of variation of the particle size distribution was 5.0. %, average particle size 0.2μm) was changed to spherical silica particles ("seahoster KE-S30" manufactured by Nippon Shokubai Co. The coefficient of variation of the size distribution is 3.1%, and the average particle size is 0.3 μm) 110 parts. A resin composition 2 for comparison was produced in the same manner as in Comparative Example 1 except for the above.

<Comparative Example 3: Production of Comparative Resin Composition 3> In Example 1, spherical silica particles ("seahoster KE-S20" manufactured by Nippon Shokubai Co., Ltd.) were surface-treated with an amine-based silane coupling agent ("KBM573" manufactured by Shin-Etsu Chemical Co., Ltd.), and the coefficient of variation of the particle size distribution was 5.0. %, average particle size 0.2μm) 170 parts changed to spherical silica ("SO-C1" manufactured by Admatechs Co., Ltd.) surface-treated with an amine-based silane coupling agent ("KBM573" manufactured by Shin-Etsu Chemical Co., Ltd.), changes in particle size distribution Factor 41%, average particle size 0.3μm,) 170 parts. A resin composition 3 for comparison was prepared in the same manner as in Example 1 except for the above.

＜Production of resin sheet A＞ A PET film ("lumirror R80" manufactured by Toray Corporation, thickness 38 μm, softening point 130°C, hereinafter sometimes referred to as " Released PET") as a support.

Each resin composition is uniformly coated on the release PET with a die coater so that the thickness of the dried resin composition layer becomes 6 μm, and the resin composition is obtained on the release PET by drying at 80°C for 1 minute. object layer. Next, by bonding the resin composition layer, a thick layer of a polypropylene film ("alphan MA-411" manufactured by Oji F-Tex Co., Ltd., thickness 15 μm) as a protective film is layered on the non-supported part of the resin composition layer. joint face. Thereby, the resin sheet A formed in the order of the release PET (support body), the resin composition layer, and the protective film was obtained.

＜Measurement of elongation at breaking point＞ The protective film of the prepared resin sheet A was peeled off, heated at 200° C. for 90 minutes to thermally harden the resin composition layer, and then the support was peeled off. The obtained cured product is referred to as "cured product B for evaluation". With respect to the cured product B for evaluation, a tensile test was performed with a Tensilon universal testing machine ("RTC-1250A" manufactured by Orientec Corporation) in accordance with Japanese Industrial Standards (JIS K7127), and the elongation at breaking point was measured.

＜Measurement of the particle size of the inorganic filler in the cross section of the hardened body＞ Among the cross-sectional views perpendicular to the surface of the cured product B for evaluation, a randomly selected range of 100 μm in width and 5 μm in depth was observed using a FIB-SEM composite device ("SMI3050SE" manufactured by SII NANOTECHNOLOGY Co., Ltd.). In each FIB-SEM image, the maximum particle size R1 (μm) of the inorganic filler within a range of 100 μm in width and 5 μm in depth and the number of particles with a particle size of (1.2×R2) μm or more were measured. Plotted as two points of the diameter, the particle diameter was calculated using the above-mentioned device. This operation was performed at any 10 locations not deliberately selected, and the respective average values are shown in the table below.

＜Arithmetic average roughness (Ra), maximum height roughness (Rz), thickness of insulating layer and evaluation of insulating properties＞ (1) Base treatment of inner circuit substrate Prepare a glass cloth substrate epoxy resin double-sided copper laminated board with a circuit conductor (copper) formed by a wiring pattern of L/S (line width/space) = 2μm/2μm on both sides (thickness of copper foil 3μm, substrate A thickness of 0.15 mm, "HL832NSF LCA" manufactured by Mitsubishi Gas Chemical Co., Ltd., size 255×340 mm) was used as an inner layer circuit board. Both surfaces of the inner layer circuit board were treated with an organic coating on the copper surface using a surface treatment solution ("FlatBOND-FT" manufactured by Mec Corporation).

(2) Lamination of resin sheets From each prepared resin sheet A, the protective film was peeled off, and the resin composition layer was brought into contact with the inner layer circuit board using a batch-type vacuum pressure laminator (manufactured by nikko-materials, two-stage build-up laminator, CVP700). , laminated on both sides of the inner circuit substrate. The lamination was carried out by pressure-bonding for 45 seconds at 130° C. and a pressure of 0.74 MPa at a pressure of 13 hPa or less under reduced pressure for 30 seconds. Next, it was hot-pressed at 120° C. and a pressure of 0.5 MPa for 75 seconds.

(3) Thermosetting of the resin composition layer The inner layer circuit board laminated with the resin sheet was placed in an oven at 100°C for 30 minutes, then moved to an oven at 180°C for 30 minutes, and then thermally cured to form an insulating layer with a thickness of 5 μm. This is substrate C.

(4) Steps for coarsening The mold release PET of the board|substrate C was peeled off, and the desmear process which is a roughening process was performed to the insulating layer. In addition, the desmearing process implements the following wet desmearing process.

Wet desmearing treatment: Soak in a swelling solution ("Swelling Dip Securiganth P" manufactured by Atotech Japan Co., an aqueous solution of diethylene glycol monobutyl ether and sodium hydroxide) at 60°C for 5 minutes, and then soak in an oxidizing agent solution ("Concentrate P" manufactured by Atotech Japan Co., Ltd. Compact CP", an aqueous solution with a concentration of potassium permanganate of about 6% and a concentration of sodium hydroxide of about 4%), immersed at 80°C for 20 minutes, and finally in a neutralizing solution ("Reduction solution Securiganth P" manufactured by Atotech Japan Co., Ltd., sulfuric acid) aqueous solution) at 40°C for 5 minutes, and then dried at 80°C for 15 minutes. This serves as a roughened substrate D.

(5) Step of forming a conductor layer (5-1) Electroless plating step In order to form a conductive layer on the surface of the insulating layer of the above-mentioned roughened substrate D, a plating step (copper plating step using a chemical solution manufactured by Atotech Japan Co., Ltd.) including the following steps 1 to 6 was performed to form a conductive layer.

1. Alkali cleaning (cleaning and charge adjustment of the surface of the insulating layer provided with via holes) The surface of the roughened substrate D was cleaned at 60° C. for 5 minutes using Cleaning Cleaner Securiganth 902 (trade name). 2. Soft etching (cleaning inside the via hole) The surface of the roughened substrate D was treated with sulfuric acidic sodium persulfate aqueous solution at 30° C. for 1 minute. 3. Pre-dipping (charge adjustment on the surface of the insulating layer for Pd) The surface of the roughened substrate D was treated with Pre.Dip Neoganth B (trade name) at room temperature for 1 minute. 4. Provision of activator (Pd provision to the surface of the insulating layer) The surface of the roughened substrate D was treated at 35° C. for 5 minutes using Activator Neoganth 834 (trade name). 5. Reduction (reduction of Pd given to the insulating layer) The surface of the roughened substrate D was treated at 30° C. for 5 minutes using a mixture of Reducer Neoganth WA (trade name) and Reducer Acceralator 810 mod. (trade name). 6. Electroless copper plating step (precipitating Cu on the surface of the insulating layer (Pd surface)) To roughen the surface of substrate D, use a mixture of Basic Solution Printganth MSK-DK (trade name) and Copper solution Printganth MSK (trade name) and Stabilizer Printganth MSK-DK (trade name) and Reducer Cu (trade name) , at 35°C for 20 minutes. The thickness of the formed electroless copper plating layer was 0.8 µm.

(5-2) Electroplating step Next, a copper electroplating step was performed under the condition that the via holes were filled with copper using a chemical solution manufactured by Atotech Japan. Then, use the resist pattern for patterning by etching: a land pattern with a diameter of 1 mm that is connected to the via hole and a circular conductor pattern with a diameter of 10 mm that is not connected to the underlying conductor. On the surface of the insulating layer, a conductor layer having pads and conductor patterns was formed with a thickness of 10 μm. Next, an annealing treatment was performed at 200° C. for 90 minutes. This substrate was referred to as "substrate E for insulation evaluation".

(6) Measurement of arithmetic mean roughness (Ra) and maximum height roughness (Rz) Use a non-contact surface roughness meter (WYKO NT3300 manufactured by Veeco Instruments Co., Ltd.) for the roughened substrate D, divide the VSI into contact mode, 50 times lens, and set the measurement range to 121 μm × 92 μm to obtain the value obtained. Ra value, Rz value. Each is measured by averaging 10 randomly selected points.

(7) Measurement of the thickness of the insulating layer between conductor layers The cross section of the substrate E for insulation evaluation was observed using a FIB-SEM composite device ("SMI3050SE" manufactured by SII NANOTECHNOLOGY Co., Ltd.). In detail, the section in the direction perpendicular to the surface of the conductor layer is cut by FIB (Fluster Ion Beam), and the thickness of the insulating layer between the conductor layers is measured from the SEM image of the section. For each sample, observe the cross-sectional SEM images of 5 randomly selected places, and use the average value as the thickness (μm) of the insulating layer between the conductor layers, as shown in the following table.

(8) Evaluation of Insulation Reliability (Insulation) of the Insulation Layer The round conductor side of the insulation evaluation substrate E obtained above is used as the + electrode, and the pad with a diameter of 1 mm is connected to the grid conductor of the inner layer circuit board. The (copper) side is used as the -electrode, using a highly accelerated life tester ("PM422" manufactured by ETAC Corporation), under the conditions of 130°C, 85% relative humidity, and 3.3V DC voltage, using electrochemical migration (electrochemical migration) test The insulation resistance value after 200 hours was measured with a device ("ECM-100" manufactured by J-RAS Co., Ltd.). This measurement was carried out 6 times, and all 6-point test pieces were evaluated as "○" when the resistance value was 10 ⁷ Ω or more, and "×" when even one piece did not reach 10 ⁷ Ω. The evaluation results were compared with the insulation resistance value All are shown in the table below. The insulation resistance value recorded in the following table is the lowest value of the insulation resistance value of the 6-point test piece.

<Preparation of substrate for evaluation of laser processability> (1) Via hole formation For substrate C, use a CO ₂ laser processing machine (YB-HCS03T04) manufactured by Panasonic Welding Systems Co., Ltd. at a frequency of 2000 Hz with a pulse width of 8 μs and a number of impacts Under the conditions of 3, the insulating layer was subjected to hole processing to form a via hole with a top diameter (diameter) of 25 μm in the surface of the insulating layer and a diameter of 20 μm in the bottom of the via hole in the bottom surface of the insulating layer.

(2) Steps for coarsening The release PET was peeled off, and the desmearing treatment was performed on the insulating layer as a roughening treatment. In addition, the desmearing process implements the following wet desmearing process.

Wet desmearing treatment: Soak in a swelling solution ("Swelling Dip Securiganth P" manufactured by Atotech Japan Co., an aqueous solution of diethylene glycol monobutyl ether and sodium hydroxide) at 60°C for 5 minutes, and then soak in an oxidizing agent solution ("Concentrate P" manufactured by Atotech Japan Co., Ltd. Compact CP", an aqueous solution with a concentration of potassium permanganate of about 6% and a concentration of sodium hydroxide of about 4%), immersed at 80°C for 20 minutes, and finally in a neutralizing solution ("Reduction solution Securiganth P" manufactured by Atotech Japan Co., Ltd., sulfuric acid) aqueous solution) at 40°C for 5 minutes, and then dried at 80°C for 15 minutes.

＜Evaluation of Laser Processability＞ Observe the surroundings of the bottom of the via hole with a scanning electron microscope (SEM), and measure the maximum residue length from the wall surface at the bottom of the via hole from the obtained image. When the maximum residue length was less than 3 μm, the evaluation was “◯”, and when the maximum residue length was 3 μm or more, the evaluation was “×”.

In Examples 1 to 5, it was confirmed that even if the components (D) to (G) were not contained, although there was a difference in degree, it was concluded that it was the same result as in the above-mentioned Examples.

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

Claims (15)

A resin composition, which is a resin composition comprising (A) epoxy resin, (B) active ester compound and (C) inorganic filler, wherein when the non-volatile components in the resin composition are set to 100% by mass, The content of the component (A) is not less than 1% by mass and not more than 40% by mass, and when the non-volatile components in the resin composition are taken as 100% by mass, the content of the component (B) is not less than 1% by mass and not more than 30% by mass, (C) The coefficient of variation of the particle size distribution of the component is 30% or less, and the average particle size is 0.01 μm or more and 5 μm or less. The resin composition of claim 1, wherein the content of component (C) is 50% by mass or more when the non-volatile components in the resin composition are set to 100% by mass. The resin composition according to claim 1, wherein the average particle diameter of component (C) is not less than 0.1 μm and not more than 3 μm. The resin composition according to claim 1 is used for forming an insulating layer of a printed wiring board. The resin composition according to claim 1 is used for circuit formation in which the ratio (L/S) of the circuit width (L (μm)) to the width between circuits (S (μm)) is 10 μm/10 μm or less. The resin composition according to claim 1, which is a resin composition for forming an insulating layer having a surface having an arithmetic average roughness (Ra) of 150 nm or less. The resin composition according to claim 1, which is a resin composition for forming via holes by laser irradiation. Such as the resin composition of claim 1, which is to select any 10 positions on the surface of the hardened product after the resin composition is cured at 200°C for 90 minutes, and observe in the cross-sectional view perpendicular to the surface of the hardened product at that place. When a range of 100 μm in width and 5 μm in depth is selected arbitrarily, when the maximum particle size of component (C) is set as R1 (μm), and the average particle size of component (C) is set as R2 (μm), R1<1.4×R2 is satisfied relation. Such as the resin composition of claim 1, which is to select any 10 positions on the surface of the hardened product after the resin composition is cured at 200°C for 90 minutes, and observe in the cross-sectional view perpendicular to the surface of the hardened product at that place. In the randomly selected range of 100 μm in width and 5 μm in depth, when the average particle size of component (C) is R2 (μm), the number of particles with a particle size of (1.2×R2) μm or more is 4 or less. A resin sheet comprising a support, and a resin composition comprising the resin composition according to any one of claims 1 to 9 disposed on the support object layer. The resin sheet according to claim 10, wherein the thickness of the resin composition layer is 15 μm or less. A resin sheet comprising a support, and a resin composition layer provided on the support and containing a resin composition containing (C) an inorganic filler, the resin composition is a non-volatile component in the resin composition. When it is 100% by mass, contain more than 50% by mass of (C) inorganic filler, select any 10 places on the surface of the cured product that are cured by heating the resin composition at 200°C for 90 minutes, and perpendicular to the surface of the cured product at that place In the cross-sectional view, when observing the randomly selected range of 100 μm in width and 5 μm in depth, the maximum particle size of (C) inorganic filler is set to R1 (μm), and the average particle size of (C) inorganic filler is set to R2 (μm), satisfy the relationship of R1<1.4×R2. A resin sheet comprising a support, and a resin composition layer provided on the support and containing a resin composition containing (C) an inorganic filler, the resin composition is a non-volatile component in the resin composition. When it is 100% by mass, contain more than 50% by mass of (C) inorganic filler, select any 10 places on the surface of the cured product that are cured by heating the resin composition at 200°C for 90 minutes, and perpendicular to the surface of the cured product at that place Sectional view of Among them, when observing the randomly selected range of 100 μm in width and 5 μm in depth, when the maximum particle size of (C) inorganic filler is R2 (μm), the number of particles with a particle size of (1.2×R2) μm or more is 4 less than one. A printed wiring board, which is 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, and the insulating layer is as in claim items 1 to 9 A cured product of any one of the resin compositions. A semiconductor device comprising the printed wiring board according to claim 14.

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